WO2025028631A1 - 積層体とその製造方法、包装材及びコーティング剤 - Google Patents

積層体とその製造方法、包装材及びコーティング剤 Download PDF

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Publication number
WO2025028631A1
WO2025028631A1 PCT/JP2024/027627 JP2024027627W WO2025028631A1 WO 2025028631 A1 WO2025028631 A1 WO 2025028631A1 JP 2024027627 W JP2024027627 W JP 2024027627W WO 2025028631 A1 WO2025028631 A1 WO 2025028631A1
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Prior art keywords
laminate
substrate
resin
heating
coating layer
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PCT/JP2024/027627
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English (en)
French (fr)
Japanese (ja)
Inventor
倫孝 間宮
光 浦辺
裕紀 杉
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Toyo Ink Co Ltd
Artience Co Ltd
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Toyo Ink Co Ltd
Artience Co Ltd
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Priority to JP2025537523A priority Critical patent/JPWO2025028631A1/ja
Publication of WO2025028631A1 publication Critical patent/WO2025028631A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • Embodiments of the present invention relate to a laminate having excellent heat resistance, suitability for bag making, and adhesion, and a method for producing the same.
  • embodiments of the present invention relate to a packaging material using the laminate, and a coating agent that can be suitably used to form the laminate.
  • Packaging bags for flexible packages are made by combining multiple types of plastic materials.
  • biaxially oriented films such as polypropylene or polyester are used to provide the mechanical strength of the packaging bag
  • polyethylene, polypropylene, ethylene-vinyl acetate copolymer, etc. are used as heat seal materials for sealing the contents of the packaging bag.
  • the selection of the above materials has traditionally been based on the importance of their suitability for each process, such as packaging of the contents, transportation, storage, opening, etc.
  • importance has been placed on resource conservation and recyclability of various products.
  • Patent Document 1 discloses a laminate having a substrate, an adhesive layer, and a sealant layer, in which the substrate and sealant layer are made of polyethylene from the perspective of mono-materialization, thereby improving recyclability.
  • the bag making process for producing packaging bags involves folding the laminate so that the sealant layers overlap, and then clamping the laminate from the outer surface side of the base layer with a high-temperature tool to apply pressure and heat seal.
  • the tool of the heat sealing machine is at a high temperature, and the outer surface side of the base layer that directly contacts the tool is exposed to high temperatures. Therefore, when producing packaging bags using the laminate described in Patent Document 1, the base layer may be affected by heat, causing thermal shrinkage of the heat-sealed portion and/or a phenomenon in which the heat-sealed portion is cut off from the laminate (melting), and the suitability for bag making is insufficient.
  • Patent Document 2 discloses a laminate including a coating layer, a base layer, and a sealant layer, in which the base layer and the sealant layer are made of polyethylene, and the coating layer further contains a heat-resistant resin.
  • the invention described in Patent Document 2 is a laminate that aims to improve the heat sealability by forming a coating layer made of a resin with excellent heat resistance. However, the heat resistance and adhesion of the coating layer are insufficient, and the bag-making suitability is still insufficient.
  • the objective of the present invention is therefore to provide a laminate that has excellent heat resistance, suitability for bag making, and adhesion.
  • One embodiment of the present invention is a laminate having a substrate 1, an adhesive layer, and a substrate 2 in this order, and further having a coating layer,
  • the substrate 1 and the substrate 2 each contain a polyolefin resin
  • the coating layer contains a resin (A) having a glass transition point of 115° C. or higher
  • Another embodiment of the present invention is a laminate having a coating layer and a substrate 1,
  • the substrate 1 contains a polyethylene resin
  • the coating layer contains a resin (A) having a glass transition point of 115° C. or higher
  • the present invention relates to a laminate having a shrinkage rate, expressed by the following formula 1, of 30 area % or less when heated and pressed under the following heating and pressing conditions.
  • heating and pressure time 1 second
  • Shrinkage rate (area %) ⁇ 1-(area after heating and pressing)/(area before heating and pressing) ⁇ 100
  • Another embodiment of the present invention is a method for producing a laminate having a substrate 1, an adhesive layer, and a substrate 2 in this order, and further having a coating layer, A step of printing a coating agent containing a resin (A) having a glass transition point of 115° C. or higher on one surface of the substrate 1 to form a coating layer; A step of printing an adhesive on the other surface of the substrate 1 or on the coating layer to form an adhesive layer; and a step of bonding a substrate 2 onto the adhesive layer.
  • the present invention relates to a method for producing a laminate, in which the laminate has a shrinkage percentage, expressed by the following formula (1), of 30 area % or less when heated and pressed under the following heating and pressing conditions.
  • Another embodiment of the present invention is a coating agent used to form the coating layer of a laminate having a substrate 1, an adhesive layer, and a substrate 2 in this order, and further having a coating layer, the substrate 1 and the substrate 2 containing a polyolefin resin,
  • a coating agent comprising a resin (A) having a glass transition point of 115° C. or higher and a solvent.
  • the present invention provides a laminate that has excellent heat resistance, suitability for bag making, and adhesion.
  • FIG. 1 is a plan view for explaining a method for measuring the shrinkage rate of a laminate under heating and pressurization, and shows the area before heating and pressurization when a laminate cut to a size of 50 mm ⁇ 25 mm is heated and pressurized in an area of 20 mm ⁇ 10 mm.
  • FIG. 2 is a plan view for explaining a method for measuring the shrinkage rate of a laminate under heating and pressurization, and shows the area after heating and pressurization when a laminate cut to a size of 50 mm ⁇ 25 mm is heated and pressurized in an area of 20 mm ⁇ 10 mm.
  • the laminate has a substrate 1, an adhesive layer, and a substrate 2 in this order, and further has a coating layer, wherein the substrate 1 and the substrate 2 contain a polyolefin-based resin, and the laminate has a shrinkage percentage of 30 area % or less when heated and pressed under the heating and pressing conditions described below, the shrinkage percentage being represented by the following formula 1.
  • the shrinkage rate is preferably 30 area % or less, more preferably 15 area % or less, and even more preferably 5 area % or less.
  • the shrinkage rate is preferably 30 area % or less, more preferably 15 area % or less, and even more preferably 5 area % or less.
  • Laminate structure examples include, but are not limited to, the following structures.
  • “/" indicates the boundary between layers.
  • Coating layer/substrate 1/adhesive layer/substrate 2 (2) Substrate 1/coat layer/adhesive layer/substrate 2 (3) Substrate 1/adhesive layer/coating layer/substrate 2 (4) Coating layer/substrate 1
  • the coating layer is adjacent to the substrate 1, and it is also preferable that the coating layer is located as the outermost layer of the laminate.
  • the coating layer suppresses shrinkage of the laminate, and it is possible to provide a laminate with even better heat resistance and suitability for bag making.
  • the coating layer is adjacent to at least one of the substrate 1 and the substrate 2. It is preferable that the coating layer is adjacent to the substrate 1, and it is more preferable that the coating layer is provided on one side of the substrate 1 and constitutes the outermost surface of the laminate.
  • a film of a polyolefin resin such as polyethylene or polypropylene (hereinafter, also referred to as a polyolefin film or a polyolefin substrate) can be suitably used.
  • the substrate 1 and the substrate 2 may be made of the same material or different materials, but from the viewpoint of recyclability, it is preferable that they are made of the same material.
  • the following aspects are preferred examples of the laminate configuration.
  • the color change (color change) of the laminate due to heating is small.
  • the color change ⁇ E of the laminate before and after heating is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the coating layer makes it easy to adjust the color change of the laminate before and after heating to within the above range, and therefore the recyclability of the film can be easily improved.
  • the color change ⁇ E can be measured according to a method known in the art. For example, the method described in the examples below can be applied.
  • the coating layer may be mainly composed of a binder resin (hereinafter referred to as resin) and/or particles.
