WO2022202856A1 - Étiquette multicouche - Google Patents

Étiquette multicouche Download PDF

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Publication number
WO2022202856A1
WO2022202856A1 PCT/JP2022/013336 JP2022013336W WO2022202856A1 WO 2022202856 A1 WO2022202856 A1 WO 2022202856A1 JP 2022013336 W JP2022013336 W JP 2022013336W WO 2022202856 A1 WO2022202856 A1 WO 2022202856A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin layer
multilayer label
layer
filler
Prior art date
Application number
PCT/JP2022/013336
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English (en)
Japanese (ja)
Inventor
直紀 田矢
慶一 佐藤
壮 宮田
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2023509222A priority Critical patent/JPWO2022202856A1/ja
Publication of WO2022202856A1 publication Critical patent/WO2022202856A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D11/00Carrying forward or transferring entries from one page to another, e.g. for book-keeping
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/80Packaging reuse or recycling, e.g. of multilayer packaging
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to multilayer labels.
  • multi-layer labels having a multi-layer structure have been widely used for delivery slips used for delivery of packages.
  • This multilayer label usually comprises a base material such as thermal paper for printing information, a resin layer, and an adhesive layer for attaching to a package, and the base material and the resin layer, or a plurality of resin layers are separated once. Later, those that are difficult to adhere to each other are used.
  • the layers laminated under specific conditions can be separated by delamination, adhesion in a mode that does not exhibit re-adhesiveness and adhesiveness after separation is referred to as "pseudo-adhesion".
  • two layers that are quasi-adhered to each other may be referred to as “pseudo-adhesion layers”.
  • the peeled base material or the peeled resin layer-attached base material may be collectively referred to as “separated base material", and the member of the multilayer label remaining after the separation base material is peeled off may be referred to as "residual member”.
  • the resin layer on the side of the remaining member that is quasi-bonded may be referred to as a "residual resin layer”
  • the resin layer on the side of the separation substrate may be referred to as a "separated resin layer”.
  • the pseudo-adhesive layers of a multilayer label are required to have both good pseudo-adhesiveness, that is, adhesiveness to the extent that they do not come off unintentionally, and releasability to the extent that they can be easily removed by hand. Furthermore, when managing the peeled separation base material as a slip, various performances are required even after peeling, such as ease of handling of the peeled separation base material and ease of disposal of the separation base material and the remaining members. Sometimes.
  • a pseudo-adhesion laminate having a good pseudo-adhesion property of the pseudo-adhesion layer includes a substrate and a pseudo-adhesion layer laminated on one surface of the substrate, and the pseudo-adhesion layer discloses a pseudo-adhesive laminate containing an olefinic resin, an emulsifier having a melting point of 25° C. or higher, and a release agent.
  • the delivery slip may be attached to a position where it is stacked on both the packing material such as cardboard and the tape for sealing the packing material.
  • the residual resin layer remains in a state straddling over the packing material and the tape.
  • delivery slips are sometimes used in such a manner that only part of the separation base material constituting the multilayer label is peeled off.
  • the separation substrate may also remain in a state straddling over the packing material and the tape. If an attempt is made to peel the tape from the packing material in this state, the resin layer may become an obstacle and the tape may not be easily peeled off.
  • the present invention has been made in view of the above problems, and has a substrate, one or more resin layers, and an adhesive layer in this order, and the substrate and the one or more layers A multilayer label in which any one of the layers of a laminated structure composed of resin layers is releasably adhered, wherein the material forming the resin layer has a low environmental impact and the releasably adhered layers have a peeling force.
  • a multi-layer label which has an appropriate tear resistance and is excellent in tearability.
  • the present inventors have found that the above problems can be solved by using a biodegradable resin and a filler having a specific particle size as the material for forming the resin layer, and have completed the present invention.
  • the present invention relates to the following [1] to [12].
