Polyethylene-based resin composition and its film

Abstract

To provide a polyethylene-based resin composition suitable for calendar rolling film forming, and its film.SOLUTION: A polyethylene-based resin composition for calendar rolling film forming comprises (A) polyethylene, (B) an antioxidant, (C) one or more selected from the group consisting of zinc fatty acid and magnesium fatty acid, and (D) an inorganic filler, wherein the polyethylene (A) has (1) a melt mass flow rate of 3.0 g / 10 min or less when measured under the conditions of a temperature of 190°C and a load of 21.18 N based on JIS K7210:1999, and (2) a density of 930 kg / m3 or more when measured by the water displacement method based on JIS K7112:1999. The component (C) preferably contains a zinc salt of a saturated higher fatty acid with a carbon number of 16 to 20 and a magnesium salt of a saturated higher fatty acid with a carbon number of 16 to 20. The polyethylene (A) preferably includes biomass-derived olpyethylene.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a polyethylene resin composition and a film thereof. More specifically, the present invention relates to a polyethylene resin composition suitable for use in calender roll film formation, and a film formed from the polyethylene resin composition using a calender roll film formation device. [Background technology]

[0002] Decorative sheets have been applied to the surface of substrates made of wood-based materials such as wood, plywood, laminated lumber, particle board, and hardboard; substrates made of resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or substrates made of metal-based materials such as iron and aluminum to create decorative designs for home appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture such as display shelves, storage chests, cupboards, and desks; and building components such as floors, walls, and bathrooms. Decorative sheets (so-called wallpaper) have also been applied to the surface of building walls made of wood-based materials such as wood, plywood, laminated lumber, particle board, and hardboard; metal-based materials such as iron and aluminum; and inorganic materials such as gypsum to create decorative designs. Films of polyethylene resin compositions are often used as the film substrate for such decorative sheets. This is because polyethylene-based resin compositions have good inclusion properties for inorganic fillers such as inorganic pigments and are also economically efficient. Furthermore, in order to meet the diverse design requirements for decorative sheets, a wide variety of colors are required for film substrates. Therefore, as a film production method, the use of a calender roll film-forming device is generally desired from the perspective of efficiently producing a wide variety of film substrates. However, when films are produced using a calender roll film-forming device, there is a disadvantage in that vertical streaks are likely to occur in films of polyethylene-based resin compositions. Furthermore, inorganic fillers such as inorganic pigments are often blended into film substrates for decorative sheets, and the problem of vertical streaks becomes more pronounced when inorganic fillers are blended into the polyethylene-based resin composition.

[0003] In recent years, the use of biomass-derived polyethylene instead of petroleum-derived polyethylene has been proposed from the perspective of reducing the environmental impact. However, it has been found that when biomass-derived polyethylene is used instead of petroleum-derived polyethylene, there is a disadvantage in that the thickness of films produced using a calender roll film-forming device varies widely. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 46-041463 [Patent Document 2] Japanese Patent Application Publication No. 06-080836 [Patent Document 3] Japanese Patent Application Publication No. 07-026077 [Patent Document 4] Japanese Patent Application Publication No. 09-227730 [Patent Document 5] Japanese Patent Application Publication No. 11-310669 [Patent Document 6] Japanese Patent Application Laid-Open No. 2001-151954 [Patent Document 7] Japanese Patent Application Laid-Open No. 2015-203035 [Patent Document 8] Japanese Patent Publication No. 2023-081823 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polyethylene resin composition suitable for use in calender roll film formation, and a film formed from the polyethylene resin composition using a calender roll film formation device. Here, the fact that a polyethylene resin composition is suitable for use in calender roll rolling film production means that at least a significant deterioration in the appearance of the surface of a film product caused by calender roll rolling can be suppressed (preferably, a deterioration in the appearance of the surface of a film product can be sufficiently suppressed). In another preferred embodiment, the polyethylene resin composition being suitable for use in calender roll film formation means that, particularly when biomass-derived polyethylene is used instead of petroleum-derived polyethylene, significant deterioration in the appearance of the film product due to calender roll rolling can be suppressed, and significant thickness unevenness can be suppressed. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above object can be achieved by using a specific resin composition.

[0007] That is, the various aspects of the present invention are as follows. [1]. (A) 100 parts by mass of polyethylene, (B) 0.01 to 5 parts by mass of an antioxidant, (C) 0.1 to 5 parts by mass of one or more selected from the group consisting of fatty acid zinc and fatty acid magnesium, and (D) containing 10 to 150 parts by mass of an inorganic filler, Here, (A) polyethylene is (1) The melt mass flow rate measured in accordance with JIS K7210:1999 at a temperature of 190°C and a load of 21.18N is 3.0 g / 10 min or less; (2) Density measured by the underwater displacement method according to JIS K7112:1999 is 930 kg / m 3 That's all. Polyethylene resin composition for calender roll film formation. [2]. The polyethylene resin composition for calender roll film formation according to item [1], wherein (C) one or more selected from the group consisting of zinc fatty acids and magnesium fatty acids comprises a zinc salt of a saturated higher fatty acid having 16 to 20 carbon atoms and a magnesium salt of a saturated higher fatty acid having 16 to 20 carbon atoms. [3]. The polyethylene resin composition for use in calender roll film formation according to item [1] or [2], further comprising 0.01 to 10 parts by mass of (E) an acrylic processing aid. [4]. The polyethylene resin composition for use in calender roll film formation according to any one of items [1] to [3], wherein the polyethylene (A) comprises biomass-derived polyethylene. [5]. The polyethylene-based resin composition for calender roll film formation according to any one of items [1] to [4], wherein the (D) inorganic filler contains calcium carbonate, and the amount of calcium carbonate blended is 10 parts by mass or more per 100 parts by mass of the (A) polyethylene. [6]. (D) The specific surface area of ​​calcium carbonate, an inorganic filler, measured by the air permeability method is 1.4 to 3.5 m 2 / g of the polyethylene resin composition for use in calender roll film formation according to [5]. [7]. The polyethylene-based resin composition for use in calender roll film formation according to [6], wherein the polyethylene (A) contains biomass-derived polyethylene. [8]. (A) Polyethylene a mixture comprising 90 to 20 mass% of polyethylene (a1) having a relatively high melt mass flow rate and 10 to 80 mass% of polyethylene (a2) having a relatively low melt mass flow rate, The polyethylene resin composition for calender roll film formation according to any one of items [1] to [7], wherein the ratio (MFR-a1 / MFR-a2) of the melt mass flow rate (MFR-a1) of the polyethylene (a1) to the melt mass flow rate (MFR-a2) of the polyethylene (a2) is greater than 1.0 and not greater than 20: Here, the melt mass flow rates of (a1) polyethylene and (a2) polyethylene are measured in accordance with JIS K7210:1999 under conditions of a temperature of 190°C and a load of 21.18N. [9]. The polyethylene resin composition for calender roll film formation according to any one of items [1] to [8], which does not contain cellulose.

[10] . A calender roll-formed film formed from the polyethylene resin composition for calender roll-formed films according to any one of items [1] to [9].

[11] . A decorative sheet comprising the calender roll-formed film according to item

[10] . [Effects of the Invention]

[0008] The polyethylene resin composition of the present invention can suppress the occurrence of vertical streaks when a film is formed using a calender roll rolling film-forming apparatus. A preferred polyethylene resin composition of the present invention can suppress the occurrence of vertical streaks when a film is formed using a calender roll rolling film-forming apparatus, even if a large amount of inorganic filler is blended. A preferred polyethylene resin composition of another embodiment of the present invention can reduce thickness variation when a film is formed using a calender roll rolling film-forming apparatus, even if biomass-derived polyethylene is used instead of petroleum-derived polyethylene. Therefore, a film formed using the polyethylene resin composition of the present invention using a calender roll rolling film-forming apparatus can be suitably used as a film substrate for decorative sheets. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a photograph showing the surface appearance of Film 1 of Example 16. [Figure 2] FIG. 2 is a conceptual diagram showing one example of an embodiment of the decorative sheet of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, the term "resin" is used to include a resin mixture containing two or more resins, and a resin composition containing components other than resin.