  • resin binder resin
  • main component is meant that it is present in an amount of 50% by mass or more relative to the total mass of the coating layer.
  • the coating layer preferably contains at least a resin, preferably contains a resin and particles, and more preferably contains a resin and inorganic particles.
  • the resin contained in the coating layer may be a film-forming resin known as a binder resin, but preferably contains a resin (A) having a glass transition point of 115°C or higher. It is more preferable that the resin (A) has a glass transition point of 120°C or higher.
  • the resin (A) more preferably contains a resin having a ring structure such as a cellulose-based resin, and more preferably contains at least one selected from the group consisting of nitrocellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • the coating layer preferably further contains particles. The particles are not particularly limited, but preferably contain at least one selected from the group consisting of silica, calcium carbonate, barium sulfate, titanium oxide, and zinc oxide, and more preferably contain barium sulfate.
  • the coating layer has excellent adhesion to the polyolefin substrate, the coating film flows little when heated, and the thermal shrinkage of the polyolefin substrate can be significantly suppressed, so that it is easy to satisfy the shrinkage ratio represented by the above formula (1).
  • the laminate has the configuration (1) or (4) exemplified above, and the coating layer contains a resin and inorganic particles. It is more preferable that the laminate has the configuration (1) or (4) above, and the coating layer contains a resin (A) with a glass transition point of 120°C or higher, and inorganic particles. It is even more preferable that the laminate has the configuration (1) or (4) above, and the coating layer contains a resin with a ring structure and inorganic particles. It is particularly preferable that the laminate has the configuration (1) or (4) above, and the coating layer contains a cellulose-based resin and at least one selected from the group consisting of silica, calcium carbonate, barium sulfate, titanium oxide, and zinc oxide.
  • the difference between the peak temperature of the loss tangent (tan ⁇ ) of the laminate and the peak temperature of the tan ⁇ of the laminate excluding the coating layer is preferably 1.0° C. or more as shown in the following (Equation 2) with respect to the peak temperature of the loss tangent (tan ⁇ ) measured at 80° C. to 200° C. based on JIS K 7244.
  • Equation 2 the same embodiment as the shrinkage rate described above is preferable.
  • the coating layer adheres closely to the polyolefin substrate, and the coating film does not flow much when heated, which reduces the shrinkage rate of the laminate. Due to the above effects, it is believed that the laminate of this embodiment can achieve high levels of improvement in heat resistance, bag-making suitability, adhesion, and blocking resistance. Note that this explanation is based solely on technical considerations and does not limit the invention in any way.
  • the coating layer can be formed by printing a coating agent and removing volatile components.
  • the laminate of this embodiment can be easily constructed using a coating agent described later.
  • the coating layer is preferably a heat-resistant coating layer, which adheres closely to the polyolefin substrate, has a small flow of the coating film when heated, and can suppress the thermal shrinkage of the polyolefin substrate. Therefore, the shrinkage rate represented by the above formula (1) can be reduced, and the laminate can be provided with heat resistance and bag-making suitability.
  • the thickness of the coating layer is preferably 0.3 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 2 ⁇ m. When the coating layer thickness is within the above range, the heat resistance and suitability for bag making are good.
  • the resin constituting the coating layer preferably includes a resin (A) having a glass transition point of 115°C or higher.
  • the glass transition point of the resin (A) may be 120°C or higher, 130°C or higher, or 140°C or higher.
  • the glass transition point of the resin (A) may be 220°C or lower, 210°C or lower, or 200°C or lower.
  • the glass transition point of the resin (A) is more preferably 120°C to 220°C, even more preferably 130°C to 210°C, and particularly preferably 140°C to 200°C.
  • the glass transition point of the resin constituting the coating layer is 115°C or higher, and more preferably 120°C or higher, it tends to exhibit excellent heat resistance, reduce the shrinkage rate represented by the above formula (1), and easily improve the heat resistance and bag-making suitability of the laminate when heated. Also, when the glass transition point of the resin constituting the coating layer is 220°C or lower, it tends to be easier for the coating layer to adhere to the substrate, and easily improve the adhesion and heat resistance of the laminate.
  • One embodiment of the present invention relates to a coating agent comprising a binder resin containing a resin (A) having a glass transition point of 115° C. or more, and a solvent.
  • the coating agent preferably further comprises particles.
  • the coating agent of this embodiment can be suitably used to form the laminate, and more suitably used to form a coating layer of the laminate.
  • the composition of the coating agent will be described below.
  • the coating agent contains a resin (A) having a glass transition point of 115°C or higher as a binder resin.
  • the glass transition point of the resin (A) is preferably 120°C to 250°C, more preferably 120°C to 220°C, even more preferably 130°C to 210°C, and particularly preferably 140°C to 200°C.
  • the coating layer contains a resin (A) having a glass transition point of 115°C or higher, more preferably 120°C or higher, thereby exhibiting excellent heat resistance, reducing the shrinkage rate represented by the above formula (1), and improving the heat resistance and bag-making suitability of the laminate when heated.
  • the glass transition point of the resin (A) is 250°C or lower, the coating layer adheres to the substrate, and the adhesion and heat resistance of the laminate are also improved.
  • the glass transition point is a value measured by DSC (differential scanning calorimetry).
  • Resin (A) having a glass transition point of 115°C or higher may be one type of resin or a combination of two or more types of resin. In the case of a resin that does not have a glass transition point, any resin having a softening point or melting point of 115°C or higher may be used, and in this specification, such resins are also included in resin (A) having a glass transition point of 115°C or higher.
  • the glass transition point of resin (A) is a weighted average value calculated based on the blending ratio of the two or more types of resin.
  • the glass transition point of resin (A) is preferably 115°C or higher, more preferably 120°C to 250°C, even more preferably 120°C to 220°C, particularly preferably 130°C to 210°C, and most preferably 140°C to 200°C.
  • the content of resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70 to 95% by mass, based on the mass of the total solids in the coating agent (100% by mass of the coating layer).
  • the content of resin (A) is within the above range, the heat resistance and bag-making suitability of the laminate are good.
  • the mass average molecular weight (Mw) of the resin (A) is preferably 13,000 to 70,000.
  • the mass average molecular weight is more preferably 13,000 to 50,000, and even more preferably 13,000 to 40,000.
  • the mass average molecular weight of the resin (A) is 13,000 or more, excellent heat resistance is exhibited, and the heat resistance and bag-making suitability of the laminate are good.
  • the mass average molecular weight of the resin (A) is 70,000 or less, the solid content of the coating agent can be increased, so that the film thickness of the heat-resistant coating layer can be set in an appropriate range, and the bag-making suitability of the laminate is improved.
  • the mass average molecular weight is measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the resin (A) examples include urethane resin, acrylic resin, epoxy resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, cellulose-based resin, and composite resins obtained by combining these resins. Among these, resins having a ring structure such as cellulose-based resins are preferred.
  • the resin (A) may contain one or more of these resins. Among these, in some embodiments, from the viewpoint of heat resistance and adhesion, it is preferred that the resin (A) contains a resin having a ring structure.
  • the resin (A) is preferably a resin having one or more ring structures, and more preferably a cellulose-based resin.
  • the resin (A) is preferably a combination of a resin having a ring structure and a polyamide resin, and more preferably a combination of a cellulose-based resin and a polyamide resin.
  • the resin (A) it is easy to achieve both heat resistance and substrate adhesion and to satisfy the heat shrinkage rate of formula 1.
  • the resin having a ring structure may be a resin having an aromatic hydrocarbon such as a pyranose ring or a benzene ring, or an alicyclic hydrocarbon such as a cyclohexanone ring.
  • the above-mentioned ring structure tends to improve heat resistance.
  • the resin having a ring structure include cellulose resins, polyimide resins, polyamideimide resins, etc., and may also be copolymers of the resins described above as examples of resin (A) with monomers having a ring structure such as aromatic hydrocarbon monomers or alicyclic hydrocarbon monomers.