  • [1] having a substrate, a resin layer, and one or more adhesive layers in this order, Any layer of a laminated structure composed of the base material and the one or more resin layers is detachably adhered, At least one of the one or more resin layers contains a biodegradable resin (A) and a resin layer (B) having an average particle diameter (D 50 ) of 0.1 to 20 ⁇ m ( X), a multi-layer label.
  • A biodegradable resin
  • B having an average particle diameter (D 50 ) of 0.1 to 20 ⁇ m ( X)
  • FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the multilayer label of the present embodiment
  • FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the multilayer label of the present embodiment
  • It is a schematic diagram for demonstrating the peelability evaluation method.
  • the lower and upper limits described stepwise can be independently combined.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
  • the multilayer label of this embodiment is Having a substrate, one or more resin layers, and an adhesive layer in this order, Any layer of a laminated structure composed of the base material and the one or more resin layers is detachably adhered, At least one resin layer among the one or more resin layers is a biodegradable resin (A) and a filler (B) having an average particle size (D 50 ) of 0.1 to 20 ⁇ m (hereinafter simply referred to as “filler (B)” is a resin layer (X) containing It is a multilayer label.
  • FIG. 1(a) shows a schematic cross-sectional view of a multilayer label 1a that is an example of the present embodiment.
  • the multilayer label 1a has a structure in which a substrate 10, a resin layer (X), and an adhesive layer 20 are directly laminated in this order.
  • the interlayer S between the substrate 10 and the resin layer (X) is detachably adhered.
  • the adhesion between the base material 10 and the resin layer (X) corresponds to pseudo-adhesion, which does not show re-adhesion or stickiness after peeling.
  • FIG. 1(a) shows a schematic cross-sectional view of a multilayer label 1a that is an example of the present embodiment.
  • the multilayer label 1a has a structure in which a substrate 10, a resin layer (X), and an adhesive layer 20 are directly laminated in this order.
  • the interlayer S between the substrate 10 and the resin layer (X) is detachably adhered.
  • FIG. 1(b) shows a schematic cross-sectional view of a multilayer label 1b that is another example of the present embodiment.
  • the multilayer label 1b has a configuration in which a release sheet 30 is attached to the surface of the adhesive layer 20 of the multilayer label 1a shown in FIG. 1(a).
  • FIG. 2 shows a schematic cross-sectional view of a multilayer label 2 that is an example of this embodiment.
  • the multilayer label 2 has a configuration in which a substrate 10, a first resin layer (X), a second resin layer (X), and an adhesive layer 20 are laminated in this order.
  • the interlayer S1 between the resin layer (X) and the second resin layer (X) is detachably adhered.
  • the multilayer label according to the present embodiment includes a resin layer (X) and a resin layer that does not contain at least one of the biodegradable resin (A) and the filler (B) (hereinafter also referred to as "resin layer (Y)"). may or may not have Next, the configuration of a multilayer label having a resin layer (Y) together with the resin layer (X) will be described.
  • FIG. 3(a) shows a cross-sectional schematic diagram of a multilayer label 3 having a resin layer (Y), which is another example of the multilayer label of the present embodiment.
  • the multilayer label 3 has a configuration in which a substrate 10, a resin layer (Y), a resin layer (X), and an adhesive layer 20 are laminated in this order.
  • the interlayer S2 between the substrate 10 and the resin layer (Y) or the interlayer S3 between the resin layer (Y) and the resin layer (X) are detachably adhered.
  • FIG. 3(b) shows a schematic cross-sectional view of a multilayer label 4, which is another example of a multilayer label having a resin layer (Y).
  • the multilayer label 4 has a configuration in which a substrate 10, a resin layer (X), a resin layer (Y), and an adhesive layer 20 are laminated in this order.
  • the interlayer S4 between the substrate 10 and the resin layer (X) or the interlayer S5 between the resin layer (X) and the resin layer (Y) are detachably adhered.