[0011] In this specification, the term "film" is used interchangeably or interchangeably with "sheet." In this specification, the terms "film" and "sheet" are used to refer to materials that can be industrially wound into rolls. The term "plate" is used to refer to materials that cannot be industrially wound into rolls. In addition, in this specification, laminating one layer and another layer in order includes both directly laminating the layers and laminating the layers with one or more additional layers, such as an anchor coat, interposed between them.

[0012] In this specification, the term "more than or equal to" in relation to a numerical range means a certain number or more than a certain number. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" in relation to a numerical range means a certain number or less than a certain number. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "to" in relation to a numerical range means a certain number, more than a certain number and less than another certain number, or another certain number. Here, another certain number is a number greater than the certain number. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of a numerical range can be arbitrarily combined, and embodiments incorporating such combinations can be interpreted. For example, from a statement regarding the numerical range of a certain characteristic such as "usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less," or "usually 10 to 40%, preferably 20 to 30%," it can be read that the numerical range of the certain characteristic is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment.

[0013] Other than in the examples, or where otherwise specified, all numerical values ​​used in the specification and claims should be understood to be modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of the number of significant digits and by applying ordinary rounding techniques.

[0014] In this specification, terms specifying shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, are intended to include not only the strict meanings but also substantially the same states.

[0015] In this specification, when it is explained that "comprises a certain substance," it is to be understood that, in one embodiment, it contains a certain substance, consists of a certain substance, or consists only of a certain substance. For example, from the explanation that "composition A comprises substances a1 and a2," it is to be understood that, in one embodiment, composition A comprises substances a1 and a2, composition A consists of substances a1 and a2, or composition A consists only of substances a1 and a2.

[0016] 1.Resin composition The polyethylene resin composition of the present invention comprises (A) polyethylene, (B) an antioxidant, (C) one or more selected from the group consisting of fatty acid zinc and fatty acid magnesium (hereinafter sometimes referred to as "fatty acid zinc, etc."), and (D) an inorganic filler. In one preferred embodiment, the polyethylene resin composition of the present invention further comprises (E) an acrylic processing aid. In another preferred embodiment, the polyethylene resin composition of the present invention comprises (A) a biomass-derived polyethylene. Each component will be described below.

[0017] (A) Polyethylene The polyethylene resin composition of the present invention contains (A) polyethylene. (A) Polyethylene is a polymer (including copolymer) containing primarily ethylene-derived structural units. Here, "mainly containing" means that the polyethylene contains ethylene-derived structural units in an amount sufficient to satisfy the range of property (2) density, which will be described later.

[0018] Examples of (A) polyethylene include ethylene homopolymers and copolymers of ethylene with a small amount of α-olefins. Here, "a small amount" means that the amount of α-olefin copolymerized is small enough to satisfy the range of property (2) density, which will be described later. Non-limiting examples of the α-olefins include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene, 2-ethyl-3-methyl-1-butene, 2,3,3-trimethyl-1-butene, 1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 2-ethyl-1-pentene, 3-ethyl-1-pentene, 4-ethyl-1-pentene, 2,4-dimethyl-1-pentene, 3,3-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-pentene, 2,4,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2-methyl-1-hexene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 2-ethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 1-heptene, 2-propyl-1-heptene, 3-propyl-1-heptene, 5-ethyl-2-methyl-1-heptene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. As the α-olefin, one or more of these can be used.

[0019] The (A) polyethylene (1) has a melt mass flow rate measured according to JIS K7210:1999 at a temperature of 190°C and a load of 21.18 N, and is generally 3.0 g / 10 min or less, from the viewpoint of suppressing the occurrence of vertical streaks in the film product and from the viewpoint of achieving both a large amount of inorganic filler inclusion and good mechanical properties of the film. The (A) polyethylene (1) melt mass flow rate may be preferably 2.0 g / 10 min or less, more preferably 1.2 g / 10 min or less, even more preferably 0.90 g / 10 min or less, and most preferably 0.60 g / 10 min or less. On the other hand, the above-mentioned property (1) melt mass flow rate of the (A) polyethylene may be preferably 0.01 g / 10 min or more, more preferably 0.05 g / 10 min or more, even more preferably 0.10 g / 10 min or more, and most preferably 0.15 g / 10 min or more, from the viewpoint of lowering the calender roll setting temperature of the calender roll film-forming device. In a preferred embodiment, the above-mentioned property (1) of the polyethylene (A) is that the melt mass flow rate is 0.01 g / 10 min or more and 3.0 g / 10 min or less, 0.01 g / 10 min or more and 2.0 g / 10 min or less, 0.01 g / 10 min or more and 1.2 g / 10 min or less, 0.01 g / 10 min or more and 0.90 g / 10 min or less, 0.01 g / 10 min or more and 0.60 g / 10 min or less, 0.05 g / 10 min or more and 3.0 g / 10 min or less, 0.05 g / 10 min or more and 2.0 g / 10 min or less, 0.05 g / 10 min or more and 1.2 g / 10 min or less, 0.05 g / 10 min or more and 0.90 g / 10 min or less, 0.05 ...05 g / 10 min or more and 0.05 g / 10 min or more and 0.05 g / 10 min or more and 0.05 g / 10 min or more and 0.60 g / 10 min or less, 0.05 g / 10 min or more and 0.05 g / 10 min or more and 0.05 g / 10 min or more and 0.05 g / 10 min or more The viscosity may be 10 minutes or more and 0.60g / 10 minutes or less, 0.10g / 10 minutes or more and 3.0g / 10 minutes or less, 0.10g / 10 minutes or more and 2.0g / 10 minutes or less, 0.10g / 10 minutes or more and 1.2g / 10 minutes or less, 0.10g / 10 minutes or more and 0.90g / 10 minutes or more, 0.10g / 10 minutes or more and 0.60g / 10 minutes or less, 0.15g / 10 minutes or more and 3.0g / 10 minutes or less, 0.15g / 10 minutes or more and 2.0g / 10 minutes or less, 0.15g / 10 minutes or more and 1.2g / 10 minutes or less, 0.15g / 10 minutes or more and 0.90g / 10 minutes or less, or 0.15g / 10 minutes or more and 0.60g / 10 minutes or less.

[0020] (A) The density of polyethylene (2) measured by the underwater displacement method in accordance with JIS K7112:1999 is usually 930 kg / m, from the viewpoint of preventing the unevenness of the surface of the substrate from spreading to the visible surface of the decorative sheet when a decorative sheet containing the film product is laminated to the surface of the substrate. 3 (A) The above-mentioned properties of polyethylene (2) The density is preferably 940 kg / m 3 More preferably, 945 kg / m 3 More preferably, 950 kg / m 3 On the other hand, the above-mentioned property (2) density of (A) polyethylene is preferably 965 kg / m from the viewpoint of lowering the calender roll temperature setting of the calender roll rolling film-forming device. 3 Less than or equal to 960 kg / m 3 It may be the following: In a preferred embodiment, the above-mentioned characteristic (2) density of (A) polyethylene is 930 kg / m 3 More than 965kg / m 3 Below, 930kg / m 3 More than 960kg / m 3 Below, 940kg / m 3 More than 965kg / m 3 Below, 940kg / m 3 More than 960kg / m 3 Below, 945kg / m 3 More than 965kg / m 3 Below, 945kg / m 3 More than 960kg / m 3 Below 950kg / m 3 More than 965kg / m 3 or less, or 950 kg / m 3 More than 960kg / m 3 It may be the following:

[0021] In one preferred embodiment, the (A) polyethylene may contain biomass-derived polyethylene, which can reduce the environmental impact. Here, "biomass-derived polyethylene" refers to polyethylene produced using biomass-derived monomers as at least a portion of raw material monomers such as ethylene. Furthermore, the "biomass" is not particularly limited as long as it is a biological resource such as a plant resource, and may be, for example, sugarcane. In one embodiment, the ratio of the biomass-derived monomer to the total amount of (A) polyethylene may be 10% by mass or more and 100% by mass or less, 15% by mass or more and 100% by mass or less, 20% by mass or more and 100% by mass or less, 25% by mass or more and 100% by mass or less, 30% by mass or more and 100% by mass or less, 35% by mass or more and 100% by mass or less, 40% by mass or more and 100% by mass or less, 45% by mass or more and 100% by mass or less, 50% by mass or more and 100% by mass or less, 55% by mass or more and 100% by mass or less, 60% by mass or more and 100% by mass or less, 65% by mass or more and 100% by mass or less, 70% by mass or more and 100% by mass or less, 75% by mass or more and 100% by mass or less, 80% by mass or more and 100% by mass or less, 85% by mass or more and 100% by mass or less, 90% by mass or more and 100% by mass or less, or 95% by mass or more and 100% by mass or less. In an embodiment in which the (A) polyethylene contains polyethylene other than biomass-derived polyethylene, the polyethylene other than biomass-derived polyethylene may typically be petroleum-derived polyethylene.