  • the resin having a ring structure is preferably a cellulose resin from the viewpoint of heat resistance.
  • monomers having a ring structure include, but are not limited to, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene benzyl acrylate, cyclohexyl acrylate, cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, 1,5-cyclooctanediol, and 1,4-cyclohexanedimethanol.
  • cellulose-based resins include nitrocellulose, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, and carboxymethylcellulose.
  • the resin is preferably one or more selected from the group consisting of nitrocellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, and more preferably one or more selected from the group consisting of nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate.
  • These cellulose-based resins may be used alone or in combination of two or more.
  • the content of the resin having a ring structure is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70 to 95% by mass, based on the mass of the total solids in the coating agent (100% by mass of the coating layer).
  • the content of the resin having a ring structure such as a cellulose-based resin, is within the above range, the laminate has good heat resistance and bag-making suitability.
  • the nitrocellulose content in the coating layer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. When the nitrocellulose content in the coating layer is within the above range, the colorability after heating is good.
  • the content of the cellulose-based resin may be 55% by mass or more in 100% by mass of the resin (A).
  • the above content is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the content of the cellulose-based resin is within the above range, the heat resistance and bag-making suitability of the laminate are good.
  • the coating agent more preferably contains, as the binder resin, a resin (A) having a glass transition point of 115°C or more and a resin (B) having a glass transition point of less than 115°C.
  • the glass transition point of the resin (B) is preferably 100°C or less, more preferably 90°C or less, and even more preferably 80°C or less.
  • the glass transition point of the resin (B) is preferably -50°C or more, more preferably -30°C or more, and even more preferably -10°C or more.
  • the glass transition point of the binder resin calculated as a weighted average with the resin (A) is preferably 115°C or more, more preferably 120°C to 250°C, even more preferably 120°C to 220°C, particularly preferably 130°C to 210°C, and most preferably 140°C to 200°C.
  • resin (B) examples include urethane resin, acrylic resin, epoxy resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, and composite resins obtained by combining these resins, and the resin may contain one or more of these.
  • resin (B) contains at least one selected from the group consisting of urethane resin, polyvinyl butyral resin, and polyamide resin, and it is more preferable that the resin is a urethane resin and/or a polyvinyl butyral resin.
  • the content of resin (B) is preferably 20% by mass or less, more preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass, based on the mass of the total solid content in the coating agent (100% by mass of the coating layer).
  • the content of resin (B) is within the above range, the adhesion and heat resistance of the laminate are good.
  • the mass average molecular weight of resin (B) is preferably 5,000 to 200,000. More preferably, it is 8,000 to 150,000, and even more preferably, it is 10,000 to 100,000. When the mass average molecular weight of resin (B) is within the above range, excellent adhesion and heat resistance are exhibited, and the heat resistance and bag-making suitability of the laminate are good.
  • the mass average molecular weight is measured by gel permeation chromatography (GPC).
  • the difference in Hansen solubility parameter (HSP) between the two resins can be used as an index of their mutual solubility.
  • HSP is an index showing the solubility of a certain substance, and is expressed by the dispersion term ⁇ d, the polarity term ⁇ p, and the hydrogen bond term ⁇ h.
  • the combination of two types of resins may be, for example, a combination of two types of resin (A), specifically, a combination of a cellulose-based resin and a polyamide.
  • Another example may be a combination of resin (A) and resin (B).
  • a combination of resin (A) and resin (B) is preferred.
  • the HSP difference between the two types of resins may be preferably 14 to 21, more preferably 15 to 21, and even more preferably 16 to 21. When the HSP difference is within the above range, it is easy to form a microphase separation structure.
  • the microphase-separated resin (B) adheres to the substrate surface, which further improves the adhesion between the coating layer and the substrate, and the microphase-separated resin (A) tends to improve heat resistance. Note that the above description is based on technical considerations, and the present invention is not limited by theory.
  • the coating agent forming the coat layer preferably contains particles.
  • the particles may be either organic or inorganic, but are preferably inorganic from the viewpoint of heat resistance.
  • the content of the particles is preferably 1 to 90% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, based on the mass of the total solid content in the coating agent (100% by mass of the coating layer).
  • the average particle size of the particles is preferably 3,000 nm or less, and more preferably 10 to 1,000 nm.
  • the average particle size of the particles is preferably 10 to 500 nm, more preferably 20 to 300 nm, and even more preferably 30 to 150 nm.
  • the average particle size is measured by dynamic light scattering, and the peak of the obtained volume particle size distribution (histogram) is taken as the average particle size.
  • the coating agent forming the coat layer preferably contains inorganic particles.
  • inorganic particles include extender pigments such as silica, calcium carbonate, barium sulfate, and silicon dioxide, and metal oxides such as titanium oxide, zinc oxide, iron oxide, and aluminum oxide, and the like, and the coating layer may contain one or more of these.
  • the coating layer preferably contains one or more selected from the group consisting of calcium carbonate, barium sulfate, titanium oxide, and zinc oxide.
  • the coating layer more preferably contains one or more selected from the group consisting of calcium carbonate, barium sulfate, and zinc oxide, and even more preferably contains barium sulfate.
  • the content of the inorganic particles is preferably 1 to 90% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, based on the mass of the total solid content in the coating agent (100% by mass of the coating layer).
  • the average particle size of the inorganic particles is preferably 3,000 nm or less, and more preferably 10 to 1,000 nm. In some embodiments, the average particle size of the inorganic particles is preferably 10 to 500 nm, more preferably 20 to 300 nm, and even more preferably 30 to 150 nm.
  • the oil absorption of the particles is preferably 100 ml/100 g or less, more preferably 50 ml/100 g or less, and even more preferably 30 ml/100 g or less.
  • the oil absorption can be measured based on JIS K5101-13-1.
  • the refractive index of the particles is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.8 or less. When particles having a refractive index in the above range are used, a coating layer having excellent transparency can be easily obtained.
  • the ratio of the mass of the particles to 100% by mass of the resin (A) in the coating agent is preferably 1 to 900% by mass, more preferably 10 to 233% by mass, even more preferably 20 to 150% by mass, and particularly preferably 30 to 100% by mass.
  • organic particles examples include polyurethane resins, polynylon resins, polyacrylic resins, polysilicone resins, polystyrene resins, melamine resins, polyester resins, polyethylene resins, and benzoguanamine resins.
  • the particles in the coating agent may contain one or more of these.
  • Other preferred forms of organic particles are the same as those described above for inorganic particles.
  • the coating agent for forming the coat layer may contain any additives such as an adhesion imparting agent, a plasticizer, an amide wax, a hydrocarbon wax, a chelating crosslinking agent, etc. Among these, it is preferable to contain an adhesion imparting agent.
  • the coating agent forming the coat layer preferably contains an adhesion promoter from the viewpoint of improving adhesion to the substrate.
  • adhesion promoter include chlorinated polyolefins and acid-modified polyolefins, and chlorinated polyolefins are particularly preferred.
  • the chlorine content of the chlorinated polyolefin is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass% in 100 mass% of the chlorinated polyolefin.
  • the chlorine content in the present invention refers to the mass% content of chlorine atoms in 100 mass% of the chlorinated polyolefin.
  • the mass average molecular weight of the chlorinated polyolefin is preferably 5,000 to 80,000, and more preferably 13,000 to 50,000.
  • the amount of chlorine atoms (mmol/g) may be 1.3 or less, 1.0 or less, 0.7 or less, or may be 0, based on the total mass of the solid content of the coating agent forming the coating layer.
  • the chlorinated polyolefin has a structure in which hydrogen atoms in an ⁇ -olefin polymer represented by the following general formula (1) are substituted with chlorine atoms.
  • Chlorinated polyolefins have flexible alkyl groups as branched structures, so they remain viscous even at low temperatures, improving the adhesion of the coating layer to the substrate.