  • the configuration of the multilayer label according to the present embodiment preferably does not have a resin layer (Y) from the viewpoint of further enhancing the effects of the present invention, which is shown in FIG.
  • the base material, the resin layer (X), and the adhesive layer 20 are laminated in this order, and the base material and the resin layer (X) are releasably adhered. is more preferable.
  • Each constituent member of the multilayer label of this embodiment will be described in detail below.
  • the base material of the multilayer label according to this embodiment is not particularly limited, and is appropriately selected according to the purpose of use of the multilayer label.
  • substrates include paper substrates such as woodfree paper, kraft paper, glassine paper, parchment paper, rayon paper, gravure paper, art paper, coated paper, recycled paper, and synthetic paper; Resin films such as resins, polyvinylidene chloride-based resins, and polyolefin-based resins; laminated sheets obtained by laminating two or more layers of these; and the like.
  • the substrate is preferably a paper substrate, more preferably thermal paper, kraft paper, fine paper, or glassine paper, and still more preferably thermal paper.
  • the substrate is preferably an information display substrate that displays information about the adherend.
  • the information on the adherend includes the sender, the destination, the name or name of the delivery company, the address, the telephone number, the contents of the article to be delivered, a two-dimensional barcode, and the like.
  • the substrate of the multilayer label according to the present embodiment preferably has thermochromic properties from the viewpoint of use as an information display substrate. Printing and printing by a thermal printer or the like become possible when the base material has thermochromic properties. It is preferable that the substrate having thermochromic properties has a thermochromic layer provided on the surface of the substrate opposite to the resin layer.
  • the thermosensitive coloring layer include those containing a leuco dye and a developer that reacts with the leuco dye.
  • the thermosensitive color-developing layer is formed, for example, by applying a coating liquid containing the leuco dye and the developer as well as a binder, wax, solvent, etc., to the surface of the substrate opposite to the resin layer. It is formed.
  • the basis weight of the paper base material is not particularly limited, but is preferably 10 to 100 g/m 2 , more preferably 20 to 90 g/m 2 , still more preferably 40 to 80 g/m 2 . 2 .
  • the basis weight of the paper substrate is within the above range, the strength of the substrate and the peel strength between the pseudo-adhesive layers tend to be better.
  • the thickness of the substrate is not particularly limited, it is preferably 10 to 250 ⁇ m, more preferably 20 to 200 ⁇ m, still more preferably 30 to 150 ⁇ m.
  • the thickness of the base material is at least the above lower limit, it tends to be possible to suppress the occurrence of wrinkles, tears, and the like in the base material.
  • the thickness of the base material is equal to or less than the above upper limit value, the base material tends to be economically efficient, and the rigidity does not become too high, and the transportability and handleability when performing printing and printing with a printer or the like tend to be excellent.
  • the "thickness of the base material” means the thickness of the entire base material. means.
  • the multilayer label according to the present embodiment has one or more resin layers, and at least one of the one or more resin layers contains a biodegradable resin (A) and an average particle size (D 50 ).
  • biodegradable resin (A) examples include polyesters such as aliphatic polyesters, aliphatic polyester carbonates, aliphatic polyester amides, and aliphatic polyester ethers; polyvinyl alcohol; polyamino acids; cellulose, cellulose acetate, hydroxyethyl cellulose, hydroxyl polysaccharides such as propylcellulose, starch, chitin, chitosan, mannan; and other thermoplastic resins.
  • polyesters are preferred, and aliphatic polyesters and derivatives thereof are more preferred.
  • polyesters and derivatives thereof examples include polybutylene succinate resins, polycaprolactone, polybutylene adipate terephthalate, polylactic acid, and polyesters containing 3-hydroxyalkanoic acid as monomer units.
  • polybutylene succinate-based resins are preferred from the viewpoint of moldability and biodegradability.
  • the melting point of the biodegradable resin (A) is not particularly limited, it is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher.