[0022] On the other hand, it has been found that when (A) polyethylene contains biomass-derived polyethylene, there is a disadvantage in that the thickness of the film produced using a calender roll film-forming device varies greatly. While not intending to be bound by theory, the reason why the thickness variation of the polyethylene resin composition of the present invention is small even when (A) polyethylene contains biomass-derived polyethylene is considered as follows. According to JP 2023-081823 A, biomass-derived polyethylene contains more impurities than petroleum-derived polyethylene, and films produced using this polyethylene are more likely to develop fish eyes. Therefore, when (A) polyethylene contains biomass-derived polyethylene, the thickness of the film produced using a calender roll film-forming device tends to vary greatly. On the other hand, in the polyethylene resin composition of the present invention, the synergistic effect of (B) antioxidant and (C) fatty acid zinc or the like suppresses the formation of fish eyes. Furthermore, the inclusion of a large amount of component (D) inorganic filler physically eliminates any fish eyes that do form. As a result, in the polyethylene resin composition of the present invention, even if the (A) polyethylene contains biomass-derived polyethylene, the thickness variation of the film product can be reduced.

[0023] The ratio of the above biomass-derived monomers to the total monomers constituting the biomass-derived polyethylene is determined by radiocarbon (C 14 ) concentration. 14 Measurement of the concentration of ) and conversion into the proportion of biomass-derived monomers can be outsourced to an analytical institution such as Accelerator Analysis Laboratory, Inc.

[0024] In another preferred embodiment, from the viewpoint of suppressing the occurrence of longitudinal streaks in the film product, the (A) polyethylene is a mixture of 90 to 20 mass% of polyethylene (a1) having a relatively high melt mass-flow rate and 10 to 80 mass% of polyethylene (a2) having a relatively low melt mass-flow rate, wherein the ratio (MFR-a1 / MFR-a2) of the melt mass-flow rate (MFR-a1) of the (a1) polyethylene to the melt mass-flow rate (MFR-a2) of the (a2) polyethylene may be greater than 1.0 and not greater than 20. The melt mass-flow rate is measured in accordance with JIS K 7210:1999 at a temperature of 190°C and a load of 21.18 N. In this embodiment, the sum of the amounts of the (a1) polyethylene and the (a2) polyethylene is typically 100 mass% (i.e., in this embodiment, the (A) polyethylene typically consists solely of the (a1) polyethylene and the (a2) polyethylene).

[0025] In this embodiment, it goes without saying that the above-mentioned property (1) melt mass-flow rate and property (2) density may be satisfied by a mixture consisting of (a1) polyethylene and (a2) polyethylene, etc. Also, in this embodiment, the (a1) polyethylene may be biomass-derived polyethylene, or the (a2) polyethylene may be biomass-derived polyethylene, or both the (a1) polyethylene and the (a2) polyethylene may be biomass-derived polyethylene.

[0026] The blend ratio of (a1) polyethylene and (a2) polyethylene may preferably be 70 to 40% by mass of (a1) polyethylene and 30 to 60% by mass of (a2) polyethylene.

[0027] The ratio (MFR-a1 / MFR-a2) may be more preferably 1.5 to 12, and even more preferably 2.0 to 8.0.

[0028] The (A) polyethylene may be a mixture of one or more polyethylenes. When the (A) polyethylene is a mixture of one or more polyethylenes, the mixture as a whole may satisfy the above-mentioned property (1) melt mass-flow rate and property (2) density, and may optionally further satisfy one or more of the above-mentioned preferred properties or amounts.

[0029] (B) Antioxidants The polyethylene resin composition of the present invention contains (B) an antioxidant. Without intending to be bound by theory, it is believed that (B) the antioxidant acts to suppress the occurrence of vertical streaks in film products due to a synergistic effect with (C) the fatty acid zinc salt, etc. Furthermore, as described above, it is believed that (B) the antioxidant acts to suppress the occurrence of fisheyes in film products due to a synergistic effect with (C) the fatty acid zinc salt, etc., even when (A) the polyethylene contains biomass-derived polyethylene.

[0030] Examples of the (B) antioxidant include hindered phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants, and amine-based antioxidants.

[0031] The hindered phenol-based antioxidant is not particularly limited, but examples thereof include triethylene glycol-bis 3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2-thio-diethylenebis Examples of suitable hydroxybenzoates include octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2-thiobis(4-methyl-6-t-butylphenol), N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphate-diethyl ester, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

[0032] The phosphite antioxidant is not particularly limited, and examples thereof include: (i) trialkyl phosphites such as trioleyl phosphite, trilauryl phosphite, triisodecyl phosphite, and tris(2-ethylhexyl) phosphite; alkylaryl phosphites such as 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, diphenyldecyl phosphite, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite; and compounds having one phosphite structure in one molecule, such as triaryl phosphites such as tris-(2,4-di-tert-butylphenyl) phosphite, trisnonylphenyl phosphite, tricresyl phosphite, and triphenyl phosphite; and (ii) tetrafluoroborate antioxidants. Examples of suitable phosphite compounds include phenyldipropylene glycol diphosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenylditridecylphosphite), bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra-dodecyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and compounds having two or more phosphite structures in one molecule, such as 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0033] The thioether antioxidant is not particularly limited, but examples thereof include pentaerythritol tetrakis(3-dodecylthiopropionate), didodecylthiodipropionate, ditridecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and 2-mercaptobenzimidazole.

[0034] The amine-based antioxidant is not particularly limited, but examples thereof include 4,4'-dioctyldiphenylamine, N,N'-diphenyl-p-phenylenediamine, and polymers of 2,2,4-trimethyl-1,2-dihydroquinoline.

[0035] As the (B) antioxidant, it is preferable to use the above hindered phenol-based antioxidant and the above phosphite-based antioxidant in combination.

[0036] As the (B) antioxidant, one of these or a mixture of two or more of them can be used.

[0037] The blend amount of (B) antioxidant may be usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.10 part by mass or more, even more preferably 0.20 part by mass or more, and most preferably 0.30 part by mass or more, per 100 parts by mass of (A) polyethylene, from the viewpoint of ensuring the effect of use. On the other hand, the blend amount of (B) antioxidant may be usually 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, still more preferably 1.5 parts by mass or less, and most preferably 1.0 part by mass or less, per 100 parts by mass of (A) polyethylene, from the viewpoint of suppressing bleed-out. (B) The amount of the antioxidant may be generally 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.01 parts by mass or more and 4 parts by mass or less, 0.01 parts by mass or more and 3 parts by mass or less, 0.01 parts by mass or more and 2 parts by mass or less, 0.01 parts by mass or more and 1.5 parts by mass or less, and 0.01 parts by mass or more, based on 100 parts by mass of (A) polyethylene. 1.0 part by mass or less, 0.05 part by mass or more and 5 parts by mass or less, 0.05 part by mass or more and 4 parts by mass or less, 0.05 part by mass or more and 3 parts by mass or less, 0.05 part by mass or more and 2 parts by mass or less, 0.05 part by mass or more and 1.5 parts by mass or less, 0.10 part by mass or more and 5 parts by mass or less, 0.10 part by mass or more and 4 parts by mass or less Bottom, 0.10 parts by mass to 3 parts by mass, 0.10 parts by mass to 2 parts by mass, 0.10 parts by mass to 1.5 parts by mass, 0.10 parts by mass to 1.0 parts by mass, 0.20 parts by mass to 5 parts by mass, 0.20 parts by mass to 4 parts by mass, 0.20 parts by mass to 3 parts by mass, 0.20 parts by mass to 2 parts by mass, 0.20 parts by mass The amount may be at least 1.5 parts by mass, at least 0.20 parts by mass and at most 1.0 parts by mass, at least 0.30 parts by mass and at most 5 parts by mass, at least 0.30 parts by mass and at most 3 parts by mass, at least 0.30 parts by mass and at most 2 parts by mass, at least 0.30 parts by mass and at most 1.5 parts by mass, or at least 0.30 parts by mass and at most 1.0 parts by mass.