  • polyolefin structure there are no particular limitations on the polyolefin structure in chlorinated polyolefins, but resins containing homopolymers or copolymers of ⁇ -olefin-based unsaturated hydrocarbons such as polypropylene, poly-1-butene, and poly-4-methyl-1-pentene are preferred. Of these, those containing a polypropylene structure (i.e., a chlorinated polypropylene structure) are particularly preferred.
  • organic solvents examples include non-aromatic organic solvents such as hydrocarbons such as methylcyclohexane and ethylcyclohexane; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone; esters such as ethyl acetate, n-propyl acetate, and butyl acetate; and alcohols such as methanol, ethanol, propanol, isopropanol (IPA), and butanol.
  • the organic solvent may be appropriately selected in consideration of reducing the amount of solvent remaining in the coating after printing, and one type may be used alone, or two or more types may be mixed and used.
  • the content of the organic solvent is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and particularly preferably 70 to 85% by mass, in 100% by mass of the coating agent.
  • the coating agent for forming the coat layer preferably contains the binder resin and/or the inorganic particles, and further, in order to improve the handling, heat resistance, and bag-making suitability of the coating agent, optional components such as the adhesion imparting agent, organic solvent, co-resin, and other additives can be added to the coating agent alone or in combination.
  • the coating agent can be obtained, for example, by charging a resin solution in which a resin is dissolved in an organic solvent and/or inorganic particles, and an organic solvent in a mixer equipped with a stirring blade, rotor, or the like, and mixing and stirring them.
  • the stirring speed is not particularly limited, and can be performed at 50 to 30,000 rpm.
  • the substrate 1 and the substrate 2 described later may be a single layer, may be simply laminated with each other, or may be laminated with a substrate different from the plastic substrate via an adhesive layer or the like.
  • the "substrate different from the plastic substrate” may be, for example, a plastic substrate and a paper substrate having different properties, and may be of any type.
  • a laminated substrate it may be in a form including an adhesive layer.
  • the method of laminating the substrates is not particularly limited, and may be a conventionally known method such as a co-extrusion method, heat fusion, or pressure bonding via an adhesive layer.
  • the substrate 1 and substrate 2 described below preferably contain additives such as antistatic agents, antifogging agents, and ultraviolet protection agents by coating or kneading, have an easily adhesive coating layer (e.g., a layer containing polyvinyl alcohol and/or its derivatives), or have a substrate surface that has been corona-treated or low-temperature plasma-treated.
  • additives such as antistatic agents, antifogging agents, and ultraviolet protection agents by coating or kneading
  • an easily adhesive coating layer e.g., a layer containing polyvinyl alcohol and/or its derivatives
  • the above-mentioned additions and processing are also carried out for the purpose of improving the wettability of printing inks and other coating agents, or for the purpose of imparting specific functionality to the film.
  • they are suitably used to provide packaging materials with excellent visibility of the contents by preventing fogging of the packaging material due to moisture.
  • the substrate 1 preferably contains a polyolefin resin.
  • a film of a polyolefin resin can be preferably used.
  • OPP biaxially oriented polypropylene
  • CPP non-oriented polypropylene
  • a polypropylene film such as an acid-modified polypropylene or a copolymer polypropylene
  • a polyethylene film such as a low-density
  • a film of a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE), a medium-density polyethylene (MDPE), or a high-density polyethylene (HDPE) is preferable.
  • the thickness of the substrate 1 is not particularly limited. In some embodiments, the thickness of the substrate 1 may be preferably 5 ⁇ m or more and 150 ⁇ m or less, more preferably 10 ⁇ m or more and 70 ⁇ m or less.
  • the surface of the substrate 1 on which the coating layer is to be formed is a corona treatment.
  • the elemental ratio of oxygen on the corona-treated surface of the substrate 1 is preferably 2% or more, more preferably 3% or more, and even more preferably 4% or more.
  • the oxygen element ratio on the surface of the substrate 1 is the composition ratio of oxygen atoms when narrow measurement of carbon atoms and oxygen atoms is performed using an X-ray photoelectron spectrometer.
  • the measurement conditions using the X-ray photoelectron spectrometer may be, for example, as follows.
  • Equipment Quantera SXM manufactured by ULVAC-PHI X-ray source: Monochrome AlK ⁇ ⁇ X Ray setting: 100 ⁇ m ⁇ [15kV, 25W] Photoelectron take-off angle: 45° to the sample surface Bond energy correction: The peak due to the C-C bond in the C1s spectrum is corrected to 285.0 eV.
  • Charge neutralization conditions Use of an electron neutralization gun and an Ar ion gun (neutralization mode) in combination.
  • the substrate 1 is preferably a uniaxially stretched substrate or a biaxially stretched substrate from the viewpoint of printability and processability.
  • the uniaxially stretched substrate is a film stretched in the machine direction (MD). It can be obtained by any suitable film forming method, but is preferably obtained by stretching a sheet shaped by the T-die method.
  • the preferred stretch ratio in the machine direction (MD) of the uniaxially stretched substrate is 2 to 10 times, more preferably 2 to 8 times.
  • the biaxially stretched substrate is a film stretched in the machine direction (MD) and the transverse direction (TD).
  • the film that can be used as the substrate can be generally shaped by the T-die method, stretched in the machine direction (MD) and then stretched in the transverse direction (TD) in the same manner as the substrate film of a conventional laminate film.
  • the stretching in the biaxial direction may be the above-mentioned sequential biaxial stretching or simultaneous biaxial stretching, either of which is well used.
  • the preferred stretching ratio in the machine direction (MD) of the biaxially stretched substrate is 2 to 10 times, more preferably 2 to 8 times.
  • the preferred stretching ratio in the transverse direction (TD) is 2 to 10 times, more preferably 4 to 10 times.
  • the higher the stretch ratio of the film the greater the thermal shrinkage rate tends to be, but the stretching direction does not affect the thermal shrinkage rate.
  • the thermal shrinkage rate can be satisfied in the stretching direction of a uniaxially stretched film, the thermal shrinkage rate will be satisfied in the non-stretching direction of the uniaxially stretched film (the direction perpendicular to the stretching direction).
  • the polyolefin contained in the substrate 1 preferably has a density of 0.860 to 0.970 g/cm 3.
  • examples of polyethylene include an ethylene homopolymer or a copolymer component of ethylene and an olefin comonomer having a density of 0.940 to 0.970 g/cm 3 and an MFR of 0.1 to 10 g/10 min, and a copolymer component of ethylene and an olefin comonomer having a density of 0.860 to 0.926 g/cm 3 and an MFR of 1.0 to 30.0 g/10 min.
  • the substrate 2 contains a polyolefin resin and may be the same as or different from the substrate 1, but is preferably a sealant layer.
  • the sealant layer refers to a layer having heat sealability.
  • the substrate 2 is preferably the outermost layer of the laminate.
  • the description of the substrate 1 above can be used as the polyolefin resin contained in the substrate 2.
  • the substrate 2 is preferably a non-oriented polypropylene (CPP) film, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), or high density polyethylene (HDPE).
  • the melting point of the substrate 2 is preferably 80°C to 140°C, and more preferably 90°C to 120°C.
  • the thickness of the substrate 2 is preferably 20 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and even more preferably 20 to 60 ⁇ m.
  • substrate 1 may be a uniaxially oriented polyethylene film, a biaxially oriented polyethylene film, an unoriented high-density polyethylene film, or a biaxially oriented polypropylene film
  • substrate 2 may be an unoriented linear low-density polyethylene or an unoriented polypropylene.
  • the laminate of the present embodiment includes an adhesive layer.
  • the components of the adhesive layer are not particularly limited, and suitable examples thereof include dry lamination adhesives such as olefin adhesives, acrylic adhesives, ethylene-vinyl acetate copolymer adhesives, and reactive urethane adhesives, non-solvent lamination adhesives, imine anchor coating agents, butadiene anchor coating agents, isocyanate anchor coating agents, and thermoplastic resins used in extrusion lamination.