  • the melting point of the biodegradable resin (A) is equal to or higher than the above lower limit, it is possible to prevent the resin layer (X) from melting under the general usage environment of the multilayer label according to the present embodiment. As a result, unintentional peeling of the resin layer (X) as the pseudo-adhesive layer due to melting of the resin layer (X) can be suppressed.
  • the upper limit of the melting point of the biodegradable resin (A) is not particularly limited, it is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower.
  • the melting point of the biodegradable resin (A) is equal to or lower than the above upper limit, the biodegradable resin (A) can be easily processed, and the productivity of the multilayer label tends to be excellent.
  • the melting point of the biodegradable resin (A) can be measured by the method described in Examples.
  • the glass transition temperature (Tg) of the biodegradable resin (A) is not particularly limited, but is preferably 0°C or lower, more preferably -10°C or lower, and still more preferably -20°C or lower.
  • the resin layer (X) has appropriate flexibility under the general usage environment of the multilayer label according to the present embodiment. will have As a result, unintentional peeling of the resin layer (X) as the pseudo-adhesive layer due to bending, impact, or the like can be suppressed.
  • the lower limit of the glass transition temperature (Tg) of the biodegradable resin (A) is not particularly limited, but in consideration of the balance with other physical properties, it may be, for example, -150°C or higher, or -100°C. or higher, or -50° C. or higher.
  • the glass transition temperature of the biodegradable resin (A) can be measured by the method described in Examples.
  • the biodegradable resin (A) preferably has a glass transition temperature of 0°C or lower and a melting point of 40°C or higher.
  • the glass transition temperature and the melting point of the biodegradable resin (A) are within the above ranges, it is possible to achieve a high degree of compatibility between the effects obtained from both physical properties.
  • the content of the biodegradable resin (A) with respect to the total amount (100 parts by mass) of the resin contained in the resin layer (X) is not particularly limited, but from the viewpoint of further reducing the environmental load, it is preferably 80. ⁇ 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, still more preferably 99 to 100% by mass.
  • the multilayer label according to the present embodiment has excellent tearability, and is less likely to become an obstacle when the packing material is opened.
  • the filler (B) promotes the biodegradability of the biodegradable resin (A)
  • the multilayer label according to this embodiment has a much smaller environmental load.
  • a filler (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the filler (B) contained in the resin layer (X) has an average particle size (D 50 ) of 0.1 to 20 ⁇ m.
  • the average particle size (D 50 ) of the filler (B) is 0.1 ⁇ m or more, the tearability of the resin layer (X) becomes sufficiently good.
  • the average particle diameter (D 50 ) of the filler (B) is 20 ⁇ m or less, the peeling force of the resin layer (X) as a pseudo-adhesive layer becomes too small due to the unevenness of the filler (B). can be suppressed, resulting in a multilayer label having good peel strength.
  • the average particle diameter (D 50 ) of the filler (B) is preferably 0.5 to 15 ⁇ m, more preferably 0.8 to 10 ⁇ m.
  • the average particle size (D 50 ) of the filler (B) in the present embodiment is the volume-median particle size (D 50 ), which can be measured by the method described in Examples.
  • the filler (B) may have been subjected to surface modification treatment, but is preferably not subjected to surface modification treatment with an organic component.
  • the filler (B) is not subjected to a surface modification treatment with an organic component, excessive adhesion between the biodegradable resin (A) and the filler (B) is suppressed, and tearability is improved. tend to be better.
  • shape of filler (B) is not particularly limited, it is preferably non-spherical.
  • the non-spherical shape of the filler (B) tends to improve the tearability of the resin layer (X).
  • non-spherical as used in the present embodiment means a three-dimensional shape other than a spherical shape, such as polygonal, plate-like, flake-like, angular, needle-like, rod-like, and the like.
  • the filler (B) preferably has a polygonal shape.
  • the polygonal filler (B) preferably has an irregular shape, more preferably a crushed shape.