[0038] (C) Fatty acid zinc, etc. The polyethylene resin composition of the present invention contains (C) one or more selected from the group consisting of fatty acid zinc salts and fatty acid magnesium salts. That is, component (C) may be one or more fatty acid zinc salts, or one or more fatty acid magnesium salts, or a mixture of one or more fatty acid zinc salts and one or more fatty acid magnesium salts. The fatty acid zinc salt is a salt of zinc with a fatty acid (a monocarboxylic acid having a carboxy group (-COOH) in the hydrocarbon chain). The fatty acid magnesium salt is a salt of magnesium with a fatty acid (a monocarboxylic acid having a carboxy group (-COOH) in the hydrocarbon chain).

[0039] While not intending to be bound by theory, it is believed that (C) fatty acid zinc salts, etc., work to suppress the occurrence of vertical streaks in film products through a synergistic effect with (B) antioxidants. Also, as mentioned above, it is believed that (C) fatty acid zinc salts, etc., work to suppress the occurrence of fisheyes in film products through a synergistic effect with (B) antioxidants, even when (A) polyethylene contains biomass-derived polyethylene.

[0040] The fatty acids constituting (C) fatty acid zinc, etc. are not particularly limited, but examples thereof include saturated higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, unsaturated higher fatty acids such as oleic acid, linoleic acid, ricinoleic acid, behenic acid, and erucic acid, and hydroxy higher fatty acids such as 12-hydroxystearic acid, etc. Here, higher fatty acids refer to fatty acids having 6 or more carbon atoms, preferably 10 or more carbon atoms.

[0041] From the viewpoint of suppressing bleed-out from the film product, the (C) fatty acid zinc salt or the like may preferably comprise one or more selected from the group consisting of zinc salts of saturated higher fatty acids and magnesium salts of saturated higher fatty acids, more preferably one or more selected from the group consisting of zinc salts of saturated higher fatty acids having 12 to 22 carbon atoms and magnesium salts of saturated higher fatty acids having 12 to 22 carbon atoms. In a more preferred embodiment, the (C) fatty acid zinc salt or the like may comprise a zinc salt of saturated higher fatty acids having 16 to 20 carbon atoms from the viewpoint of suppressing longitudinal streaks in the film product. In another more preferred embodiment, the (C) fatty acid zinc salt or the like may comprise a magnesium salt of saturated higher fatty acids having 16 to 20 carbon atoms from the viewpoint of releasability from calender rolls. In another even more preferred embodiment, the (C) fatty acid zinc salt or the like may comprise a zinc salt of saturated higher fatty acids having 16 to 20 carbon atoms and a magnesium salt of saturated higher fatty acids having 16 to 20 carbon atoms.

[0042] As (C) fatty acid zinc or the like, any one of the substances exemplified above or a mixture of two or more of them can be used.

[0043] The amount of (C) fatty acid zinc or the like to be blended is usually 0.1 part by mass or more, preferably 0.2 part by mass or more, more preferably 0.3 part by mass or more, even more preferably 0.4 part by mass or more, and most preferably 0.5 part by mass or more, per 100 parts by mass of (A) polyethylene, from the viewpoint of ensuring the effect of use. On the other hand, the amount of (C) fatty acid zinc or the like to be blended may be usually 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, still more preferably 1.5 parts by mass or less, and most preferably 1.0 part by mass or less, per 100 parts by mass of (A) polyethylene, from the viewpoint of suppressing bleed-out. The blending amount of (C) fatty acid zinc or the like may be usually 0.1 parts by mass or more and 5 parts by mass or less, and preferably 0.1 parts by mass or more and 4 parts by mass or less, 0.1 parts by mass or more and 3 parts by mass or less, 0.1 parts by mass or more and 2 parts by mass or less, 0.1 parts by mass or more and 1.5 parts by mass or less, 0.1 parts by mass or more and 1.0 parts by mass or less, 0.2 parts by mass or more and 5 parts by mass or less, 0.2 parts by mass or more and 4 parts by mass or less, 0.2 parts by mass or more and 3 parts by mass or less, 0.2 parts by mass or more and 2 parts by mass or less, 0.2 parts by mass or more and 1.5 parts by mass or less, 0.2 parts by mass or more and 1.0 parts by mass or less, 0.3 parts by mass or more and 5 parts by mass or less, 0.3 parts by mass or more and 4 parts by mass, The following: 0.3 parts by mass to 3 parts by mass, 0.3 parts to 2 parts by mass, 0.3 parts to 1.5 parts by mass, 0.3 parts to 1.0 parts by mass, 0.4 parts to 5 parts by mass, 0.4 parts to 4 parts by mass, 0.4 parts to 3 parts by mass, 0.4 parts by mass to 2 parts by mass, 0.4 parts by mass 0.4 parts to 1.0 parts by weight, 0.5 parts to 5 parts by weight, 0.5 parts to 4 parts by weight, 0.5 parts to 3 parts by weight, 0.5 parts to 2 parts by weight, 0.5 parts to 1.5 parts by weight, or 0.5 parts to 1.0 parts by weight.

[0044] (D) Inorganic filler The polyethylene resin composition of the present invention contains (D) an inorganic filler. Without intending to be bound by theory, as described above, it is believed that (D) the inorganic filler serves to reduce the variation in thickness of a film formed using a calender roll film-forming device, even when (A) the polyethylene contains biomass-derived polyethylene.

[0045] (D) The inorganic filler is not particularly limited, but examples thereof include metal carbonates such as calcium carbonate and magnesium carbonate; silicon compounds such as silica (silicon dioxide), natural silicic acid, synthetic silicic acid (white carbon), and magnesium silicate; metal oxides such as alumina, zirconia, titanium dioxide (titania, for example, rutile-type titanium dioxide), zinc oxide, magnesium oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; nitrides such as aluminum nitride and boron nitride; and talc, mica, clay, hydrotalcite, zeolite, barium sulfate, and carbon black. Other examples of (D) inorganic fillers include inorganic complex oxide colorants such as CI Pigment Blue 28, CI Pigment Blue 36, CI Pigment Brown 24, CI Pigment Yellow 53, CI Pigment Green 17, CI Pigment Black 28, CI Pigment Black 26, CI Pigment Green 50, and CI Pigment Green 26; and inorganic colorants such as red iron oxide (ferric oxide), copper-chromium alloy, iron-chromium-tin-titanium alloy, nickel-antimony-titanium alloy, and chromium-antimony-titanium alloy.

[0046] In one preferred embodiment, even when the (A) polyethylene contains biomass-derived polyethylene, the (D) inorganic filler may contain calcium carbonate from the viewpoint of further reducing the variation in thickness of the film formed using a calender roll film-forming device.

[0047] The specific surface area of ​​the (D) inorganic filler calcium carbonate measured by an air permeability method is preferably 1.4 m², even if the (A) polyethylene contains biomass-derived polyethylene, from the viewpoint of reducing the variation in the thickness of the film formed using a calender roll film-forming device. 2 / g or more, more preferably 1.7m 2 / g or more, more preferably 1.9m 2 / g or more, most preferably 2.0m 2 On the other hand, the specific surface area of ​​calcium carbonate measured by the air permeability method is preferably 3.5 m / g or more from the viewpoint of peelability between the film product and the calender roll. 2 / g or less, more preferably 3.0m 2 / g or less, more preferably 2.5m 2 / g or less. The specific surface area of ​​calcium carbonate measured by the air permeability method is preferably 1.4 m 2 / g or more 3.5m 2 / g or less, 1.4m 2 / g or more 3.0m 2 / g or less, 1.4m 2 / g or more 2.5m 2 / g or less, 1.7m 2 / g or more 3.5m 2 / g or less, 1.7m 2 / g or more 3.0m 2 / g or less, 1.7m 2 / g or more 2.5m 2 / g or less, 1.9m 2 / g or more 3.5m 2 / g or less, 1.9m 2 / g or more 3.0m 2 / g or less, 1.9m 2 / g or more 2.5m 2 / g or less, 2.0m 2 / g or more 3.5m 2 / g or less, 2.0m 2 / g or more 3.0m 2 / g or less, or 2.0m 2 / g or more 2.5m 2 / g or less.

