Stacked body and packaging material

Abstract

A laminate having a heat-resistant coating layer (A) and an olefin resin layer (B1) mainly composed of an olefin resin (b1), the laminate satisfying (1) and (2), etc. (1) The difference between the dynamic viscoelasticity (DMA) value E'1 (MPa) of the laminate having a heat-resistant coating layer (A) on one or both sides of the olefin resin layer (B1) at temperature T1 (°C) and the dynamic viscoelasticity (DMA) value E'2 (MPa) of the olefin resin layer (B1) alone at temperature T1 (°C) is 1 (MPa) or more. (2) The percentage of the linear expansion coefficient (CTE1) obtained by dividing the value of the linear expansion coefficient (CTE2) of the olefin resin layer (B1) with a heat-resistant coating layer (A) on one or both sides of the olefin resin layer (B1) at temperature T1 (°C) by the value of the linear expansion coefficient (CTE2) of the olefin resin layer (B1) at temperature T1 (°C) is 10% to 100%. T1 (°C) = Melting point of olefin resin layer (B1) (°C) - 35 (°C) E'1 (MPa) - E'2 (MPa) ≥ 1 (MPa) 10 (%) ≤ ((CTE1) / (CTE2)) × 100 ≤ 100 (%).

Description

Technical Field

[0001] This invention relates to a film-like laminate suitable for use in packaging materials, to a film-like laminate with good adaptability to packaging machinery and reusability, and to packaging materials comprising the laminate. Background Technology

[0002] Previously, laminated films manufactured using adhesives through lamination were not only for simple packaging purposes, but also developed to meet the requirements of achieving various high functions such as barrier properties, moisture resistance, and retort resistance with a single packaging material, as well as sealing for the sake of sealing. This led to the development of films made from different resin types. However, in recent years, there have been concerns that these laminated films made from different resin types reduce the quality of recycled plastics, highlighting the need for high-performance and reusable packaging materials.

[0003] As a method to improve the quality of recycled plastics without reducing the functionality of packaging materials as much as possible, there is a trend of "making packaging materials from a single type of raw material as much as possible" (sometimes called single-material packaging). For example, for plastic materials as the main raw material, it has been proposed to use laminated films (sometimes called single-material films) made of polyolefin films such as polyethylene films and stacked in multiple layers as packaging materials.

[0004] For example, Patent Document 1 discloses a polyethylene laminate comprising a substrate layer and a heat-sealing layer, wherein the substrate layer comprises a material with a density of 0.930 g / cm³. 3 The above-mentioned polyethylene, wherein the heat-sealing layer contains a density of less than 0.930 g / cm³. 3 The aforementioned substrate layer and the aforementioned heat-sealing layer are made of polyethylene with a density of 0.930 g / cm³. 3 The above-mentioned polyethylene has a density of less than 0.930 g / cm³. 3 It is formed by co-extrusion molding of polyethylene, and the above-mentioned substrate layer has been treated with electron beam irradiation.

[0005] However, when this laminate is used as packaging material for pillow bags, stand-up pouches, etc., there are sometimes problems with packaging machinery adaptability, especially with the polyethylene layer in contact with the heat-sealing bar used in automated packaging, such as distortion or shrinkage.

[0006] Especially when the laminated film is thick, heat has difficulty reaching the heat-sealing layer. Therefore, the set temperature of the heat-sealing rod is set to a certain degree higher than the softening and welding temperature of the heat-sealing layer. However, due to this high temperature, the shrinkage of the polyethylene layer in contact with the heat-sealing rod becomes more significant. Although this shrinkage problem of the polyethylene layer can be solved by reducing the sealing temperature and sealing speed during bag making, productivity is still affected.

[0007] The shrinkage problem of the polyethylene layer is not easily generated in laminated films with different resin types, such as laminated films with a polyethylene layer as a heat-sealing layer and layers in contact with the heat-sealing layer using nylon or polyethylene terephthalate (PET).

[0008] That is, it is desirable to have a single-material film, which is a single-material film composed only of polyolefin film, so that even if the set temperature of the heat sealing rod is a temperature slightly higher than the softening and welding temperature of the polyethylene layer in contact with the heat sealing rod (usually, it is desirable to be a temperature about 10-20°C higher than the softening and welding temperature), it is not easy to produce problems such as shrinkage and wrinkles.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 2020-55176 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] The objective of this invention is to provide a film-like laminate that is not prone to shrinkage or wrinkling caused by heating, has excellent sealing strength, and is reusable, and a packaging material using the same.

[0014] Methods for solving problems

[0015] That is, the present invention provides a laminate having a heat-resistant coating layer (A) and an olefin resin layer (B1) with olefin resin (b1) as the main component, wherein the laminate satisfies (1) and (2) or (1) and (3).

[0016] (1) The difference between the dynamic viscoelasticity (DMA) value E'1 (MPa) of the laminate in which a heat-resistant coating layer (A) is provided on one or both sides of the olefin resin layer (B1) and the dynamic viscoelasticity (DMA) value E'2 (MPa) of the laminate in which only the olefin resin layer (B1) is provided at temperature T1 (°C) is 1 (MPa) or more.

[0017] T1 (°C) = Melting point of olefin-based resin layer (B1) (°C) - 35 (°C)

[0018] E'1(MPa)-E'2(MPa)≥1(MPa)

[0019] (2) The percentage of the linear expansion coefficient (CTE1) of the laminate in which a heat-resistant coating layer (A) is provided on one or both sides of the olefin resin layer (B1) at temperature T1 (°C) is divided by the linear expansion coefficient (CTE2) of the olefin resin layer (B1) alone at temperature T1 (°C) is 10% to 100%.

[0020] 10(%)≤((CTE1) / (CTE2))×100≤100(%)

[0021] (3) The percentage of the linear expansion coefficient (CTE3) obtained by dividing the linear expansion coefficient (CTE4) of the olefin resin layer (B1) alone at temperature T2 (°C) by the linear expansion coefficient (CTE4) of the olefin resin layer (B1) at temperature T2 (°C) by the sum of temperature T1 (°C) and 20 (°C).

[0022] 10(%)≤≤((CTE3) / (CTE4))×100≤100(%)

[0023] In addition, the present invention provides a packaging material which is made using the laminate described above.

[0024] Invention Effects

[0025] The laminate of this invention is less prone to shrinkage and wrinkles caused by heating, and exhibits excellent sealing strength. Furthermore, because it can be made from a single material, it can provide renewable packaging materials. Detailed Implementation

[0026] The laminate of the present invention is characterized in that it has a heat-resistant coating layer (A) and an olefin resin layer (B1) with olefin resin (b1) as the main component (hereinafter, sometimes simply referred to as olefin resin layer (B1)), the laminate satisfying (1) and (2) or (1) and (3).

[0027] (1) The difference between the dynamic viscoelasticity (DMA) value E'1 (MPa) of the laminate in which a heat-resistant coating layer (A) is provided on one or both sides of the olefin resin layer (B1) and the dynamic viscoelasticity (DMA) value E'2 (MPa) of the laminate in which only the olefin resin layer (B1) is provided at temperature T1 (°C) is 1 (MPa) or more.

[0028] T1 (°C) = Melting point of olefin-based resin layer (B1) (°C) - 35 (°C)

[0029] E'1(MPa)-E'2(MPa)≥1(MPa)

[0030] (2) The percentage of the linear expansion coefficient (CTE1) of the laminate in which a heat-resistant coating layer (A) is provided on one or both sides of the olefin resin layer (B1) at temperature T1 (°C) is divided by the linear expansion coefficient (CTE2) of the olefin resin layer (B1) alone at temperature T1 (°C) is 10% to 100%.

[0031] 10(%)≤((CTE1) / (CTE2))×100≤100(%)

[0032] (3) The percentage of the linear expansion coefficient (CTE3) obtained by dividing the linear expansion coefficient (CTE4) of the olefin resin layer (B1) alone at temperature T2 (°C) by the linear expansion coefficient (CTE4) of the olefin resin layer (B1) at temperature T2 (°C) by the sum of temperature T1 (°C) and 20 (°C).

[0033] 10(%)≤((CTE3) / (CTE4))×100≤100(%)

[0034] As shown in the formula above, the temperature T1 (°C) is a value obtained by subtracting 35 (°C) from the melting point (°C) of the olefin resin layer (B1).