  • the adhesive layer preferably comprises a reactive urethane adhesive reaction product of a polyisocyanate and a polyol.
  • the adhesive layer may also comprise an inorganic compound for the purpose of improving the barrier properties of the laminate.
  • the thickness of the adhesive layer is preferably 0.5 ⁇ m or more and 20 ⁇ m or less, more preferably 0.8 ⁇ m or more and 5 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 4.5 ⁇ m or less.
  • the mass average molecular weight (Mw) of the polyol is preferably from 2,000 to 80,000, more preferably from 5,000 to 60,000, and even more preferably from 10,000 to 60,000. Furthermore, by using a polyol having a molecular weight distribution (Mw/Mn) of 1.5 to 10, the leveling property during adhesive application and the lamination strength between layers can be improved.
  • the molecular weight distribution (Mw/Mn) is preferably 3.0 to 10.0, and more preferably 3.0 to 8.0.
  • the molecular weight distribution (Mw/Mn) is preferably 1.5 to 5.0, and more preferably 2.0 to 4.0.
  • the acid value of the polyol is not particularly limited, but is preferably 0 to 50 mgKOH/g, more preferably 0 to 40 mgKOH/g.
  • the hydroxyl value of the polyol is not particularly limited, but is preferably 1 to 200 mgKOH/g, more preferably 3 to 150 mgKOH/g.
  • the isocyanate curing agent functions as a curing agent in the reactive adhesive, and can be used without any limitation as long as it is for use in ordinary two-component reactive adhesives and contains a functional group that is reactive with a hydroxyl group. By having an isocyanate group, the adhesive strength and cohesive force are increased, and it is possible to cure at a low temperature around room temperature.
  • the isocyanate curing agent a diisocyanate or a urethane prepolymer which is a reaction product of a diisocyanate and a polyol is preferable.
  • the diisocyanate various known aromatic, aliphatic or alicyclic diisocyanates can be used.
  • diisocyanates include 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophor
  • the functional group equivalent ratio NCO/OH between the hydroxyl group derived from the polyol and the isocyanate group derived from the isocyanate resin is preferably 1.5 to 8.0, more preferably 2.0 to 5.0.
  • Other components known for use in adhesives can be blended into the base agent or curing agent of the adhesive.
  • Usable commercially available polyols include TM-320 and TM340 manufactured by Toyo-Morton Co., Ltd. Also, usable commercially available isocyanate hardeners include CAT-13B and CAT-29B manufactured by Toyo-Morton Co., Ltd.
  • the laminate of the present embodiment may include additional layers depending on the intended use in addition to the substrate 1, the adhesive layer, the substrate 2, and the coating layer.
  • the laminate may further include a printing layer, a deposition layer, a barrier layer, an intermediate substrate, and the like, which will be described later.
  • the laminate of the present embodiment may have a printed layer.
  • the printed layer preferably contains a resin and a colorant.
  • the printed layer may be a layer that displays any picture, pattern, character, symbol, etc. for the purpose of providing decoration or aesthetics; displaying the contents, expiration date, and manufacturer or seller.
  • the printed layer may be a solid printed layer having no design, pattern, letter, symbol, or the like.
  • the method for forming the printed layer is not particularly limited, and the printed layer may be formed using a printing ink.
  • the printed layer may have a single layer structure or a multi-layer structure, and may be printed on the surface layer of the laminate.
  • the mass per unit area of the printed layer is preferably 0.1 to 12 g/ m2 , more preferably 0.5 to 6 g/ m2, and even more preferably 1 to 3 g/ m2 .
  • the laminate of the present embodiment may have a deposition layer and/or a barrier layer for the purpose of controlling the gas permeability of the film.
  • the deposition layer exists for the purpose of imparting oxygen barrier properties and/or water vapor barrier properties to the laminate, and examples thereof include deposition layers made of metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, and tin oxide.
  • the barrier layer exists mainly for the purpose of imparting oxygen barrier properties to the laminate, and preferably contains a polyvinyl alcohol-based resin.
  • the form of the barrier layer may be any known form, but it is preferably a barrier coat layer formed by a barrier coating agent.
  • the laminate of this embodiment may have an intermediate substrate.
  • a specific example of the intermediate substrate is preferably a plastic substrate mainly containing polyolefin resin as a raw material, similar to the substrate 1 and substrate 2.
  • the intermediate substrate include polyolefin resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer, propylene homopolymer, and ethylene-propylene copolymer.
  • the intermediate substrate may also be a composite substrate produced by a co-extrusion method.
  • the intermediate substrate is preferably made of the same (same) material as the substrate 1 and/or substrate 2, and more preferably made of the same (same) material as the substrate 1 and substrate 2.
  • the same (same) material include combinations of polypropylene and polyethylene.
  • typical examples of the laminate structure include the following. Coating layer/substrate 1/printing layer/adhesive layer/substrate 2 Coating layer/substrate 1/printing layer/barrier layer/adhesive layer/substrate 2 Coating layer/substrate 1/printing layer/adhesive layer/intermediate substrate layer/adhesive layer/substrate 2
  • the manufacturing method includes a step of printing a coating agent on one or both sides of the base layer 1 to form a coat layer, a step of printing an adhesive on the base layer 1 or the coat layer to form an adhesive layer, and a step of bonding the base material 2 onto the adhesive layer.
  • the method for forming the coat layer is not particularly limited, and the coat layer can be formed by printing the coating agent by a known printing method and removing the volatile components.
  • the printing method include non-plate printing methods such as the inkjet method, the spray method, the dipping method, the slot die method, and the spin coat method; and plate printing methods such as the offset gravure coater, the gravure coater, the doctor coater, the kiss coater, the bar coater, the blade coater, the flexo coater, and the roll coater.
  • the method for forming the adhesive layer and the method for bonding each layer are not particularly limited, and may be any of the conventionally known methods such as extrusion lamination, dry lamination, and non-solvent lamination.
  • the laminate of this embodiment can be suitably used for packaging materials such as packaging bags.
  • a packaging bag can be produced, for example, by folding the laminate so that the sealant layers overlap, and then applying pressure with a high-temperature tool to sandwich and heat seal the laminate.
  • a packaging bag can also be produced by overlapping two laminates and heat welding them.
  • the laminate of this embodiment can be suitably used for packaging bags, particularly for gusseted packaging bags such as gusseted bags and stand-up bags.
  • the gusset bag can be manufactured, for example, by the method described in JP 2020-059535 A.
  • a gusset bag the joint for forming the shape of the bag is in a state where multiple layers of packaging material are overlapped, so the film thickness is thick, and heat is difficult to transmit to the inside during heat sealing. Therefore, in the manufacture of a gusset bag, the heat sealing temperature must often be set high in order to transmit heat to the inside of the joint where the packaging material is overlapped. For this reason, in the manufacture of a gusset bag, the surface of the packaging material that comes into direct contact with the heat sealing tool is required to have higher heat resistance. Similarly, high heat resistance is required in the manufacture of stand-up bags.
  • the laminate of this embodiment has excellent heat resistance, so it can be suitably used as a packaging material not only for general packaging bags, but also for cases where high heat resistance is required, such as gusset bags.
  • One method for recycling mono-material packaging materials is heating and melt kneading using an extruder or the like.
  • the heating temperature in this melt kneading is higher than the heat sealing temperature during packaging bag production, so there is a high possibility that the resin will discolor due to heating during recycling.
  • the laminate of this embodiment has excellent heat resistance, so that discoloration due to heating and pressurization during packaging bag production can be easily suppressed, and a packaging material with excellent recyclability can be realized.
  • the coating layer contains nitrocellulose resin
  • the components in the nitrocellulose resin react with the substrate due to heat, and the substrate tends to be easily discolored. From this perspective, by adjusting the content of nitrocellulose resin in the coating layer, it becomes easier to suppress discoloration of the substrate due to heat.