[0048] The specific surface area is measured by the air permeability method in accordance with JIS R5201:2015, 8.1 Specific Surface Area Test. The actual density value is used (as mentioned in Note a) of Table 1 of JIS R5201:2015, 8.1 Specific Surface Area Test, the actual density value can be obtained in accordance with JIS 7 Density Test). When creating the bed, care should be taken to ensure the tightest packing and the smallest void ratio. The void ratio value calculated for the created bed is used.

[0049] In one preferred embodiment, the polyethylene resin composition of the present invention may contain titanium dioxide (titania) as the inorganic filler (D). The use of titanium dioxide (titania) in the polyethylene resin composition can easily impart to the film product a hiding property suitable for use as a film substrate for decorative sheets.

[0050] In one of the more preferred embodiments, the polyethylene resin composition of the present invention may contain titanium dioxide (titania) and calcium carbonate.

[0051] As the (D) inorganic filler, one or a mixture of two or more of any of the above-exemplified substance groups can be used.

[0052] The blending amount of the (D) inorganic filler is usually 150 parts by mass or less, preferably 120 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the (A) polyethylene, from the viewpoint of suppressing the occurrence of vertical streaks in the film product. On the other hand, the blending amount of the (D) inorganic filler may be usually 10 parts by mass or more, preferably 15 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 40 parts by mass or more, and most preferably 60 parts by mass or more, per 100 parts by mass of the (A) polyethylene, even if the (A) polyethylene contains biomass-derived polyethylene, from the viewpoint of reducing variation in thickness of the film formed using a calender roll film-forming apparatus. The amount of the (D) inorganic filler, relative to 100 parts by mass of the (A) polyethylene, may typically be 10 parts by mass or more and 150 parts by mass or less, preferably 10 parts by mass or more and 120 parts by mass or less, 10 parts by mass or more and 100 parts by mass or less, 15 parts by mass or more and 150 parts by mass or less, 15 parts by mass or more and 120 parts by mass or less, 15 parts by mass or more and 100 parts by mass or less, 25 parts by mass or more and 150 parts by mass or less, 25 parts by mass or more and 120 parts by mass or less, 25 parts by mass or more and 100 parts by mass or less, 40 parts by mass or more and 150 parts by mass or less, 40 parts by mass or more and 120 parts by mass or less, 40 parts by mass or more and 100 parts by mass or less, 60 parts by mass or more and 150 parts by mass or less, 60 parts by mass or more and 120 parts by mass or less, or 60 parts by mass or more and 100 parts by mass or less.

[0053] In an embodiment in which the (D) inorganic filler contains calcium carbonate, the amount of calcium carbonate may be, from the viewpoint of reliably obtaining the above-described effects, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and most preferably 35 parts by mass or more, per 100 parts by mass of the (A) polyethylene. In this embodiment, it goes without saying that the total amount of calcium carbonate and the amount of the (D) inorganic filler other than calcium carbonate should be within any of the ranges described above for the amount of the (D) inorganic filler.

[0054] (E) Acrylic processing aids In one preferred embodiment, the polyethylene resin composition of the present invention may contain (E) an acrylic processing aid from the viewpoint of suppressing vertical streaks in film products.

[0055] The (E) acrylic processing aid is an acrylic polymer compound (acrylic thermoplastic resin) primarily containing structural units derived from (meth)acrylic acid alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. Here, methyl (meth)acrylate refers to methyl acrylate or methyl methacrylate. The same applies to other compounds. "Mainly containing structural units derived from (meth)acrylic acid alkyl esters" means that the acrylic polymer compound contains structural units derived from (meth)acrylic acid alkyl esters in an amount of 60 mol% or more of all structural units. In one embodiment, the content of structural units derived from (meth)acrylic acid alkyl esters may be 70 mol% or more, 80 mol% or more, 90 mol% or more, or 95 to 100 mol%.

[0056] As the (E) acrylic processing aid, any one of the substances exemplified above can be used alone or in combination with two or more of them.

[0057] The amount of the (E) acrylic processing aid is not particularly limited, since it is an optional component. From the viewpoint of reliably obtaining the effects of use, the amount of the (E) acrylic processing aid may be preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the (A) polyethylene. On the other hand, from the viewpoint of film surface smoothness, the amount of the (E) acrylic processing aid may be preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 4 parts by mass or less, and most preferably 2 parts by mass or less, per 100 parts by mass of the (A) polyethylene. The amount of the (E) acrylic processing aid may be, relative to 100 parts by mass of the (A) polyethylene, preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7 parts by mass, 0.01 to 4 parts by mass, 0.01 to 2 parts by mass, 0.1 to 10 parts by mass, 0.1 to 7 parts by mass, 0.1 to 4 parts by mass, 0.1 to 2 parts by mass, 0.5 to 10 parts by mass, 0.5 to 7 parts by mass, 0.5 to 4 parts by mass, or 0.5 to 2 parts by mass.

[0058] The polyethylene resin composition of the present invention may further contain optional components other than (A) to (E) as desired, to the extent that the object of the present invention is not adversely affected. Examples of such optional components include thermoplastic resins other than (A) polyethylene and (E) acrylic processing aids, additives other than (B) antioxidants and (C) fatty acid zinc salts, etc., organic flame retardants, and organic pigments.

[0059] Examples of thermoplastic resins other than (A) polyethylene and (E) acrylic processing aids include ethylene-α-olefin copolymer elastomers, ethylene-α-olefin copolymer plastomers, linear low-density polyethylene, high-pressure low-density polyethylene, ethylene-vinyl acetate copolymers, and ethylene-(meth)acrylic acid alkyl ester copolymers.

[0060] Examples of additives other than the (B) antioxidant and the (C) fatty acid zinc salt, etc., include weathering agents such as antioxidants, light stabilizers, and ultraviolet absorbers; lubricants such as acid amides, fatty acids, fatty acid metal salts other than the (C) fatty acid zinc salt, etc., such as calcium stearate, wax, silicone oil, and modified silicone oil; nucleating agents such as aromatic phosphate metal salts and gelol-based agents; and antistatic agents such as glycerin fatty acid ester-based agents.

[0061] As optional components other than (A) to (E), one or more of the substances exemplified above can be used.

[0062] The blending amount of the optional components other than (A) to (E) is not particularly limited as long as it does not contradict the object of the present invention, since they are components that are used optionally. The blending amount of the optional components other than (A) to (E) (if used) is usually more than 0 part by mass or 0.01 part by mass or more, and may be about 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 1 part by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of polyethylene (A).

[0063] In one embodiment, the polyethylene resin composition of the present invention may not contain any one or more of the optional components other than (A) to (E).

[0064] As used herein, "not containing a certain component in a polyethylene resin composition" means that the component is not intentionally blended. In the technical field of resin compositions, when the component is intentionally blended, it is typically blended in an amount of 0.01 part by mass or more relative to the total mass of the resin composition. Therefore, "not containing a certain component in a polyethylene resin composition" can also be rephrased as "the content of the component is typically 0 part by mass or more and less than 0.01 part by mass, preferably 0.001 part by mass or less, and more preferably 0.0001 part by mass or less, relative to 100 parts by mass of (A) polyethylene."

[0065] In one preferred embodiment, the polyethylene resin composition of the present invention may not contain fibers such as cellulose, from the viewpoint of imparting suitable mechanical properties to the film product as a film substrate for a decorative sheet.

[0066] 2. Manufacturing method of resin composition The polyethylene resin composition of the present invention can be obtained by using any melt kneader to charge the above components (A) to (D) and any optional components used as desired into the melt kneader simultaneously or in any order and melt kneading them, usually at a resin temperature of 180°C to 240°C, preferably 190°C to 230°C.

[0067] Examples of the melt kneader include batch kneaders such as pressure kneaders and mixers, extrusion kneaders such as single-screw extruders, co-rotating twin-screw extruders, and counter-rotating twin-screw extruders, and calendar roll kneaders, etc. These may be used in any combination.

[0068] The resin composition obtained can be pelletized by any method and then formed into a film using any calender roll film-forming device. The pelletization can be performed by methods such as hot cutting, strand cutting, and underwater cutting.

[0069] In one embodiment, the polyethylene resin composition in the form of blocks, rods, or strands discharged from the melt kneader may be sent directly to any calender roll film-forming device to be formed into a film.