[0035] As shown in the above formula, the temperature T2 (°C) is the sum of temperature T1 (°C) and 20 (°C), that is, the value obtained by subtracting 15 (°C) from the melting point (°C) of the olefin resin layer (B1).

[0036] In addition, in (1) above, E'1 (MPa) or E'2 (MPa) are values ​​measured by the dynamic viscoelasticity measuring device and conditions shown below.

[0037] Dynamic viscoelasticity measuring device: RSA-G2 (manufactured by TA Instruments).

[0038] Measurement mode: Tension

[0039] Measurement frequency: 1Hz

[0040] Amplitude: 0.1%

[0041] Measurement direction of the sample: MD direction

[0042] Sample dimensions (distance between clamps × width): 10mm × 5mm

[0043] Measurement temperature: -40℃~170℃

[0044] Heating rate: 3℃ / min

[0045] In this invention, the value defined in (1) above is preferably 1 (MPa) or more. The upper limit of the value defined in (1) above is not particularly limited, but considering currently available raw materials, 500 (MPa) or less is appropriate. More preferably, the lower limit of the value defined in (1) above is 50 (MPa) or more, and more preferably, the upper limit is 500 (MPa) or less.

[0046] In addition, the values ​​of linear expansion coefficients (CTE1) and (CTE2) in the thermomechanical analysis in (2) above, and the values ​​of linear expansion coefficients (CTE3) and (CTE4) in the thermomechanical analysis in (3) above, are all values ​​determined by the thermomechanical analysis apparatus and conditions shown below.

[0047] Thermomechanical analysis apparatus: TMA-60 (manufactured by Shimadzu Corporation)

[0048] Measurement method: Tensile

[0049] Sample size (sample length × sample width): 20mm × 5mm

[0050] Measurement direction of the sample: MD direction

[0051] Initial load: 12g (for olefin resin layers (B1): OPE1, OPE4), 2g (for olefin resin layers (B1): OPE2, OPE3, OPP)

[0052] Measurement temperature: 30℃~170℃

[0053] Heating rate: 3℃ / min

[0054] In this invention, the value defined in (2) or (3) above is preferably 10% or more and 100% or less, more preferably 10% or more and 60% or less.

[0055] In this invention, by satisfying (1) and (2) above, or (1) and (3) above, it is possible to obtain a laminate that is not prone to shrinkage or wrinkles caused by heating and has excellent sealing strength, which is the subject of this invention. The reason for this is as follows.

[0056] The wrinkles caused by the shrinkage of the olefin resin layer (B1) are believed to be due to the shrinkage stress generated when the oriented polymer chains attempt to return to the unoriented state, exceeding the strength that the elasticity of the olefin resin layer (B1) can maintain. Typically, the storage modulus in the stretching direction of a stretched film is higher than that in the unstretched state due to the orientation of the molecular chains, but it gradually decreases as the number of unoriented polymer chains increases due to heating. This invention is based on the assumption that by using a heat-resistant coating layer (A) with higher elasticity than the olefin resin layer (B1), an elastic modulus capable of withstanding shrinkage stress can be imparted, thereby improving heat resistance. The inventors have studied in detail the relationship between the shrinkage behavior and storage modulus of various films and found that shrinkage behavior begins to be observed near a temperature T1 (°C), which is a value obtained by subtracting 35 (°C) from the melting point (°C) of the olefin resin layer (B1). Therefore, it is believed that when the storage modulus E'1 (MPa) of the olefin resin layer (B1) with the heat-resistant coating layer (A) at temperature T1 (°C) and the storage modulus E'2 (MPa) of the olefin resin layer (B1) itself at temperature T1 (°C) satisfy the above (1), an enhancement effect is exhibited.

[0057] On the other hand, it is believed that the shrinkage stress of the olefin resin layer (B1) is related to the value of the linear expansion coefficient in thermomechanical analysis. Therefore, under the condition that (2) above is satisfied, it is inferred that the shrinkage stress of the laminate of the heat-resistant coating layer (A) and the olefin resin layer (B1) is smaller than that of the olefin resin layer (B1) alone.

[0058] It should be noted that, in the case of olefin resins with relatively high shrinkage initiation temperatures, shrinkage behavior is sometimes difficult to observe at the temperature T1 (°C) used in the above formula (2), which is the value obtained by subtracting 35 (°C) from the melting point (°C) of the olefin resin layer (B1). In the case of such olefin resins, as shown in formula (3), it is preferable to use T2 (°C), which is the sum of temperature T1 (°C) and 20 (°C), that is, the temperature T2 (°C) obtained by subtracting 15 (°C) from the melting point (°C) of the olefin resin layer (B1). As an example of applying formula (2), this corresponds to a density of less than 0.94 g / m³. 2 Polyethylene film and polypropylene film.

[0059] Based on the above, when satisfying (1) and (2) above, or (1) and (3) above, a laminate that satisfies the subject matter of the present invention is formed.

[0060] (Structure of a layered structure)

[0061] The laminate of the present invention may be a laminate having a heat-resistant coating layer (A) and an olefin resin layer (B1) with olefin resin (b1) as the main component, or it may be a laminate having other layers. Examples of other layers include, but are not limited to, an adhesive layer (C) containing an adhesive (c1), a barrier resin layer (D), an olefin resin layer (B2) with olefin resin (b2) as the main component, a printing layer (E), a sealing layer (F), or a vapor-deposited layer (G).

[0062] The stacking order of the aforementioned layers (C), (D), (B2), (E), (F), and (G) is not particularly limited. Regarding the printing layer (E), for the purpose of imparting cosmetic properties, various information related to the contents, and functionality to the packaging material used as the laminate of the present invention, it is preferable that the printing layer (E) is in contact with an olefin resin layer (B1) whose main component is an olefin resin (b1). Specifically, the printing layer (E) is preferably printed on an olefin resin layer (B1) whose main component is an olefin resin (b1). When the printing surface is provided on the side in contact with the heat-resistant coating layer (A), the printing ink is preferably an ink suitable for surface printing. When the printing surface is provided on the back side of the side in contact with the heat-resistant coating layer (A), from the perspective of aesthetics and durability, it is preferable to use a lamination-specific ink.

[0063] In addition, in order to seal the contents of the package, the sealing layer (F) is preferably located on the outermost layer of the laminate.

[0064] An example of a specific embodiment of the laminate of the present invention is shown below, but the present invention is not limited thereto, as long as it has a heat-resistant coating layer (A) and an olefin resin layer (B1) with olefin resin (b1) as the main component.

[0065] Here is an example of a specific method. It should be noted that " / " indicates a layer-to-layer contact.

[0066] • Heat-resistant coating (A) / Olefin resin layer (B1) / Sealing layer (F)

[0067] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Sealing layer (F)

[0068] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Adhesive layer (C) / Olefin resin layer (B2)

[0069] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Adhesive layer (C) / Olefin resin layer (B2)

[0070] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Adhesive layer (C) / Evaporated layer (G) / Olefin resin layer (B2)

[0071] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0072] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0073] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Adhesive layer (C) / Barrier resin layer (D) / Evaporated layer (G) / Olefin resin layer (B2) / Sealing layer (F)

[0074] • Heat-resistant coating (A) / Olefin resin layer (B1) / Heat-resistant coating (A) / Sealing layer (F)

[0075] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Heat-resistant coating (A) / Sealing layer (F)

[0076] • Heat-resistant coating (A) / Olefin resin layer (B1) / Vaporized layer (G) / Heat-resistant coating (A) / Sealing layer (F)

[0077] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Heat-resistant coating (A) / Sealing layer (F)

[0078] • Heat-resistant coating (A) / Olefin resin layer (B1) / Barrier resin layer (D) / Sealing layer (F)

[0079] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Sealing layer (F)

[0080] • Heat-resistant coating (A) / Olefin resin layer (B1) / Evaporated layer (G) / Barrier resin layer (D) / Sealing layer (F)

[0081] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Barrier resin layer (D) / Sealing layer (F)

[0082] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Olefin resin layer (B2)

[0083] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Barrier resin layer (D) / Olefin resin layer (B2)

[0084] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Evaporated layer (G) / Olefin resin layer (B2)