  • the substrate 1 and the substrate 2 contain a polyolefin resin
  • Shrinkage rate (area %) ⁇ 1-(area after heating and pressing)/(area before heating and pressing) ⁇ 100
  • a laminate having a coating layer and a substrate 1 contains a polyethylene resin, A laminate having a shrinkage rate of 30 area % or less, as represented by the following formula (1), when the laminate is heated and pressed under the following heating and pressing conditions.
  • Shrinkage rate (area %) ⁇ 1-(area after heating and pressing)/(area before heating and pressing) ⁇ 100
  • [7] A laminate according to any one of [1] to [6], in which the coating layer contains a chlorinated polyolefin resin.
  • a method for producing a laminate having a substrate 1, an adhesive layer, and a substrate 2 in this order, and further having a coating layer comprising: A step of printing a coating agent to form a coating layer; printing an adhesive to form an adhesive layer; and a step of bonding a substrate 2 onto the adhesive layer.
  • the various measurement methods are as follows. ⁇ Glass transition temperature> The glass transition point of the resin was measured by DSC (differential scanning calorimeter manufactured by TA Instruments Co., Ltd.). Specifically, about 2 mg of a sample obtained by drying the coating agent was weighed on an aluminum pan, the aluminum pan was set in a DSC measurement holder, and the baseline shift to the endothermic side in the DSC curve obtained under the temperature increase condition of 5° C./min was read to obtain the glass transition point.
  • DSC differential scanning calorimeter manufactured by TA Instruments Co., Ltd.
  • the weight average molecular weight was determined by measuring the molecular weight distribution using a gel permeation chromatography (GPC) device (HLC-8220 manufactured by Tosoh Corporation) and calculating the molecular weight converted using polystyrene as a standard substance. The measurement conditions are shown below.
  • GPC gel permeation chromatography
  • the amine value is the amount of potassium hydroxide (mg) equivalent to the amount of hydrochloric acid required to neutralize the amino groups contained in 1 g of sample, and was measured in accordance with JIS K 0070.
  • Bromophenol blue was added as an indicator to the resulting solution, and the resulting solution was titrated with a 0.2 mol/L ethanolic hydrochloric acid solution (titer: f).
  • ⁇ Oxygen element ratio on the surface of substrate 1 The element ratio of oxygen on the surface of the substrate 1 was determined by narrow measurement of carbon atoms and oxygen atoms using an X-ray photoelectron spectrometer.
  • the measurement conditions for the X-ray photoelectron spectrometer were as follows (measurement conditions): Equipment: Quantera SXM manufactured by ULVAC-PHI X-ray source: Monochrome AlK ⁇ ⁇ X Ray setting: 100 ⁇ m ⁇ [15kV, 25W] Photoelectron take-off angle: 45° to the sample surface Bond energy correction: The peak due to the C-C bond in the C1s spectrum is corrected to 285.0 eV.
  • Charge neutralization conditions Use of an electron neutralization gun and an Ar ion gun (neutralization mode) in combination.
  • a solution of a terminal isocyanate prepolymer was gradually added at room temperature to a mixture of 1.7 parts of isophorone diamine, 0.2 parts of n-dibutylamine, 18 parts of ethyl acetate, and 28 parts of isopropyl alcohol. After the addition, the mixture was reacted at 50° C. for 1 hour to obtain a urethane resin A solution with a solid content of 30%.
  • the urethane resin A had a mass average molecular weight of 70,000, an amine value of 4 mgKOH/g, and a glass transition temperature of -42°C.
  • Synthesis Example 2 Synthesis of Urethane Resin B Into a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 195 parts of Polylite RX-4800 (manufactured by DIC Corporation, polycarbonate polyol, solids content 100%), 5 parts of 1,4-butanediol, 44.2 parts of isophorone diisocyanate, and 61.1 parts of ethyl acetate were charged and reacted at 80° C. for 4 hours under a nitrogen stream to obtain a solvent solution of a terminal isocyanate prepolymer.
  • Polylite RX-4800 manufactured by DIC Corporation, polycarbonate polyol, solids content 100%
  • the urethane resin B had a glass transition point of 40° C., an amine value of 6.0 mg KOH/g, and a weight average molecular weight of 60,000.
  • the previously prepared isocyanate-terminated prepolymer solution was gradually added to a mixture of 8.21 parts of isophorone diamine and 527.9 parts of a 50/50 mixed solvent of ethyl acetate and isopropanol at 40° C. After the addition, the mixture was reacted at 80° C. for 1 hour to obtain a urethane resin C solution with a solid content of 30%.
  • the urethane resin C had a glass transition point of 0° C., an amine value of 7.0 mg KOH/g, and a weight average molecular weight of 59,000.
  • Coating Agent 1 5.0 parts of barium sulfate (average particle size: 0.05 ⁇ m, solid content 100%, oil absorption 20 ml/100 g, refractive index 1.64), 0.1 parts of BYK-111 (manufactured by BYK-Chemie, resin having an acidic functional group, solid content 95%), 8.0 parts of ethyl acetate, 1.0 part of 2-propanol, and 1.0 part of propylene glycol monomethyl ether were stirred and mixed, and dispersed using a bead mill (using zirconia beads).
  • nitrocellulose resin solution DLX5-8 manufactured by ICI Novel enterprises, nitrocellulose, nitrogen content 12.0%, solid content 30%, 2-propanol solution
  • Superchron 370M chlorinated polypropylene
  • Coating Agents 2 to 19 were obtained in the same manner as in Production Example 1, except that the raw materials and compounding ratios shown in Table 1 were used.
  • CAP cellulose acetate propionate
  • CAB cellulose acetate butyrate
  • CA cellulose acetate
  • a mixed solvent of ethyl acetate/2-propanol/propylene glycol monomethyl ether (8/1/1) was used, and the solid content was adjusted to 30%.
  • (Binder resin) S-2800: Polyamide resin manufactured by Kao Corporation, glass transition point 115°C, mass average molecular weight 3500 (solid content 30% 2-propanol/toluene 30/70 solution)
  • CAP-482-0.5 Cellulose acetate propionate manufactured by Eastman Co., glass transition point 142°C, mass average molecular weight 25,000
  • CAP-504-0.2 Cellulose acetate propionate manufactured by Eastman Co., glass transition point 159°C, mass average molecular weight 15,000
  • CAP-482-20 Cellulose acetate propionate manufactured by Eastman Co., glass transition point 147°C, mass average molecular weight 75,000 CAB-553-0.4: Cellulose acetate butyrate manufactured by Eastman Co., glass transition point 136°C, mass average molecular weight 20,000 CAB-531-1: Cellulose acetate butyrate manufactured by Eastman Co., glass transition point 115°C, mass average molecular weight 10,000 CAB-381
  • the glass transition point of the resin in the coating agent was 85° C., and the mass average molecular weight could not be measured.
  • the glass transition point of the resin in the coating agent was 260°C and the mass average molecular weight was 6000.
  • Coating Agent 22 jER1004 an epoxy resin manufactured by Mitsubishi Chemical Corporation
  • Coronate L manufactured by Tosoh Corporation
  • the glass transition point of the resin in the coating agent was 104 °C.
  • Coating Agent 23 20 parts of polyamide resin solution S-2800 (solid content 30%), 20 parts of cellulose resin solution DLX5-8 (solid content 30%), 30 parts of inorganic pigment CR-80 (solid content 100%, Ishihara Sangyo Kaisha, Ltd., rutile crystal structure, surface treatment with silica and alumina, average particle size 0.25 ⁇ m, oil absorption 20 ml/100 g), 0.8 parts of hydrocarbon wax (solid content 100%, needle penetration 13, melting point 110 ° C.), 20.4 parts of propyl acetate, and 8.8 parts of 2-propanol were mixed. The resulting mixture was kneaded and dispersed in a sand mill for 20 minutes to obtain coating agent 23.