[0070] 3. Film The film of the present invention is a film formed from the polyethylene resin composition of the present invention, and can be suitably used as a film substrate for decorative sheets.

[0071] The film of the present invention can be obtained by forming the polyethylene resin composition of the present invention using a calender roll film-forming apparatus equipped with a calender roll processing machine and a winding device. More preferably, the film can be formed using the calender roll film-forming apparatus under the condition of a roll temperature of 160°C to 200°C.

[0072] Examples of the calender roll rolling machine include an upright three-roll machine, an upright four-roll machine, an L-shaped four-roll machine, an inverted L-shaped four-roll machine, and a Z-roll machine.

[0073] The thickness of the film of the present invention can be appropriately determined taking into consideration film-forming properties, applications and required properties, and handling properties. From the viewpoints of film-forming properties, handling properties, and hiding properties, the thickness of the film of the present invention may be usually 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more, and even more preferably 45 μm or more. On the other hand, from the viewpoint of meeting the demand for thinner articles containing the film, the thickness of the film of the present invention may be usually 500 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. The thickness of the film of the present invention may usually be 20 μm or more and 500 μm or less, preferably 20 μm or more and 200 μm or less, 20 μm or more and 150 μm or less, 20 μm or more and 100 μm or less, 30 μm or more and 500 μm or less, 30 μm or more and 200 μm or less, 30 μm or more and 150 μm or less, 30 μm or more and 100 μm or less, 40 μm or more and 500 μm or less, 40 μm or more and 200 μm or less, 40 μm or more and 150 μm or less, 40 μm or more and 100 μm or less, 45 μm or more and 500 μm or less, 45 μm or more and 200 μm or less, 45 μm or more and 150 μm or less, or 45 μm or more and 100 μm or less.

[0074] The film of the present invention may be transparent or opaque. Furthermore, the film of the present invention may be colored or uncolored. Furthermore, the film of the present invention may be colored and transparent, or colored and opaque.

[0075] The film of the present invention in a transparent embodiment can be suitably used, for example, as a film substrate for a decorative sheet to be attached to glass, such as a glass decorative film, etc. The film of the present invention in an opaque or concealing embodiment can be suitably used, for example, as a film substrate for a decorative sheet to be used for the decoration and / or ornamentation of home appliances, furniture, and building components, and for wallpaper to be used for the decoration and / or ornamentation of building walls.

[0076] 4. Decorative sheets The decorative sheet of the present invention comprises the film of the present invention. The decorative sheet of the present invention is typically a decorative sheet having the film of the present invention as a film substrate. In a non-limiting and typical embodiment, the decorative sheet of the present invention is a decorative sheet having the film of the present invention, in an embodiment having opaque or concealing properties, as a film substrate (hereinafter sometimes abbreviated as "(α) decorative sheet"). This typical embodiment will be described below.

[0077] (α) Decorative sheets include, for example, those having the following structure: In actual use, starting from the side that is normally visible, (α1) a decorative sheet having a surface protective layer and a film substrate layer; (α2) a decorative sheet having a surface protective layer, a printing layer, and a film substrate layer; (α3) a decorative sheet having a surface protective layer, a transparent resin layer, a printing layer, and a film substrate layer; (α4) a decorative sheet having a surface protective layer, a printed layer, a transparent resin layer, and a film substrate layer; (α5) a decorative sheet having a surface protective layer, a printed layer, a transparent resin layer, another printed layer, and a film substrate layer; (α6) decorative sheet having a surface protective layer, a transparent resin layer, and a film substrate layer; (α7) decorative sheet having a transparent resin layer and a film substrate layer, and (α8) Decorative sheet having a transparent resin layer, a printed layer, and a film substrate layer. The decorative sheets (α1) to (α8) may further have a pressure-sensitive adhesive layer on the back surface of the film substrate layer. In this specification, "actual use state" refers to the state in which the decorative sheet is used for the make-up and decoration of an article. "Front" means the side that is normally visible in the actual use state of the layer. "Back" means the side opposite to the side that is normally visible in the actual use state of the layer (the side opposite to the front). The film of the film substrate layer and the polyethylene resin composition that constitutes it have been described above in "1. Resin composition," "2. Method for producing resin composition," and "3. Film." Hereinafter, each layer other than the film substrate layer will be described.

[0078] surface protection layer The surface protective layer serves to impart scratch resistance, and preferably to impart scratch resistance and stain resistance.

[0079] The material used to form the surface protective layer is not particularly limited as long as it can impart scratch resistance, preferably scratch resistance and contamination resistance, and can be appropriately selected taking into account the use of the decorative sheet. Examples of materials used to form the surface protective layer include thermosetting resin composition paints such as curable urethane resin composition paints (e.g., two-component curing urethane paints), curable silicone resin composition paints, and curable fluorine resin composition paints, active energy ray curable resin composition paints (e.g., polyfunctional (meth)acrylate (a compound having two or more acryloyl groups or methacryloyl groups in one molecule) composition paints), and thermoplastic resin composition paints (e.g., thermoplastic urethane resin composition paints, thermoplastic silicone resin composition paints, and thermoplastic fluorine resin composition paints). The material used to form the surface protective layer can be one of these or a mixture of two or more of them.

[0080] The surface protective layer can be formed using the above-mentioned materials by a known web coating method.

[0081] The thickness of the surface protective layer is not particularly limited and can be appropriately selected taking into consideration the workability when forming the surface protective layer and the intended use of the decorative sheet (such as the required level of scratch resistance and contamination resistance). From the viewpoint of scratch resistance, the thickness of the surface protective layer may usually be 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, even more preferably 3 μm or more, and most preferably 5 μm or more. On the other hand, from the viewpoint of workability when forming the surface protective layer, the thickness of the surface protective layer may preferably be 100 μm or less, more preferably 60 μm or less, and even more preferably 30 μm or less. The thickness of the surface protective layer may typically be 0.5 μm or more and 100 μm or less, preferably 0.5 μm or more and 60 μm or less, 0.5 μm or more and 30 μm or less, 1 μm or more and 100 μm or less, 1 μm or more and 60 μm or less, 1 μm or more and 30 μm or less, 2 μm or more and 100 μm or less, 2 μm or more and 60 μm or less, 2 μm or more and 30 μm or less, 3 μm or more and 100 μm or less, 3 μm or more and 60 μm or less, 3 μm or more and 30 μm or less, 5 μm or more and 100 μm or less, 5 μm or more and 60 μm or less, or 5 μm or more and 30 μm or less.

[0082] transparent resin layer The transparent resin layer functions to impart a sense of depth to the design and / or to protect the printed layer. In a typical embodiment, the transparent resin layer may be formed by laminating a film made of a transparent resin. In other embodiments, the transparent resin layer may be formed by laminating a transparent resin using a melt extrusion method.

[0083] Examples of transparent resins constituting the transparent resin layer include polyvinyl chloride resins, polyester resins such as polyethylene terephthalate and glycol-modified polyethylene terephthalate (PETG), fluorine-containing resins such as polyvinylidene fluoride, aromatic polycarbonate resins, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane-methyl (meth)acrylate copolymers, polyolefin resins such as polyethylene, polypropylene, and poly-4-methyl-pentene-1, cellulose ester resins such as triacetyl cellulose, cyclic hydrocarbon resins such as ethylene-norbornene copolymers, polyamide resins, polyarylate resins, polymeric urethane acrylate resins, and polyimide resins. The transparent resin may be one or a mixture of two or more of these.

[0084] Examples of films made of transparent resin that are laminated as the transparent resin layer include unstretched films, uniaxially stretched films, and biaxially stretched films of the transparent resin, as well as laminated films in which two or more layers of one or more of these films are laminated.

[0085] The thickness of the transparent resin layer is not particularly limited and can be appropriately selected taking into consideration the desired design, workability in forming the transparent resin layer, and the intended use of the decorative sheet. The thickness of the transparent resin layer may be, for example, 1 to 200 μm, 5 to 120 μm, 10 to 100 μm, 20 to 80 μm, or 30 to 50 μm.

[0086] printing layer The printed layer is a layer provided to enhance design, and can be formed by laminating one or more printed layers entirely or partially on the front surface of the film substrate layer, the front surface of the transparent resin layer, and / or the back surface of the transparent resin layer, either directly or via an anchor coat.