[0085] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Adhesive layer (C) / Olefin resin layer (B2)

[0086] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0087] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Evaporated layer (G) / Barrier resin layer (D) / Adhesive layer (C) / Olefin resin layer (B2)

[0088] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Adhesive layer (C) / Evaporated layer (G) / Barrier resin layer (D) / Olefin resin layer (B2)

[0089] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Olefin resin layer (B2)

[0090] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Adhesive layer (C) / Olefin resin layer (B2)

[0091] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Barrier resin layer (D) / Adhesive layer (C) / Olefin resin layer (B2)

[0092] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0093] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Barrier resin layer (D) / Printed layer (E) / Adhesive layer (C) / Olefin resin layer (B2)

[0094] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Evaporated layer (G) / Printed layer (E) / Olefin resin layer (B2)

[0095] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Evaporated layer (G) / Printed layer (E) / Adhesive layer (C) / Olefin resin layer (B2)

[0096] • Heat-resistant coating (A) / Olefin resin layer (B1) / Printed layer (E) / Barrier resin layer (D) / Adhesive layer (C) / Olefin resin layer (B2) / Sealing layer (F)

[0097] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Evaporated layer (G) / Printed layer (E) / Barrier resin layer (D) / Adhesive layer (C) / Olefin resin layer (B2)

[0098] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Adhesive layer (C) / Barrier resin layer (D) / Evaporated layer (G) / Olefin resin layer (B2)

[0099] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Evaporated layer (G) / Barrier resin layer (D) / Printed layer (E) / Adhesive layer (C) / Olefin resin layer (B2)

[0100] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Barrier resin layer (D) / Printed layer (E) / Adhesive layer (C) / Evaporated layer (G) / Olefin resin layer (B2)

[0101] (Heat-resistant coating (A))

[0102] The heat-resistant coating layer (A) used in this invention is disposed on the olefin resin layer (B1) described later, or disposed in between the printed layer (E) described later. The heat-resistant coating layer (A) is the outermost layer when viewed from the contents during bag making of the laminated products of this invention, and is the layer that is in contact with the heat-sealing rod during bag making.

[0103] Since the laminate having the heat-resistant coating layer (A) and the olefin resin layer (B1) described later needs to satisfy (1) and (2) above, the heat-resistant coating layer (A) and the olefin resin layer (B1) described later preferably have at least a portion or all of their surface in contact. The case where the heat-resistant coating layer (A) and the olefin resin layer (B1) are in partial contact refers to the case where a printed layer (E) is envisioned between the heat-resistant coating layer (A) and the olefin resin layer (B1). However, since the printed layer is usually not printed on the entire surface of the olefin resin layer (B1), but necessarily has a portion in partial contact with the olefin resin layer (B1), the effects of this application can be achieved in the state of partial contact.

[0104] Furthermore, the heat-resistant coating layer (A) needs to be disposed on at least one side of the olefin resin layer (B1) described later, but it can also be disposed on both sides, which is preferred. By disposing it on both sides, the effects of the present invention can be further enhanced.

[0105] The heat-resistant coating layer (A) is a coating layer containing a heat-resistant coating agent (A) (hereinafter, sometimes simply referred to as coating agent (A)). As the coating agent (A), for example, it is preferable to be a compound containing a homopolymer with a glass transition temperature (hereinafter, sometimes referred to as Tg) of 100°C or higher, having a cellulose backbone, a benzene ring backbone, an isocyanuric acid ring backbone, or an alicyclic backbone. Specifically, examples of resin compositions include polyester resins having a benzene ring and / or an alicyclic backbone such as cellulose derivatives like nitrocellulose, cellulose acetate, cellulose propionate, and cellulose butyrate; phthalic acid, naphthalene, and ethylene oxide (hereinafter sometimes referred to as EO) adducts of bisphenol A; or urethane resins bonded to polyols and / or triisocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and naphthalene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and norbornene diisocyanate; and / or triisocyanate isocyanate bonded to polyols and / or tris(2-hydroxyethyl) isocyanurate. Polyisocyanates using the above-mentioned isocyanates can also be used as curing agents. Alternatively, compounds with benzene rings and unsaturated double bonds, such as styrene and phenoxydiethylene glycol acrylate, and / or compounds with alicyclic structures and unsaturated double bonds, such as isobornyl acrylate and dicyclopentyl acrylate, as well as free radical copolymers such as (meth)acrylates, may be preferred. Furthermore, considering the adhesion to olefin films, resins with low Tg may also be used in combination.

[0106] The total of the cellulose backbone, benzene ring backbone, isocyanuric acid ring backbone, and alicyclic backbone of the above-mentioned compounds is preferably 20-90% by mass in the solid composition of the above-mentioned heat-resistant coating layer (A). A value of 30-80% by mass is desirable.

[0107] Furthermore, the aforementioned coating agent (A) can be colored. There are no particular limitations on the colorant; examples include inorganic pigments, organic pigments, and dyes commonly used in inks, coatings, and recording agents used in the printing layer (E) described later. Pigments are preferred. Examples of organic pigments include soluble azo, insoluble azo, azo-based, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthraquinone-anthraquinone, bianthraquinone, anthrapyrimidine, perylene, violetone, quinacridone, thioindole, dioxazine, isoindolineone, quinolineone, azomethylazo, flavanone, pyrrolopyrroledione, isoindoline, indanone, and carbon black pigments. In addition, examples include Magenta 6B, Lake Red C, Permanent Red 2B, Diazo Yellow, Pyrazolone Orange, Magenta FB, Gommex Yellow, Gommex Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Fuchsin, Quinacridone Red, Indanthrene Blue, Pyrimidine Yellow, Thioindomarsein, Thioindofuchsin, Perylene Red, Violet Ringerone Orange, Isoindolineone Yellow, Aniline Black, Pyrrolopyrrole Dione Red, and daylight fluorescent pigments. Both untreated and acid-treated pigments can be used.

[0108] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silicon dioxide, lithopone, antimony white, and gypsum. Among inorganic pigments, titanium dioxide is particularly preferred. Titanium dioxide is white and is preferred from the viewpoints of tinting strength, hiding power, chemical resistance, and weather resistance. From the viewpoint of printability, it is preferable that the titanium dioxide has been treated with silicon dioxide and / or aluminum oxide.

[0109] Inorganic pigments other than white include, for example, aluminum particles, mica, bronze powder, chrome vermilion, chrome yellow, cadmium yellow, cadmium red, ultramarine, iron blue, iron oxide yellow, iron black, and zircon. Aluminum is available in powder or paste form. From the perspective of processability and safety, it is preferred to use it in paste form. Whether to use a floating or non-floating type should be appropriately selected based on the brightness and concentration.

[0110] Furthermore, the above-mentioned coating agent (A) exhibits excellent heat resistance when using inorganic microparticles such as alumina, magnesium oxide, titanium dioxide, zirconium oxide, and silica (quartz, pyrolytic silica, precipitated silica, anhydrous silica, fused silica, crystalline silica, ultrafine amorphous silica, etc.) as aggregates, and is therefore preferred. Alternatively, boron nitride, aluminum nitride, alumina, titanium oxide, magnesium oxide, zinc oxide, and silica are preferred due to their excellent thermal conductivity. Inorganic microparticles can be used alone or in combination.

[0111] There are no particular limitations on the shape of silica particles; spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped silica particles can be used. For example, commercially available hollow silica particles can be SiliNaX manufactured by Nippon Steel Mining Co., Ltd.

[0112] The primary particle size of the aforementioned inorganic particles is preferably in the range of 5 to 200 nm. If it is 5 nm or larger, the dispersion of inorganic particles in the dispersion becomes better; if the diameter is within 200 nm, the strength of the cured product becomes better. More preferably, it is 10 nm to 100 nm.

[0113] The aforementioned inorganic microparticles can be formulated in a ratio of 5 to 90% by weight relative to the total solid content of the aforementioned coating agent (A) and the aforementioned inorganic microparticles. The formulation amount can be changed as needed according to the purpose. Preferably, it is 20% by weight or more.