  • Coating Agent 24 5.0 parts of calcium carbonate (average particle size: 0.08 ⁇ m, solid content 100%, oil absorption 54 ml/100 g, refractive index 1.6), 0.1 parts of DA-375 (manufactured by BYK-Chemie, resin having acidic functional groups, solid content 95%), 8.0 parts of ethyl acetate, 1.0 parts of 2-propanol, and 1.0 parts of propylene glycol monomethyl ether were mixed and stirred. The resulting mixture was dispersed in a bead mill (using zirconia beads), and then 12.0 parts of CAP-504-0.2 and 1.2 parts of VINNOL E 15/40A were added and mixed with stirring to obtain a coating agent 24.
  • Coating Agents 25 to 41 were obtained in the same manner as in Production Example 24, except that the raw materials and compounding ratios shown in Table 2 were used.
  • CAP cellulose acetate propionate
  • CAB cellulose acetate butyrate
  • a mixed solvent of ethyl acetate/2-propanol/propylene glycol monomethyl ether (8/1/1) was used, and the solid content was adjusted to 30% to prepare a resin solution.
  • Glass transition point: 0° C., weight average molecular weight: 59,000 S-2800: Polyamide resin manufactured by Kao Corporation, glass transition point 115°C, mass average molecular weight 3500 (solid content 30%, 2-propanol/toluene 30/70 solution, softening point 115°C)
  • Coating agent 1 was diluted with a mixed solvent (isopropyl alcohol/ethyl acetate) to a solid content of 15%.
  • a uniaxially stretched polyethylene film MDOPE (surface oxygen element ratio 10.2%, thickness 25 ⁇ m) corona-treated on both sides was prepared as substrate 1.
  • the diluted coating agent 1 was printed on the corona-treated surface of substrate 1 to form a coating layer.
  • Coating agent 1 was printed using a gravure printing machine equipped with a gravure plate with a plate depth of 60 ⁇ m, at a printing speed of 50 m/min and an in-line oven temperature of 60° C.
  • a polyether-based reactive urethane adhesive (“TM-340V/CAT-29B” manufactured by Toyo-Morton Co., Ltd.) was applied to the corona-treated surface of the substrate 1 opposite to the surface on which the coating layer was formed, using a dry laminator equipped with a gravure plate with a plate depth of 40 ⁇ m, to form an adhesive layer. Thereafter, a low-density polyethylene (LLDPE) film (thickness 60 ⁇ m) was bonded onto the adhesive layer as the substrate 2 to produce a laminate film.
  • LLDPE low-density polyethylene
  • the laminate film prepared as described above was stored at 40° C. for 1 day to obtain a laminate having the structure (1) (coat layer/substrate 1/adhesive layer/substrate 2).
  • the thermal shrinkage rate of the obtained laminate was 0.1% or less, and the peak temperature difference of the loss tangent was 1.5° C.
  • Examples 2 to 5, 7 to 20, 23 to 29, Comparative Examples 1 to 3, 5 A laminate was obtained in the same manner as in Example 1, except that the configuration, coating agent, and printing conditions for the coating agent were changed to those shown in Table 3.
  • a high density polyethylene (HDPE) film (thickness 25 ⁇ m) was used as the substrate 1.
  • a biaxially oriented polypropylene (OPP) film (thickness 25 ⁇ m) was used as the substrate 1
  • a non-oriented polypropylene (CPP) film was used as the substrate 2.
  • the samples melted during the measurement of the shrinkage ratio, making it impossible to measure the shrinkage ratio.
  • a substrate 1 was prepared by printing a diluted coating agent 3 on the corona-treated surface of a uniaxially oriented polyethylene (MDOPE) film (thickness: 25 ⁇ m) that had been corona-treated on both sides, at a printing speed of 50 m/min and an in-line oven temperature of 60° C., by using a gravure printing machine equipped with a gravure plate having a plate depth of 60 ⁇ m, to form a coating layer, thereby obtaining a laminate having a configuration (4) (coating layer/substrate 1).
  • the thermal shrinkage of the obtained laminate was 0.1% or less, and the peak temperature difference of the loss tangent was 1.5°C.
  • the substrate 1 was a uniaxially oriented polyethylene (MDOPE) film (thickness: 25 ⁇ m) that had been corona-treated on both sides.
  • a diluted coating agent 3 was printed on the corona-treated surface of the substrate 1 using a gravure printing machine equipped with a gravure plate having a plate depth of 60 ⁇ m at a printing speed of 50 m/min and an in-line oven temperature of 60° C. to form a coating layer.
  • MDOPE uniaxially oriented polyethylene
  • a polyether-based reactive urethane adhesive (“TM-340V/CAT-29B” manufactured by Toyo-Morton) was applied onto the coating layer of the substrate 1 using a dry laminating machine equipped with a gravure plate with a plate depth of 40 ⁇ m to form an adhesive layer, and a low-density polyethylene (LLDPE) film (thickness 60 ⁇ m) was bonded onto the adhesive layer as the substrate 2 to produce a laminate film.
  • LLDPE low-density polyethylene
  • the laminate film prepared as described above was stored at 40° C. for 1 day to obtain a laminate having the structure (2) (substrate 1/coat layer/adhesive layer/substrate 2).
  • the thermal shrinkage rate of the obtained laminate was 10.9%, and the peak temperature difference of the loss tangent was 1.0° C.
  • a coating layer was formed by printing a diluted coating agent 3 on the corona-treated surface of a low-density polyethylene (LLDPE) film (thickness 60 ⁇ m) that had been corona-treated on one side as the substrate 2.
  • the printing was performed using a gravure printing machine equipped with a gravure plate with a plate depth of 60 ⁇ m under conditions of a printing speed of 50 m/min and an in-line oven temperature of 60° C.
  • a polyether-based reactive urethane adhesive (“TM-340V/CAT-29B” manufactured by Toyo-Morton Co., Ltd.) was applied onto the coating layer of the substrate 2 using a dry laminator equipped with a gravure plate with a plate depth of 40 ⁇ m to form an adhesive layer.
  • a uniaxially oriented polyethylene (MDOPE) film (thickness 25 ⁇ m) was bonded onto the adhesive layer as the substrate 1 to produce a laminate film.
  • the laminate film prepared as described above was stored at 40° C. for 1 day to obtain a laminate having the structure (3) (substrate 1/adhesive layer/coat layer/substrate 2).
  • the thermal shrinkage rate of the obtained laminate was 12.3%, and the peak temperature difference of the loss tangent was 1.0° C.
  • a polyether-based reactive urethane adhesive (“TM-340V/CAT-29B" manufactured by Toyo-Morton Co., Ltd.) was applied to the corona-treated surface of a uniaxially oriented polyethylene (MDOPE) film (thickness 25 ⁇ m) as the substrate 1 using a dry laminator equipped with a gravure plate with a plate depth of 40 ⁇ m to form an adhesive layer.
  • MDOPE uniaxially oriented polyethylene
  • LLDPE low-density polyethylene
  • the laminate film prepared as described above was stored at 40° C. for 1 day to obtain a laminate having a structure of substrate 1/adhesive layer/substrate 2. The obtained laminate was melt-cut by heating and pressing, and the thermal shrinkage rate could not be measured.
  • the coating agent 24 was diluted with a mixed solvent (isopropyl alcohol/ethyl acetate) to a solid content of 15%.
  • a uniaxially stretched polyethylene film MDOPE2 (surface oxygen element ratio 4.0%, thickness 25 ⁇ m) with double-sided corona treatment was prepared as the substrate 1.
  • the diluted coating agent 24 was printed on the corona-treated surface of the substrate 1 to form a coating layer.
  • the printing was performed using a gravure printing machine equipped with a gravure plate with a plate depth of 60 ⁇ m, under conditions of a printing speed of 50 m/min and an in-line oven temperature of 60°C.