[0087] The pattern of the printed layer is not particularly limited and may be any desired pattern, such as a metallic pattern such as a hairline, a wood grain pattern, a stone pattern imitating the surface of rock such as marble, a fabric pattern imitating a cloth grain or cloth-like pattern, a pattern imitating leather products, a tiled pattern, a brickwork pattern, a marquetry pattern, a lattice pattern or other geometric pattern, a pattern imitating letters or symbols, and a patchwork pattern.

[0088] The method for forming the printed layer is not particularly limited and can be appropriately selected taking into consideration the type of pattern to be formed and the intended use of the decorative sheet. Examples of methods for forming the printed layer include gravure printing (intaglio printing) and inkjet printing.

[0089] The printing ink used to form the printed layer is not particularly limited and can be appropriately selected taking into consideration the method for forming the printed layer and the intended use of the decorative sheet. Examples of the printing ink used to form the printed layer include an appropriate mixture of a binder and a colorant, preferably an appropriate mixture of a binder and a colorant with optional components such as a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent.

[0090] The binder is not particularly limited and can be appropriately selected taking into consideration the method for forming the printed layer, the type of colorant used, and the intended use of the decorative sheet. Examples of binders include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins, as well as active energy ray-curable resins such as polyfunctional (meth)acrylates (compounds having two or more acryloyl or methacryloyl groups per molecule). The binder can be one of these or a mixture of two or more of them.

[0091] The colorant is not particularly limited and can be appropriately selected taking into consideration the method for forming the printed layer, the type of binder used, and the intended use of the decorative sheet. Examples of colorants include inorganic colorants such as titanium dioxide (titania), red iron oxide (ferric oxide), ultramarine (ultramarine blue), and carbon black; organic colorants such as aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue; and high-brightness pigments such as glass particles coated with metal oxides and pulverized foils of vapor-deposited metal-containing compounds. The colorant can be one of these or a mixture of two or more of them.

[0092] In another embodiment, the printing layer may be formed by laminating aluminum, tin, titanium, indium, or oxides thereof by a known dry coating method such as vacuum deposition, thereby providing a metallic design.

[0093] The thickness of the printed layer is not particularly limited and can be appropriately selected taking into consideration the type of design to be imparted, the method for forming the printed layer, the type of printing ink used, and the intended use of the decorative sheet. The thickness of the printed layer (when formed by laminating two or more layers, the total thickness) may be, for example, 0.1 to 20 μm, 0.5 to 10 μm, or 1 to 5 μm.

[0094] adhesive layer The adhesive layer functions to enable the decorative sheet to be attached to an adherend regardless of the material or surface condition (surface smoothness, etc.) of the surface of the film substrate layer (decorative sheet attachment surface) to which the decorative sheet is attached. The term "adhesive" includes pressure-sensitive adhesives and adhesives.

[0095] The adhesive used to form the adhesive layer is not particularly limited and can be appropriately selected taking into consideration that the film substrate is a polyethylene resin composition, the material and surface condition (surface smoothness, etc.) of the surface of the film substrate layer (the surface to which the decorative sheet is attached) where the decorative sheet is attached to the adherend, and the use of the article decorated or ornamented with the decorative sheet (required adhesion strength, etc.). Examples of the adhesive include pressure-sensitive adhesives such as acrylic adhesives, urethane adhesives, and silicone adhesives, hot-melt adhesives such as thermoplastic polyester adhesives, and curable adhesives such as curable urethane adhesives, curable polyester adhesives, and epoxy adhesives. The adhesive can be one or a mixture of two or more of these.

[0096] The adhesive layer can be formed using the adhesive agent by a known web coating method.

[0097] The thickness of the pressure-sensitive adhesive layer can be appropriately selected taking into consideration that the film substrate is a polyethylene resin composition, the material and surface condition (surface smoothness, etc.) of the surface of the film substrate layer where the decorative sheet is attached to the adherend (the surface to which the decorative sheet is attached), and the use of the article decorated or ornamented with the decorative sheet (required bonding strength, etc.). The thickness of the pressure-sensitive adhesive layer may usually be 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 2 to 30 μm.

[0098] Manufacturing method of decorative sheet The method for producing the decorative sheet of the present invention is not particularly limited, and any known method can be selected and used as appropriate, taking into consideration the layer structure and the properties of each layer. Furthermore, the method for producing the (α) decorative sheet (i.e., a decorative sheet using the film of the present invention in an opaque or concealing embodiment as a film substrate) is not particularly limited, and any known method can be selected and used as appropriate, taking into consideration the layer structure and the properties of each layer.

[0099] A non-limiting example of a method for producing one embodiment of the (α3) decorative sheet will now be described. (1) First, an opaque or concealing film of the present invention is produced by the methods described above in "1. Resin composition," "2. Method for producing resin composition," and "3. Film." (2) Next, a print layer is formed by gravure printing on one side of the film of the present invention obtained in the above step (1), to obtain a laminate A including a film substrate layer. (3) Next, using any of the above transparent resins, a transparent resin film is produced using a calendar roll rolling film-forming device equipped with a calendar roll rolling processing machine and a winding device, or a T-die film-forming device equipped with an extruder, a T-die, and a winding device. (4) A surface protection layer is formed on one side of the transparent resin film obtained in step (3) using a two-component curing urethane paint, and a transparent hot melt adhesive layer is formed on the other side to obtain laminate B. (5) The printed layer side of the laminate A obtained in the above step (2) is superimposed on the transparent hot melt adhesive layer side of the laminate B obtained in the above step (4), and inserted between a rotating heating roll and a receiving roll, and laminate A and laminate B are thermally laminated to obtain laminate C. (6) A pressure-sensitive adhesive layer is formed on the surface of the laminate C obtained in the above step (5) on the side of the film substrate layer (film of the present invention) to obtain a decorative sheet.

[0100] Before the step (4), the surface of the transparent resin film obtained in the step (3) on which the surface protective layer is formed may be embossed. Before the step (5), the surface of the printed layer side of the laminate A may be embossed. Before or simultaneously with the step (5), the surface of the surface protective layer side of the laminate B may be embossed. After the step (5), the surface of the surface protective layer side of the laminate C may be embossed.

[0101] The embossing can be carried out by inserting the web between an appropriately heated rotating design-imparting roll and a rotating receiving roll so that the embossed surface faces the design-imparting roll, and pressing the web.

[0102] The embossed shape can be appropriately selected taking into consideration the design, the properties of the material constituting the embossed surface, and the thickness of the layer constituting the embossed surface. Examples of the embossed shape include shapes imitating natural materials such as wood grain and leather grain, hairline shapes that resemble processed metal, geometric shapes such as checkerboard patterns, stripes, and polka dots, and shapes that combine a plurality of these.

[0103] FIG. 2 is a conceptual diagram showing an example of an embodiment of the (α3) decorative sheet. The decorative sheet 10 has, in order from the side that is normally visible in actual use, a surface protection layer 1, a transparent resin layer 2, a printed layer 3, a film substrate layer 4, and a pressure-sensitive adhesive layer 5. In this example, the surface protection layer 1 is formed from a two-component curing urethane paint, the transparent resin layer 2 is formed from a non-crystalline aromatic polyester (glycol-modified polyethylene terephthalate (PETG)), and the adhesive layer 5 is formed using a hot melt adhesive. [Example]

[0104] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0105] Measurement and evaluation methods for physical properties (i) Surface appearance (presence or absence of vertical streaks) The surfaces (both sides) of the film were visually observed while irradiating the light of a fluorescent lamp at various angles of incidence, and evaluated according to the following criteria. A: No vertical lines were observed. The gloss of the film surface was uniform. B: No vertical streaks were observed, but there were some areas on the film surface where the gloss was lower than the surrounding area (very slight surface roughness was observed in some areas). C: No vertical streaks were observed, but slight surface roughness was observed. D: Vertical lines were observed. Here, a rating of rank C or higher for surface appearance (presence or absence of vertical streaks) is considered to be acceptable.

[0106] 1 shows a photograph of the surface appearance of Film 1 of Example 16 (an example outside the present invention), in which the occurrence of vertical streaks was clearly observed.