[0114] To prevent damage to the coating film, prevent adhesion during the formation of the laminate, and impart processability during bag making after the laminate is formed, the coating agent (A) mentioned above can use wax, silicone additives, or organic microspheres. Specifically, amide wax, polypropylene wax, polyethylene wax, paraffin wax, carnauba wax, rice bran wax, ethylene oxide (EO) adducts of dimethylsiloxane, silicone additives modified with silicone, and organic microspheres formed from acrylics, nylon, urethane, or epoxy resins can be added.

[0115] There are no particular limitations on the solvents used in the above-mentioned coating agent (A). Examples of solvents include aromatic hydrocarbon organic solvents such as water, toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane; and various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, various organic solvents miscible with water include alcohols such as methanol, ethanol, propanol, butanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. These can be used alone or in combination of two or more. Furthermore, defoamers and leveling agents can be used for more effective coating.

[0116] (Olefin resin layer (B1) with olefin resin (b1) as the main component)

[0117] As the olefin resin used in the olefin resin layer (B1) of this invention, polyethylene resin, polypropylene resin, or copolymers thereof can be used.

[0118] Examples of polyethylene-based resins include ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA), ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), and ethylene-methacrylic acid copolymer (EMAA). Additionally, ionomers of ethylene-acrylic acid copolymers and ionomers of ethylene-methacrylic acid copolymers can be used individually or in combination of two or more. Among these, LLDPE is preferred due to its ability to suppress the volatilization of transdermal absorbent components, reduce the adhesion performance of the patch (hereinafter sometimes referred to as the volatilization of contents), easily achieve a wide heat-sealing temperature range, and provide suitable heat-sealing properties.

[0119] As LDPE, any branched low-density polyethylene obtained by high-pressure free radical polymerization is acceptable, and branched low-density polyethylene obtained by homopolymerization of ethylene by high-pressure free radical polymerization is preferred.

[0120] LLDPE and LMDPE are substances obtained by low-pressure free radical polymerization using a single-point catalyst, with ethylene monomer as the main component, and copolymerizing it with α-olefins such as butene-1, hexene-1, octene-1, and 4-methylpentene as comonomers. The comonomer content is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1 to 18 mol%.

[0121] Examples of single-site catalysts include metallocene catalyst systems such as combinations of metallocene compounds of Group IV or V transition metals in the periodic table with organoaluminum compounds and / or ionic compounds. Furthermore, because single-site catalysts have uniform active sites, the resulting resin exhibits a sharper molecular weight distribution compared to multi-site catalysts with uneven active sites. This results in less precipitation of low-molecular-weight components during film formation, leading to a resin with excellent stability in interlayer adhesion strength, and is therefore preferred.

[0122] The MFR (190°C, 21.18N) of the aforementioned polyethylene resin is preferably 2 to 20 g / 10 min, more preferably 3 to 10 g / 10 min. If the MFR is within this range, the extrudability of the film is improved. As for the density of LLDPE, considering packaging suitability, inclusion sealing, and pinhole resistance, 0.905 g / cm³ is preferred. 3 ~0.925g / cm 3 From the perspective of easily and appropriately suppressing the volatilization of the contents, 0.915 g / cm³ is particularly preferred. 3 ~0.925g / cm 3 .

[0123] Examples of polypropylene-based resins include propylene homopolymers, propylene-α-olefin random copolymers, propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers, and metallocene-catalyzed polypropylene. These can be used individually or in combination. Propylene-α-olefin random copolymers are preferred, and propylene-α-olefin random polymers polymerized using metallocene catalysts are particularly preferred. When these polypropylene-based resins are used as the intermediate layer (B), the film's heat resistance is improved, and the softening temperature is increased. Therefore, it is suitable for use as a laminated film for packaging materials with excellent steam / high-pressure sterilization characteristics, such as boiling at 100°C or below, hot filling, or retort sterilization at 100°C or above.

[0124] Furthermore, these polypropylene resins preferably have a melt flow rate (MFR) of 0.5–30.0 g / 10 min at 230°C and a melting point of 110–165°C, more preferably an MFR of 2.0–15.0 g / 10 min at 230°C and a melting point of 115–162°C. If the MFR and melting point are within this range, the film-forming properties of the film are improved.

[0125] From the viewpoint of easily achieving appropriate adhesion, the olefin resin layer (B1) preferably has an olefin resin as its main component, and 80% or more by mass of the resin component constituting the olefin resin layer (B1) is preferably an olefin resin, more preferably 90% or more by mass, and particularly preferably 100% by mass. Furthermore, if 80% by mass of the olefin resin contained in the olefin resin layer (B1) has a density of 0.9 g / cm³... 3 The above-mentioned olefin-based resins are particularly easy to obtain with good adhesion, and therefore preferably contain 90% or more by mass. In particular, 80% by mass of the olefin-based resin contained in the olefin-based resin layer (B1) is preferably linear low-density polyethylene resin, and more preferably 90% or more by mass.

[0126] The thickness of the olefin resin layer (B1) can be adjusted appropriately according to the application method. From the perspective of achieving a good balance between mechanical strength and processability, and ensuring appropriate heat-sealing properties while appropriately suppressing the volatilization of the contents, it is preferably 5 to 300 μm, more preferably 7 to 200 μm.

[0127] (Stretched olefin resin layer)

[0128] From the perspective of coating layers that are easy to set up with heat-resistant coating layer (A), olefin resin layer (B1) is usually made of olefin resin layer in the form of film or sheet.

[0129] When the film or sheet has undergone stretching treatment, the effects of the present invention can be maximized, which is preferred. As a stretching treatment method, resin is typically melted and extruded to form a sheet using methods such as extrusion film forming, followed by uniaxial stretching, simultaneous biaxial stretching, or sequential biaxial stretching. Furthermore, in the case of sequential biaxial stretching, longitudinal stretching is usually performed first, followed by transverse stretching. Specifically, a method combining longitudinal stretching utilizing the speed difference between rollers with transverse stretching using a tenter frame is often employed.

[0130] In particular, the olefin-based resin layer (B1) suitable for the laminates satisfying the conditions of (1) and (2) above can be specifically exemplified by having a density of less than 0.94 g / cm³ after uniaxial or biaxial stretching. 3 Polyethylene or polypropylene film.

[0131] In particular, the olefin resin layer (B1) suitable for the laminates satisfying the conditions of (1) and (3) above can be specifically exemplified by having a density of 0.94 g / cm³ after uniaxial or biaxial stretching. 3 The above refers to polyethylene film.

[0132] For the surface of the above-mentioned films and sheets, various surface treatments such as flame treatment and corona discharge treatment can be applied as needed to form an adhesive layer without defects such as film breakage and shrinkage cavities.

[0133] The simplest configuration of the laminate of the present invention is a laminate formed by a heat-resistant coating layer (A) and an olefin resin layer (B1). In this case, the layer in contact with the heat-sealing rod is the heat-resistant coating layer (A), and the heat-sealing layer is the olefin resin layer (B1). When such an olefin resin layer (B1) functions as a heat-sealing layer, the olefin resin layer (B1) is preferably a resin layer that can impart heat-sealing properties and is mainly composed of polyethylene resins such as unstretched ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), low density polyethylene (LDPE), and medium density polyethylene (MDPE), or polypropylene resin.

[0134] On the other hand, for laminates such as the heat-resistant coating layer (A), olefin resin layer (B1), adhesive layer (C) containing adhesive (c1), barrier resin layer (D), olefin resin layer (B2) mainly composed of olefin resin (b2), printing layer (E), sealing layer (F), or vapor-deposited layer (G) as described later, the olefin resin layer (B1) is not the outermost layer. Therefore, heat-sealing properties are not a constraint, and the resin can be appropriately selected according to the application of the laminate. For example, in laminates with the following configuration having a printing layer, a biaxially stretched olefin resin film is mostly used as the olefin resin layer (B1).

[0135] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Printed layer (E) / Adhesive layer (C) / Olefin resin layer (B2)

[0136] • Heat-resistant coating (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Olefin resin layer (B2)

[0137] (Adhesive layer (C))

[0138] In this invention, an adhesive layer (C) may be included. The adhesive (c1) used in the adhesive layer (C) can be any adhesive that can be used in common lamination methods. Examples of lamination methods include dry lamination, wet lamination, non-solvent lamination, extrusion lamination, etc.