  • a polyether-based reactive urethane adhesive (“TM-340V/CAT-29B” manufactured by Toyo-Morton Co., Ltd.) was applied to the corona-treated surface of the substrate 1 opposite to the surface on which the coating layer was formed, using a dry laminator equipped with a gravure plate with a plate depth of 40 ⁇ m, to form an adhesive layer.
  • a low-density polyethylene (LLDPE) film (thickness 60 ⁇ m) was attached onto the adhesive layer as the substrate 2 to produce a laminate film.
  • the laminate film prepared as described above was stored at 40° C. for 1 day to obtain a laminate having the structure (1) (coat layer/substrate 1/adhesive layer/substrate 2).
  • the thermal shrinkage rate of the obtained laminate was 0.1% or less, and the peak temperature difference of the loss tangent was 1.5° C.
  • Examples 31 to 65 A laminate was obtained in the same manner as in Example 30, except that the configuration, coating agent, and printing conditions for the coating agent were changed as shown in Table 4. Details of the substrate are as follows.
  • MDOPE surface oxygen element ratio 10.2%, thickness 25 ⁇ m, stretch ratio 8 times
  • MDOPE2 surface oxygen element ratio 4.0%, thickness 25 ⁇ m, stretch ratio 8 times
  • MDOPE3 surface oxygen element ratio 10.2%, thickness 25 ⁇ m, stretch ratio 5 times
  • MDOPE4 (surface oxygen element ratio 10.2%, thickness 25 ⁇ m, stretch ratio 10 times)
  • FIGS 1 and 2 are plan views explaining a method for measuring the shrinkage rate of a laminate during heating and pressing. As shown in Figure 1, a laminate cut to 50 mm x 25 mm was heated and pressed in an area of 20 mm x 10 mm. The area (S1) before heating and pressing is consistent with the area (A) that was heated and pressed.
  • Figure 2 shows the area (S2) after heating and pressing, in which the end D1 before heating and pressing (the 25 mm side on the heated and pressed side) becomes the end D2 due to thermal shrinkage.
  • the heating and pressing conditions were as follows: Next, the appearance change of the laminate was evaluated according to the following evaluation criteria. ⁇ Heating and pressurizing conditions> Heating temperature: 160° C., pressure: 2 kg/cm 2 , heating and pressing time: 1 second, Heating and pressing direction: Heating and pressing were applied from the coating layer side of the laminate. For Examples 21 and 22 in which the coating layer was not the outermost layer, heating and pressing were applied from the substrate 1 side. (Evaluation Criteria) S: No noticeable wrinkles were observed in the heated and pressurized area (very good).
  • A The shrinkage rate in the longitudinal direction is 2.5% or more and less than 5%.
  • B The shrinkage rate in the longitudinal direction is 5% or more and less than 10%.
  • C The shrinkage rate in the length direction is 10% or more, or the film is melted and broken (unusable).
  • Adhesion Based on JIS K5600-5-6, the laminate was subjected to an adhesion test by a cross-cut method, and the adhesion was then evaluated according to the following evaluation criteria.
  • Evaluation Criteria S: The result of the adhesion test is classified as 0 to 1. That is, the peeled area is less than 5%.
  • B: The result of the adhesion test is Class 3. That is, the peeled area is 15% or more and less than 35%.
  • C The result of the adhesion test is in the category of 4 to 5. That is, the peeled area is 35% or more.
  • the laminates produced in Examples 30 to 65 were subjected to the following evaluations. The results are shown in Table 4.
  • the substrate 2 side of the obtained laminate was attached to a metal plate and heated at 200° C. for 15 minutes, and the color change ⁇ E of the laminate before and after heating was evaluated.
  • the color change ⁇ E was calculated using the following formula, based on the color values L*x, a*x, and b*x measured from the substrate 1 side of the laminate using a spectrophotometer (X-rite eXact, manufactured by X-rite Corporation).
  • HSP difference between two resins Hansen solubility parameters (HSP) are indicators of the solubility of a substance, and are represented by the dispersion term ⁇ d, the polarity term ⁇ p, and the hydrogen bond term ⁇ h.
  • Hansen solubility parameters were referenced to the values described in Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007) by Charles M. Hansen.
  • solubility tests of the substances in multiple solvents and values calculated using known computer software such as Hansen Solubility Parameters in Practice (HSPiP) were referenced.
  • HSP difference between resin (B) and substrate 1 Regarding the HSP difference between resin (B) and substrate 1, the following was used as the HSP value of substrate 1.
  • OPP Polypropylene base material
  • Comparative Examples 1, 3, and 5 were laminates that did not satisfy the requirement of a shrinkage rate of 30% or less by area, and melted when pressed, resulting in poor heat resistance and suitability for bag making.
  • Comparative Example 2 was a laminate with a shrinkage rate of more than 30% by area, resulting in poor suitability for bag making and adhesion.
  • Comparative Example 4 was a laminate without a coating layer, resulting in poor heat resistance and suitability for bag making.
  • the examples were laminates having a coating layer containing a resin with a Tg of 115°C or higher, and the shrinkage rate of the laminate when heated and pressurized was 30 area% or less, and the heat resistance, suitability for bag making, and adhesion were good.
  • the laminates of Examples 30 to 63 which are embodiments of the present invention, have a coating layer containing a resin having a glass transition temperature of 115° C. or higher, and the shrinkage rate of the laminate when heated and pressurized is 30 area % or less, so that the heat resistance, suitability for bag making, and adhesion are all good. In addition, the colorability after heating is also good, so that it is easy to improve the suitability for recycling.
  • the laminates of Examples 30, 31, and 62 were cut to 50 mm x 25 mm (when the substrate contained a uniaxially stretched film, the short side was 25 mm in the stretching direction (MD direction)), and the thermal shrinkage was evaluated.
  • the laminate was heated and pressed in a range of 20 mm x 10 mm as shown in Figures 1 and 2 using a heat seal tester with the stretching direction of the laminate changed, and the thermal shrinkage of the laminate was evaluated.
  • the thermal shrinkage of each of the laminates of Examples 30, 31, and 62 measured by the above method was the same as the result evaluated by the method described as the measurement method for heat resistance. From this, it can be seen that the same thermal shrinkage is obtained even when heated and pressed in the MD direction and the TD direction, respectively.
  • the desired characteristics can be obtained by the thermal shrinkage of the laminate being 30 area % or less, not only in Example 60 using a non-stretched substrate, but also in Examples 58 and 59 using different stretch ratios of the substrate. It is also understood that the desired properties can be improved more easily by adjusting the composition and amount of the coating agent that forms the coat layer and the amount of surface treatment of the substrate.

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JP2016055537A (ja) * 2014-09-10 2016-04-21 Dic株式会社 積層フィルム及び包装材
JP2016210129A (ja) * 2015-05-12 2016-12-15 株式会社ダイセル 積層フィルム、積層体及びその製造方法並びに燃料電池の製造方法
JP2019059528A (ja) * 2017-09-27 2019-04-18 大日本印刷株式会社 包装材
JP2020055157A (ja) 2018-09-28 2020-04-09 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ
JP2020059535A (ja) 2018-10-11 2020-04-16 共同印刷株式会社 ガセット袋
JP2020070323A (ja) * 2018-10-30 2020-05-07 株式会社日本製鋼所 多孔質フィルムの製造方法および多孔質フィルム
JP2021165023A (ja) * 2020-04-08 2021-10-14 東洋インキＳｃホールディングス株式会社 包装袋用積層体およびその製造方法
WO2022230812A1 (ja) 2021-04-26 2022-11-03 凸版印刷株式会社 積層体、包装材料及び包装袋
JP2022175645A (ja) * 2021-05-14 2022-11-25 レンゴー株式会社 ラベル
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JP2016055537A (ja) * 2014-09-10 2016-04-21 Dic株式会社 積層フィルム及び包装材
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