[0107] (ii) Thickness unevenness The thickness was measured at three locations: near the center of the film in the horizontal direction, 10 cm inside from the left edge, and 10 cm inside from the right edge, and at 10 locations every 5 m in the machine direction of the film, for a total of 30 locations.The standard deviation was calculated and evaluated according to the following criteria. A: The standard deviation was less than 2.0. B: The standard deviation was 2.0 or more and less than 3.0. C: The standard deviation was 3.0 or more and less than 6.0. D: Standard deviation was 6.0 or more. Here, a rating of rank C or higher for thickness unevenness is considered to be acceptable. If both the surface appearance (presence or absence of vertical streaks) and thickness unevenness are ranked C or higher under at least either the film-forming conditions for film 1 or the film-forming conditions for film 2 described below, it can be said to be pass (a polyethylene-based resin composition suitable for use in calender roll rolling film formation).

[0108] Raw materials used (A) Polyethylene (A-1) Braskem's biomass-derived polyethylene "GF4950" (product name). Melt mass-flow rate (190°C, 21.18N) 0.36g / 10min, density 956kg / m 3 , the proportion of biomass-derived monomers is 96% by mass. (A-2) Prime Polymer Co., Ltd.'s petroleum-derived polyethylene "HIZEX3300F" (product name). Melt mass flow rate (190°C, 21.18N) 1.1g / 10min, density 949kg / m 3 . (A-3) PTT's petroleum-derived polyethylene "HD6600B" (product name). Melt mass flow rate (190°C, 21.18N) 0.40g / 10min, density 957kg / m 3 . (A-4) PTT's petroleum-derived polyethylene "HD6000F" (product name). Melt mass flow rate (190°C, 21.18N) 0.16g / 10min, density 956kg / m 3 . (A-5) Keiyo Polyethylene Co., Ltd.'s petroleum-derived polyethylene "P-9210" (product name). Melt mass-flow rate (190°C, 21.18N) 0.11 g / 10 min, density 950 kg / m 3 .

[0109] (B) Antioxidants (B-1) ADEKA Corporation's hindered phenol antioxidant "ADEKA STAB AO-60" (trade name). Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. (B-2) ADEKA Corporation's phosphite antioxidant "ADEKA STAB HP-10" (trade name): 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite.

[0110] (C) Fatty acid zinc, etc. (C-1) Zinc stearate. CAS number 557-05-1. (C-2) Magnesium stearate. CAS number 557-04-0.

[0111] (D) Inorganic filler (D-1) Rutile titanium dioxide (white pigment) "TITONE R-11.P" (trade name) from Sakai Chemical Industry Co., Ltd. (D-2) Calcium carbonate "Softon 2200" (product name) from Bihoku Funka Kogyo Co., Ltd. Specific surface area measured by air permeability method: 2.2 m 2 / g. (D-3) Calcium carbonate "Softon 1500" (product name) from Bihoku Funka Kogyo Co., Ltd. Specific surface area measured by air permeability method: 1.5 m 2 / g. (D-4) Calcium carbonate "Softon 2600" from Bihoku Funka Kogyo Co., Ltd. (product name) with a specific surface area of ​​2.6 m2 measured by the air permeability method. 2 / g.

[0112] (E) Acrylic processing aids (E-1) Mitsubishi Chemical Corporation's acrylic processing aid "Metablen P-1050" (trade name).

[0113] Example 1 (1) Film production of film 1 A polyethylene resin composition was obtained by melt-kneading a blend consisting of 50 parts by mass of the component (A-1), 50 parts by mass of the component (A-2), 0.30 parts by mass of the component (B-1), 0.20 parts by mass of the component (B-2), 0.65 parts by mass of the component (C-1), and 20 parts by mass of the component (D-2) using a mixer kneader at a discharge resin temperature of 200°C. This polyethylene resin composition was then sent directly to a calendar roll film-forming apparatus equipped with an inverted L-shaped four-roll calendar roll mill and a take-up device, and a 60 μm-thick film 1 was formed under film-forming conditions of 175°C for the first roll, 175°C for the second roll, 180°C for the third roll, and 175°C for the fourth roll. (2) Film production of film 2 Film 2 having a thickness of 60 μm was produced in the same manner except that the film production conditions were changed to 185°C for the first roll, 185°C for the second roll, 190°C for the third roll, and 185°C for the fourth roll. (3) Evaluation of Films 1 and 2 The above tests (i) and (ii) were carried out on the obtained Film 1 and Film 2. The results are shown in Table 1.

[0114] Examples 2-24 Films 1 and 2 were obtained in the same manner as in Example 1, except that the formulation of the polyethylene resin composition was changed as shown in Table 1 or Table 2. The obtained films 1 and 2 were subjected to the above tests (i) and (ii). The results are shown in Table 1 or Table 2.

[0115] [Table 1]

[0116] [Table 2]

[0117] It has been found that the polyethylene resin composition of the present invention suppresses the occurrence of vertical streaks when a film is formed using a calender roll film-forming apparatus. It has also been found that the preferred polyethylene resin composition of the present invention, even when using biomass-derived polyethylene, has small thickness variations when a film is formed using a calender roll film-forming apparatus. Therefore, it has been considered that a film formed using the polyethylene resin composition of the present invention using a calender roll film-forming apparatus can be suitably used as a film substrate for decorative sheets. [Explanation of symbols]

[0118] 1: Surface protective layer 2: Transparent resin layer 3: Printing layer 4: Film base layer 5:Adhesive layer 10: Decorative sheet

Claims

1. (A) 100 parts by mass of polyethylene, (B) 0.01 to 5 parts by mass of an antioxidant, (C) 0.1 to 5 parts by mass of one or more selected from the group consisting of fatty acid zinc salts and fatty acid magnesium salts, and (D) 10 to 150 parts by mass of an inorganic filler, Here, (A) polyethylene is (1) The melt mass flow rate measured in accordance with JIS K7210:1999 at a temperature of 190°C and a load of 21.18N is 3.0 g / 10 min or less; (2) Density measured by underwater displacement method in accordance with JIS K7112:1999 is 930 kg / m ３ That's all. Polyethylene resin composition for calender roll film formation.

2. 2. The polyethylene-based resin composition for calender roll film formation according to claim 1, wherein (C) at least one selected from the group consisting of a zinc salt of a fatty acid and a magnesium salt of a fatty acid comprises a zinc salt of a saturated higher fatty acid having 16 to 20 carbon atoms and a magnesium salt of a saturated higher fatty acid having 16 to 20 carbon atoms.

3. The polyethylene resin composition for use in calender roll film formation according to claim 1, further comprising 0.01 to 10 parts by mass of an acrylic processing aid (E).

4. The polyethylene-based resin composition for use in calender roll film formation according to claim 1, wherein the polyethylene (A) comprises biomass-derived polyethylene.

5. 2. The polyethylene-based resin composition for use in calender roll film formation according to claim 1, wherein the inorganic filler (D) contains calcium carbonate, and the amount of calcium carbonate blended is 10 parts by mass or more per 100 parts by mass of the polyethylene (A).

6. (D) The inorganic filler calcium carbonate has a specific surface area of ​​1.4 to 3.5 m as measured by the air permeability method. ２ The polyethylene resin composition for use in calender roll film formation according to claim 5, wherein the viscosity of the resin composition is 100 MPa.

7. The polyethylene-based resin composition for use in calender roll film formation according to claim 6, wherein the polyethylene (A) comprises biomass-derived polyethylene.

8. (A) polyethylene, a mixture consisting of 90 to 20% by mass of polyethylene (a1) having a relatively high melt mass flow rate and 10 to 80% by mass of polyethylene (a2) having a relatively low melt mass flow rate, The polyethylene resin composition for calender roll film formation according to claim 1, wherein the ratio (MFR-a1 / MFR-a2) of the melt mass flow rate (MFR-a1) of the polyethylene (a1) to the melt mass flow rate (MFR-a2) of the polyethylene (a2) is more than 1.0 and not more than 20: Here, the melt mass flow rates of (a1) polyethylene and (a2) polyethylene are measured in accordance with JIS K7210:1999 under conditions of a temperature of 190°C and a load of 21.18N.

9. The polyethylene resin composition for calender roll film formation according to claim 1, which does not contain cellulose.

10. A calender roll film formed from the polyethylene resin composition for calender roll film formation according to any one of claims 1 to 9.

11. A decorative sheet comprising the calender roll-formed film according to claim 10.

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