[0139] As for the adhesive used in the aforementioned dry lamination, one-component or two-component cured or non-curing adhesives such as vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, and others, solvent-based, water-based, or emulsion-based adhesives can be used. As for two-component cured adhesives, two-component cured adhesives of polyols and isocyanate compounds can be used. As for the coating method of the aforementioned lamination adhesive, for example, direct gravure roller coating, gravure offset roller coating, coincidence coating, reverse roller coating, fountain coating, transfer molding roller coating, and other methods can be used. For example, the DICDRY series manufactured by DIC Corporation is preferably used.

[0140] Alternatively, various adhesives can be used, with pressure-sensitive adhesives being preferred. Examples of pressure-sensitive adhesives include polyisobutylene rubber, butyl rubber, rubber-based adhesives obtained by dissolving mixtures thereof in organic solvents such as benzene, toluene, xylene, and hexane, adhesives incorporating tackifiers such as rosin ester, terpene-phenol copolymer, and terpene-indene copolymer, or acrylic adhesives obtained by dissolving acrylic copolymers with a glass transition temperature below -20°C, such as 2-ethylhexyl acrylate-n-butyl acrylate copolymer and 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer, in organic solvents.

[0141] Among the adhesives mentioned above (c1), functional adhesives can be used. For example, as a barrier adhesive, the PASLIM series of oxygen barrier adhesives manufactured by DIC Corporation, which are two-component reactive adhesives of polyester polyol and isocyanate compound, can be used.

[0142] Regarding the specific configuration of the laminate of the present invention when using a barrier adhesive, the adhesive layer (C) in the above-mentioned structure, such as "heat-resistant coating layer (A) / printed layer (E) / olefin resin layer (B1) / adhesive layer (C) / olefin resin layer (B2)", can be replaced with a barrier adhesive. Specifically, the following configurations can be cited:

[0143] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier adhesive layer (C) / Olefin resin layer (B2)

[0144] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0145] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Heat-resistant coating layer (A) / Barrier adhesive layer (C) / Olefin resin layer (B2)

[0146] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Heat-resistant coating layer (A) / Barrier adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0147] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Barrier adhesive layer (C) / Olefin resin layer (B2)

[0148] • Heat-resistant coating layer (A) / Printed layer (E) / Olefin resin layer (B1) / Barrier resin layer (D) / Barrier adhesive layer (C) / Barrier resin layer (D) / Olefin resin layer (B2)

[0149] • Heat-resistant coating layer (A) / Olefin resin layer (B1) / Barrier resin layer (D) / Printed layer (E) / Barrier adhesive layer (C) / Olefin resin layer (B2).

[0150] (Barrier layer (D))

[0151] The laminate of the present invention may include a barrier resin layer (D). Examples of the barrier resin layer (D) include a method for laminating a barrier film and a method for forming a coating layer by applying a barrier coating agent. The method of forming a coating layer by applying a barrier coating agent is simple and preferred.

[0152] As barrier coatings, it is known that coatings contain polymers such as polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVOH), polysaccharides, acrylic or methacrylic acid groups, starch or starch derivatives, cellulose nanofibers (CNF), nanocrystalline cellulose (NCC), chitosan, or other cellulose derivatives, hemicellulose, polyvinylidene chloride (PVDC), or polymers containing inorganic particles such as silica, alumina, aluminum flakes, glass flakes, hydrated silicates (such as siliceous silicate minerals), and kaolinite-serpentine clay minerals (haloysite). Coating agents for various minerals including kaolinite, hydrous halloysite, dickite, pearl clay, scaly serpentine, fibrous serpentine, pyrophyllite-talc group (pyrophyllite, talc, wax serpentine, etc.), chlorophyllite group clay minerals (montmorillonite, bedeite, chlorophyllite, soapstone, lithium montmorillonite, zinc montmorillonite, magnesium montmorillonite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or mica group clay minerals (mica, phlogopite, pearl mica, tetrasilica, banded mica, etc.), chlorite group (lithium chlorite, stigma, clinoptilolite, oolitic chlorite, nickel chlorite, etc.), hydrotalcite, tabular barium sulfate, boehmite, aluminum polyphosphate, and other tabular inorganic compounds.

[0153] In this invention, known barrier coatings may be used without particular limitation. As known barrier coatings, polyester-based barrier coatings such as the "Sunbar" series manufactured by SUN CHEMICAL Co., Ltd., and those described in Japanese Patent 5617831 may be used.

[0154] In addition, as a barrier layer, a membrane with vapor-deposited layers of metals such as aluminum, silicon dioxide, and alumina, or a barrier membrane such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and vinylidene chloride can be used.

[0155] (Olefin resin layer (B2) with olefin resin (b2) as the main component)

[0156] The olefin resin layer (B2) with olefin resin (b2) as the main component used in this invention (hereinafter, sometimes simply referred to as olefin resin layer (B2)) can be the same resin layer as the olefin resin layer (B1) described above, and the olefin resin (b2) as the main component can also be the same resin as the olefin resin (b1) used in the olefin resin layer (B1) described above.

[0157] Preferably, the above-mentioned polyethylene resin or the above-mentioned polypropylene resin is used.

[0158] Regarding the olefin resin layer (B2), if the olefin resin layer (B2) functions as a heat-sealing layer in the same way as the olefin resin layer (B1) described above, the olefin resin layer (B2) is preferably a resin layer mainly composed of polyethylene resins such as unstretched ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), low density polyethylene (LDPE), and medium density polyethylene (MDPE), or polypropylene resin, which can impart heat-sealing properties. In this case, the olefin resin layer (B2) is preferably the outermost layer of the laminate.

[0159] On the other hand, in the case of a laminate in which the olefin resin layer (B2) is not the outermost layer, the resin can be appropriately selected according to the application of the laminate, without being limited by heat-sealing properties.

[0160] (Printed layer (E))

[0161] The laminate of the present invention may have a printed layer (E). The printed layer (E) used in the present invention is a layer that forms a desired pattern using liquid printing ink to impart cosmetic properties, various information and functionality related to the contents to the printed body. This printed layer is formed by printing gravure printing ink or flexographic printing ink (hereinafter referred to as liquid printing ink) containing binder resin and colorant.

[0162] The printing layer (E) used in this invention can be a single layer or multiple printing layers. In the case of multiple printing layers, the liquid printing ink used in each printing layer can be the same, have the same composition but different colorants, or have different compositions.

[0163] (Liquid printing ink)

[0164] The liquid printing ink used in this invention is used as both gravure and flexographic printing inks, and is broadly classified into organic solvent-based liquid printing inks with organic solvents as the main solvent and water-based liquid printing inks with water as the main solvent. Either type can be used in this invention. Additionally, there are so-called front-side printing inks and back-side printing inks based on lamination, but either type can be used in this invention.

[0165] Here, we will explain the mainstream organic solvent-based liquid printing inks.

[0166] Examples of binder resins (A) used in the liquid printing ink of this invention include cellulose resins such as nitrocellulose, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB), polyamide resins, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyvinyl chloride resins, polyester resins, alkyd resins, rosin resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyral, and petroleum resins.

[0167] Alternatively, a curing agent can be used in combination with the adhesive resin (A). As the curing agent, a curing agent commonly used in organic solvent-based gravure printing inks can be used, with isocyanate-based curing agents being the most common.

[0168] From the viewpoint of curing efficiency, the amount of isocyanate compound added is preferably in the range of 0.3% to 10.0% by mass relative to the solid content of liquid printing ink, and more preferably in the range of 1.0% to 7.0% by mass.

[0169] The binder resin (A) is preferably used in the range of 0.15 to 50% by mass relative to the liquid printing ink, and most preferably in the range of 1 to 40% by mass.

[0170] (solvent)

[0171] There are no particular limitations on the solvent used for the liquid printing ink in this invention. Examples of solvents include aromatic hydrocarbon organic solvents such as water, toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane; and various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and various glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. These can be used alone or in combination of two or more.

[0172] (Coloring agent)

[0173] The liquid printing ink used in this invention contains a colorant and can be used as a liquid printing ink containing a colorant for purposes such as imparting cosmetic properties. Examples of colorants include inorganic pigments, organic pigments, and dyes commonly used in inks, coatings, and recording agents, with pigments being preferred. Examples of organic pigments include soluble azo, insoluble azo, azo-based, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthraquinone-anthraquinone, bianthraquinone, anthraquinone, perylene, violetone, quinacridone, thioindole, dioxazine, isoindolineone, quinolineone, azomethylazo, flavanone, pyrrolopyrroledione, isoindoline, indanone, and carbon black pigments. In addition, examples include Magenta 6B, Lake Red C, Permanent Red 2B, Diazo Yellow, Pyrazolone Orange, Magenta FB, Gommex Yellow, Gommex Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Fuchsin, Quinacridone Red, Indanthrene Blue, Pyrimidine Yellow, Thioindomarsein, Thioindofuchsin, Perylene Red, Violet Ringerone Orange, Isoindolineone Yellow, Aniline Black, Pyrrolopyrrole Dione Red, and daylight fluorescent pigments. Both untreated and acid-treated pigments can be used.

[0174] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silicon dioxide, lithopone, antimony white, and gypsum. Among inorganic pigments, titanium dioxide is particularly preferred. Titanium dioxide is white and is preferred from the viewpoints of tinting strength, hiding power, chemical resistance, and weather resistance. From the viewpoint of printability, it is preferable that the titanium dioxide has been treated with silicon dioxide and / or aluminum oxide.

[0175] Inorganic pigments other than white include, for example, aluminum particles, mica, bronze powder, chrome vermilion, chrome yellow, cadmium yellow, cadmium red, ultramarine, iron blue, iron oxide yellow, iron black, and zircon. Aluminum is available in powder or paste form. From the perspective of processability and safety, it is preferred to use it in paste form. Whether to use a floating or non-floating type should be appropriately selected based on the brightness and concentration.

[0176] The aforementioned pigments are preferably contained in an amount sufficient to ensure the concentration and tinting strength of the liquid printing ink, i.e., 1 to 60% by mass relative to the total mass of the liquid printing ink and 10 to 90% by mass of the solid components in the liquid printing ink. Furthermore, these pigments can be used alone or in combination of two or more.

[0177] Organic solvent-based liquid printing inks may further include waxes, chelate crosslinking agents, extender pigments, leveling agents, defoamers, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc., as needed.

[0178] (Biomass liquid printing ink)

[0179] In the liquid printing ink used in this invention, considering the construction of a sustainable circular society (sustainability), it is preferable to use liquid printing ink that utilizes raw materials derived from plants.

[0180] Examples of plant-derived raw materials include cellulose acetate propionate resin, nitrocellulose and other cellulose-based resins, polyamide resins using dimer acids or polymeric fatty acids derived from natural oils such as soybean oil, palm oil, and rice bran oil, biomass polyurethanes and rosin resins synthesized from plant-derived raw materials such as succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dimer acids, glutaric acid, and malic acid as polycarboxylic acids, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, pentylene glycol, 1,10-dodecanediol, dimer glycol, and isosorbide as polyols, and 1,5-pentamethylene diisocyanate and dimer diisocyanate as polyisocyanates.

[0181] Commercially available inks can also be used as biomass liquid printing inks. These can include inks listed by the Japan Organic Resources Association, a general incorporated association.

[0182] (UV-protective ink)

[0183] In the liquid printing ink used in this invention, a UV-blocking ink with ultraviolet shielding effect is preferred. As for the UV-blocking ink, there are no particular limitations as long as it contains zinc oxide or other inks with high UV shielding effect; commercially available UV-blocking inks can be used.

[0184] (Sealing layer)

[0185] A sealing coating layer (sometimes simply referred to as a sealing layer) can be provided on the outermost layer of the laminate of the present invention. The sealing coating layer can be provided by applying a sealant formed by dispersing or dissolving a thermoplastic elastomer in a solvent, such as polyester resin, vinyl chloride-vinyl acetate resin, ethylene vinyl alcohol (EVOH), acrylic resin, polyolefin resin, or rubber resin. The film thickness of the sealing layer is not particularly limited, but is mostly 1–5 μm.

[0186] Such sealants can also be commercially available hot-melt sealants. The sealant can be applied to the desired surface of the outermost surface of the laminate, either entirely or partially, which is convenient, for example, when using the laminate of the present invention as a lid material for containers of pudding, yogurt, etc.

[0187] (Vapor-deposited layer (G))

[0188] The vapor-deposited layer (G) is an inorganic vapor-deposited layer primarily intended to impart gas barrier properties. Inorganic substances, inorganic oxides, various metals, metal oxides, metal hydroxides, metal salts, etc., can be used. For example, aluminum, alumina, silicon dioxide, zinc oxide, magnesium oxide, calcium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, etc., can be used individually, or in combination with two or more, as in binary vapor deposition of silicon dioxide and alumina. Two or more inorganic vapor-deposited layers can be formed. When two or more inorganic vapor-deposited layers are formed, each layer can have the same composition or different compositions. From the viewpoint of gas barrier properties, aluminum is preferred.

[0189] The vapor-deposited layer (G) can be deposited on the aforementioned layers or separately on the substrate using conventionally known methods. Examples of methods for forming inorganic vapor-deposited layers include physical vapor deposition (PVD) methods such as vacuum evaporation, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition.

[0190] The preferred thickness of the inorganic vapor-deposited layer is 1–200 nm. When the inorganic vapor-deposited layer is an aluminum vapor-deposited layer, its thickness is more preferably 1–100 nm, more preferably 15–60 nm, and even more preferably 10–40 nm. When the inorganic vapor-deposited layer is a silicon dioxide or aluminum oxide vapor-deposited layer, its thickness is preferably 1–100 nm, more preferably 10–50 nm, and even more preferably 20–30 nm.

[0191] Furthermore, the laminate of the present invention may further include other films and substrates. As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, may also be used. The adhesive used when bonding other substrates may be the adhesive of the present invention, or it may not be the adhesive of the present invention.

[0192] On the other hand, when using the laminate of the present invention as a single-material film, it is preferable to make most of the layers consist of layers using olefin resins.

[0193] (Total thickness of the laminate)

[0194] For the laminate of the present invention, from the perspective of appropriately suppressing the evaporation of contents, easily obtaining suitable heat-sealing and opening properties, and making it easy to laminate with other substrates, its total thickness is preferably in the range of 15 to 200 μm, more preferably in the range of 10 to 100 μm, and even more preferably in the range of 20 to 60 μm.

[0195] (Manufacturing method of laminated bodies)

[0196] The laminate of the present invention can be obtained by known methods. For example, the method of setting the heat-resistant coating layer (A) on the olefin resin layer (B1) is preferably set by a known coating method. As for the above coating method, there is no particular limitation, and spraying, spin coating, dip coating, roller coating, doctor blade coating, doctor blade roller coating, squeegee coating, curtain coating, slot coating, screen printing, inkjet printing, dispensing, mold coating, direct gravure, reverse gravure, flexographic coating, doctor blade coating, dot coating, etc. can be used.

[0197] The method of setting a printing layer (E) on an olefin-based resin layer (B1) can be achieved using known printing methods. For example, the printing layer can be fabricated by laminating the printing layer using known printing methods such as gravure printing using a gravure printing plate based on an electronically engraved gravure plate or flexographic printing using a flexographic printing plate based on a resin plate.

[0198] In addition, other layers can be laminated using known methods such as dry lamination, wet lamination, non-solvent lamination, and extrusion lamination.

[0199] To impart mechanical, chemical, electrical, magnetic, friction / wear / lubrication control, optical, thermal, and biocompatibility functions, the laminate of this invention can also undergo secondary processing. Examples of secondary processing include surface treatment (corona discharge treatment, antistatic treatment, plasma treatment, photochromic treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), embossing, painting, bonding, printing, metallization (plating, etc.), and machining. Furthermore, the laminate of this invention can also undergo lamination (dry lamination, extrusion lamination), bag making, and other post-processing to manufacture molded articles.

[0200] (Packaging materials)

[0201] The packaging material of the present invention can be obtained by overlapping and heat-sealing the olefin resin layer (B1) or olefin resin layer (B2) of the laminate of the present invention as heat-sealing layers. Alternatively, the olefin resin layer (B1) or olefin resin layer (B2) of the laminate of the present invention can be overlapped with other heat-sealing resin layers and the olefin resin layer (B1) and heat-sealed. Examples of other heat-sealing resin layers include LDPE and EVA, which have relatively weak mechanical strength. Furthermore, the packaging material can also be made by heat-sealing a laminate formed by laminating films such as LDPE and EVA with stretch films with good tear resistance, such as biaxially stretched polyethylene terephthalate film (OPET) or biaxially stretched polypropylene film (OPP).

[0202] For example, two sheets of this laminate can be cut to the desired size for packaging material, overlapped, and heat-sealed on three sides to form a bag. The unsealed side is then filled with contents and heat-sealed to seal the bag, thus making it usable as packaging material. Alternatively, an automatic packaging machine can be used to seal the ends of a roll of film into a cylindrical shape and then seal the top and bottom to form packaging material.

[0203] In packaging materials using the laminate of the present invention, in order to reduce the initial tear strength and improve the openability, it is preferable to form any tear initiation part such as a V-shaped notch, an I-shaped notch, a perforation line, or micropores in the sealing part.

[0204] Example

[0205] The present invention will be described in more detail below with specific examples and embodiments, but the present invention is not limited to these embodiments. It should be noted that in the following examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0206] (Preparation method of heat-resistant coating (A))

[0207] The coating agents (A1) to (A20) and (AH1) to (AH2) used in the preparation examples and comparative examples are shown in Tables 1-1 to 1-3. It should be noted that the abbreviations in Tables 1-1 to 1-3 are as follows. An empty column indicates no formulation.

[0208] [Table 1]

[0209]

[0210] [Table 2]

[0211]

[0212] [Table 3]

[0213]

[0214] [Table 4]

[0215]

[0216] The abbreviations are shown in Tables 1-1 to 1-4 below.

[0217] CAP-504-0.2: Cellulose acetate propionate manufactured by Eastman Chemical Company.

[0218] CAB-1000: Cellulose acetate butyrate manufactured by Eastman Chemical Company

[0219] CAP-482-0.5: Cellulose acetate propionate manufactured by Eastman Chemical Company

[0220] CAB-381-0.1: Cellulose acetate butyrate manufactured by Eastman Chemical Company

[0221] NITROCELLULOSE DLX5-8: Nitrocellulose manufactured by Nobel NC

[0222] LX-470EL: Polyurethane polyol manufactured by DIC Corporation

[0223] LX-415A: A polyurethane polyol manufactured by DIC Corporation.

[0224] Surkopak 5323: Polyurethane manufactured by BIP Company

[0225] T5652: Polycarbonate diol manufactured by Asahi Kasei Corporation

[0226] T4692: Polycarbonate diol manufactured by Asahi Kasei Corporation

[0227] ACRIT 6KW-032: An acrylic polyol manufactured by TAISEI FINE CHEMICAL.

[0228] HAKUENKA DD: Calcium carbonate manufactured by Shiraishi Kogyo Co., Ltd.

[0229] BURGESS No. 10: Kaolin produced by Burgerss Pigment Company

[0230] MEK-ST-40: Silica manufactured by Nissan Chemical Co., Ltd.

[0231] MEK-ST-ZL: Silica manufactured by Nissan Chemical Co., Ltd.

[0232] TEGO variplus 1201TF: A polyurethane polyol manufactured by Evonik.

[0233] KW-75: An aromatic polyisocyanate manufactured by DIC.

[0234] SP-60: An aromatic polyisocyanate manufactured by DIC Corporation.

[0235] ORGATIX TC-401: A titanium compound manufactured by Matsumoto Fine Chemical Co., Ltd.

[0236] SC-101: Polyurethane manufactured by DIC Company

[0237] SV-02: Carbodiimide manufactured by Nisshinbo Chemical Co., Ltd.

[0238] (Manufacturing method of laminated body (1))

[0239] The above-mentioned coating agent (A) was applied to the olefin resin layer (B1), and a coating layer (A) was formed at 70°C. Further curing at 40°C for 3 days yielded the laminates of Examples 1 through.

[0240] The combination of the coating agent (A) and the olefin resin layer (B1) used is shown in Table 2.

[0241] (Methods for determining parameters)

[0242] The laminates of the embodiments and comparative examples obtained by the above method were used to measure T1, T2, CTE1, and CTE2 under the following conditions using the dynamic viscoelasticity measuring apparatus and thermomechanical analysis apparatus shown below. The calculation formulas are as follows.

[0243] Dynamic viscoelasticity measuring apparatus: RSA-G2 (manufactured by TA Instruments)

[0244] Measurement mode: Tension

[0245] Measurement frequency: 1Hz

[0246] Amplitude: 0.1%

[0247] Measurement direction of the sample: MD direction

[0248] Sample dimensions (distance between clamps × width): 10mm × 5mm

[0249] Measurement temperature: -40℃~170℃

[0250] Heating rate: 3℃ / min

[0251] Thermomechanical analysis apparatus: TMA-60 (manufactured by Shimadzu Corporation)

[0252] Measurement method: Tensile

[0253] Sample size (sample length × sample width): 20mm × 5mm

[0254] Measurement direction of the sample: MD direction

[0255] Initial load: 12g (for olefin resin layer (B1): OPE1)

[0256] 2g (Olefin resin layer (B1): cases of OPE2, OPE3, and OPP)

[0257] Measurement temperature: 30℃~170℃

[0258] Heating rate: 3℃ / min

[0259] (Evaluation Method)

[0260] (Heat resistance (evaluation of whether film shrinkage occurs))

[0261] For the laminates of the embodiments and comparative examples, a thermal gradient heat sealing tester (manufactured by TESTER SANGYO Co., Ltd.) was used at a sealing temperature of 100°C to 160°C and a pressure of 3 kg / cm². 2 Under the condition of 1 second, the heat-sealing rod is brought into direct contact with the heat-resistant coating layer (A). The condition of the laminate after contact with the heat-sealing rod is evaluated visually at level 2.

[0262] ○: The laminated body around the sealing portion in contact with the heat-sealing rod did not shrink.

[0263] ×: The shrinkage of the laminate can be confirmed around the sealing part of the contact heat-sealing rod.

[0264] (Substrate adhesion)

[0265] Transparent tape (NICHIBAN TF-12) was pressed onto the heat-resistant coating layer (A) of the laminate in the examples and comparative examples. The degree of peeling when the tape was peeled off in one go was visually judged and evaluated on a scale of 3. It should be noted that the adhesion of Reference Examples 1 to 4 was not evaluated because no coating was formed.

[0266] ○: No peeling

[0267] △: Partial stripping

[0268] ×: Complete stripping

[0269] (Heat seal strength)

[0270] Using a thermal gradient heat sealing tester (manufactured by TESTER SANGYO Co., Ltd.), the sealing temperature was 120℃~160℃ and the pressure was 3kg / cm². 2 Under conditions of 1 second, the laminates of the examples and comparative examples were heat-sealed in such a way that the layers, equivalent to the sealing layers, were in contact with each other. The sample width was set to 15 mm, and the 90° peel strength was measured at a tensile speed of 300 mm / min as the heat seal strength.

[0271] (Oxygen barrier properties)

[0272] The laminates of the examples and comparative examples were adjusted to a size of 10cm × 10cm. Using an OX-TRAN2 / 21 (MOCON: oxygen permeability measuring device), and according to JIS-K7126 (isobaric method), the oxygen permeability (unit: cc / m³) was measured under atmospheres of 23°C 0% RH, 23°C 50% RH, or 23°C 90% RH. 2 ( / day / atm). It should be noted that RH represents humidity.

[0273] The results are shown in Tables 2-1 to 5-2. It should be noted that blank columns indicate no measurement was performed.

[0274] [Table 5]

[0275]

[0276] [Table 6]

[0277]

[0278] [Table 7]

[0279]

[0280] [Table 8]

[0281]

[0282] The abbreviations in Tables 2-1 to 2-4 are as follows.

[0283] OPE1: Uniaxially stretched polyethylene film with a thickness of 25 μm (density: 0.92 g / m³). 2 Melting point: 125℃

[0284] OPE2: Biaxially stretched polyethylene film with a thickness of 40 μm (density: 0.91 g / m³). 2 Melting point: 125℃

[0285] OPE3: OPE1: Uniaxially stretched polyethylene film with a thickness of 25μm (density: 0.94g / m³). 2 Melting point: 135℃

[0286] OPP: P2161 manufactured by Toyobo Co., Ltd. (density: 0.91 g / m³) 2 Melting point: 165℃

[0287] (Manufacturing methods of laminated bodies (2), (3), (4))

[0288] A laminate with the stacked structure described in Tables 3 to 5-1 and Table 5-2 was obtained.

[0289] (Manufacturing method of laminated body (2))

[0290] The manufacturing method of the laminate shown in Table 3 is as follows.

[0291] The aforementioned coating agent (A) was applied to the side opposite to the ink surface of an olefin resin layer (B1) having a printing layer (E) formed using printing ink. The layer was then dried in a hot air dryer set to 70°C for 1 minute, forming a heat-resistant coating layer (A) with a dried film thickness of 2.0 μm. Then, when a barrier resin layer (D) was provided, the film thickness after applying the barrier coating agent (D) was 0.3 μm.

[0292] Next, on the barrier resin layer (D), a coating is applied with a solid content of 3.0 g / m². 2 The adhesive (C) is applied in a certain way and dried. Then, the adhesive (C) coating surface of the film is bonded to the olefin resin layer (B2) using a laminator to obtain a laminate.

[0293] (Manufacturing method of laminated body (3))

[0294] The manufacturing method of the laminate shown in Table 4 is as follows.

[0295] The above-mentioned coating agent (A) is applied to the surface of the olefin resin layer (B1) which is provided with a barrier resin layer (D) and a printing layer (E), opposite to the barrier resin layer (D) and the printing layer (E), and dried in a hot air dryer set to 70°C for 1 minute to form a heat-resistant coating layer (A) with a dry film thickness of 2.0 μm.

[0296] Next, on the printed layer (E), a coating of 3.0 g / m² of solids is applied. 2 After the adhesive (C) is applied and dried, the adhesive (C) coating surface of the film is bonded to the olefin resin layer (B2) using a laminator to obtain a laminate.

[0297] (Manufacturing method of laminated body (4))

[0298] The manufacturing method of the laminate shown in Table 5 is as follows.

[0299] The above-mentioned coating agent (A) was applied to the surface of the printing ink layer (B1) on which the printing layer (E) was provided using printing ink, and dried in a hot air dryer set to 70°C for 1 minute to form a heat-resistant coating layer (A) with a dry film thickness of 2.01 μm.

[0300] Then, with a barrier resin layer (D) provided, the film thickness after applying the barrier coating agent (D) to the side of the olefin resin layer (B1) opposite to the printed layer is 0.3~.

[0301] Furthermore, when an olefin resin layer (B2) is provided, if the olefin resin layer (B2) is a film, then on the olefin resin layer (B1) or the barrier resin layer (D), the coating amount becomes a solid content of 3.0 g / m². 2 The adhesive (C) is applied by means of a lamination process, and the adhesive (C) coated surface of the film is bonded to the olefin resin layer (B2) using a laminator to obtain a laminate.

[0302] On the other hand, if the olefin resin layer (B2) is a sealing coating, the sealing coating is directly applied to the olefin resin layer (B1) or the barrier coating (D) and then dried to obtain a laminate.

[0303] [Table 9]

[0304]

[0305] [Table 10]

[0306]

[0307] [Table 11]

[0308]

[0309] [Table 12]

[0310]

[0311] [Table 13]

[0312]

[0313] The abbreviations in Tables 3 to 5-2 and Table 6 are as follows.

[0314] FINART BM Blue: Liquid printing ink (for back printing) manufactured by DIC GRAPHICS.

[0315] Glossa BM Blue: Liquid printing ink manufactured by DIC GRAPHICS (for front-side printing).

[0316] SunBar AEROBLOCK 1.1: A barrier coating manufactured by Sun Chemical Company.

[0317] SunBar AEROBLOCK ENHANCE BARX 221 / 222: Barrier coating manufactured by Sun Chemical Company.

[0318] SunBar AEROBLOCK INLINE BARX698: A barrier coating manufactured by Sun Chemical Company.

[0319] SB-503 / SA-201: Barrier coating agent manufactured by DIC Corporation.

[0320] DICDRY: A reactive adhesive manufactured by DIC Corporation.

[0321] Paslim VM: Barrier adhesive manufactured by DIC Corporation.

[0322] Paslim MB: A barrier adhesive manufactured by DIC Corporation.

[0323] CPP: P1128 manufactured by Toyobo Co., Ltd. (thickness:

[0324] OPP: P2161 manufactured by Toyobo Co., Ltd. (thickness:

[0325] A-815P: Sealant manufactured by DIC Corporation.

[0326] OPE1: Uniaxially stretched polyethylene film with a thickness of 25 μm (density: 0.92 g / m³). 2 Melting point: 125℃

[0327] LLDPE: TUX HC manufactured by Mitsui Chemicals Tohcello Co., Ltd. (Thickness:

[0328] OPE4: Uniaxially stretched polyethylene film with a thickness of 25 μm (density: 0.94 g / m³). 2 Melting point: 130℃

[0329] Tables 3 to 5-2 show the laminates of this application, which satisfy the above-mentioned (1) and (2) conditions (CTE1 / CTE2*100 (%) values ​​are in the range of 10 to 100%). Table 6 shows the laminates of this application, which satisfy the above-mentioned (1) and (3) conditions (CTE3 / CTE4*100 (%) values ​​are in the range of 10 to 100%). It can be seen that these laminates all satisfy the requirements for heat resistance and substrate adhesion.

Claims

1. A laminated body, characterized in that, It has a heat-resistant coating layer A and an olefin resin layer B1 mainly composed of olefin resin b1. The heat-resistant coating layer A is a film layer of coating agent A, which contains inorganic microparticles. The content of the inorganic microparticles is 5% to 90% by weight relative to the total solid content of the coating agent A and the inorganic microparticles. The laminate satisfies (1) and (2) or satisfies (1) and (3). (1) The difference between the dynamic viscoelasticity DMA value E'1 (MPa) of the laminate in which a heat-resistant coating layer A is provided on one or both sides of the olefin resin layer B1 at a temperature of T1 ℃ and the dynamic viscoelasticity DMA value E'2 (MPa) of the laminate in which only the olefin resin layer B1 is provided at a temperature of T1 ℃ is more than 1 MPa. T1 ℃ = Melting point (℃) of olefin resin layer B1 - 35 ℃ E'1(MPa)-E'2(MPa)≥1 MPa (2) The percentage of the linear expansion coefficient CTE1 obtained by dividing the value of the linear expansion coefficient CTE2 obtained by the thermomechanical analysis of the laminate in which a heat-resistant coating layer A is provided on one or both sides of the olefin resin layer B1 at a temperature of T1 °C by the value of the linear expansion coefficient CTE2 obtained by the thermomechanical analysis of the olefin resin layer B1 alone at a temperature of T1 °C is 10% to 100%. 10 %≤((CTE1) / (CTE2))×100≤100 % (3) The percentage of the linear expansion coefficient CTE3 obtained by dividing the value of the linear expansion coefficient CTE4 obtained by the thermomechanical analysis of the laminate in which a heat-resistant coating layer A is provided on one or both sides of the olefin resin layer B1 at temperature T1 ℃ and 20 ℃ (i.e., T2 ℃) by the value of the linear expansion coefficient CTE4 obtained by the thermomechanical analysis of the olefin resin layer B1 alone at temperature T2 ℃ is 10% to 100%. 10%≤((CTE3) / (CTE4))×100≤100%.

2. The laminated body according to claim 1, wherein, The olefin resin layer B1 is a stretched olefin resin layer.

3. The laminate according to claim 1, comprising: Heat-resistant coating layer A Olefin resin layer B1, with olefin resin B1 as the main component, and The adhesive layer C containing adhesive c1, or the barrier resin layer D, or the olefin resin layer B2 with olefin resin b2 as the main component, or the printing layer E, or the sealing layer F, or the vapor-deposited layer G.

4. The laminated body according to claim 3, wherein, The laminate has the printed layer E in contact with the olefin resin layer B1, wherein the olefin resin layer B1 is mainly composed of olefin resin b1.

5. The laminated body according to claim 1, wherein, The total thickness of the laminate is 15 μm to 200 μm.

6. A packaging material, characterized in that, It is made using the laminate as described in claim 1.

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