  • the shape of the filler (B) can be confirmed, for example, with a scanning electron microscope (SEM).
  • the content of the filler (B) in the resin layer (X) is not particularly limited, but is preferably 1 to 50% by volume, more preferably 4 to 50% by volume, relative to the volume (100% by volume) of the resin layer (X). 45% by volume, more preferably 7 to 40% by volume.
  • the content of the filler (B) in the resin layer (X) is at least the above lower limit, the tearability tends to be better.
  • the content of the filler (B) in the resin layer (X) is equal to or less than the above upper limit value, the peeling force of the resin layer (X) as a pseudo-adhesive layer is reduced due to the unevenness of the filler (B). It tends to be possible to prevent it from becoming too small.
  • the total content of the biodegradable resin (A) and the filler (B) in the resin layer (X) is not particularly limited, but is preferably 50 to 50% with respect to the mass (100% by mass) of the resin layer (X). 100 mass %, more preferably 70 to 100 mass %, still more preferably 90 to 100 mass %, still more preferably 95 to 100 mass %.
  • the total content of the biodegradable resin (A) and the filler (B) is within the above range, the environmental load of the material forming the resin layer (X) is sufficiently reduced, and excellent tearability is easily obtained. There is a tendency.
  • the thickness of the resin layer (X) is not particularly limited, it is preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m, still more preferably 15 to 30 ⁇ m.
  • the thickness of the resin layer (X) is at least the above lower limit, it becomes easier to form the resin layer (X) with a uniform thickness, and the peel force of the resin layer (X) as the pseudo-adhesive layer is set within an appropriate range. It tends to be easier to adjust to Further, when the thickness of the resin layer (X) is equal to or less than the above upper limit, the environmental load can be further reduced, and the peeling force of the resin layer (X) as a pseudo-adhesive layer tends to be better.
  • the resin layer (Y) that the multilayer label according to the present embodiment may have, a resin layer containing the biodegradable resin (A) and not containing the filler (B), a biodegradable resin layer containing the filler (B), Examples include a resin layer containing no degradable resin (A), a resin layer containing neither biodegradable resin (A) nor filler (B), and the like.
  • a resin layer containing a biodegradable resin (A) and not containing a filler (B), a biodegradable resin containing a filler (B) A resin layer that does not contain A) is preferred.
  • the description of the biodegradable resin (A) and the filler (B) that the resin layer (Y) may contain is as described for the biodegradable resin (A) and the filler (B) that the resin layer (X) contains. be.
  • resins other than the biodegradable resin (A) that may be contained in the resin layer (Y) include polyolefin resins, polyester resins, polyamide resins, etc., which are not biodegradable resins. These may be used individually by 1 type, and may use 2 or more types together.
  • the pressure-sensitive adhesive layer of the multilayer label is a layer for attaching the multilayer label to an adherend, and is appropriately selected according to the application of the multilayer label.
  • the adhesive layer is formed from, for example, an acrylic adhesive, a natural rubber adhesive, a synthetic rubber adhesive, a silicone adhesive, or the like.
  • acrylic pressure-sensitive adhesives are preferred from the viewpoint of weather resistance and economy.
  • acrylic pressure-sensitive adhesives include solvent-type acrylic pressure-sensitive adhesives and water-based emulsion-type acrylic pressure-sensitive adhesives.
  • One type of adhesive may be used alone, or two or more types may be used in combination.
  • the pressure-sensitive adhesive may or may not contain additives for pressure-sensitive adhesives used in general pressure-sensitive adhesives, other than the base polymer and the tackifier, as long as the effects of the present invention are not impaired. good too.
  • adhesive additives include fillers, softeners, heat and light stabilizers, antioxidants, and cross-linking agents. Each of these adhesive additives may be used alone or in combination of two or more.
  • the adhesive contains a pressure-sensitive adhesive additive, the content is not particularly limited, but is preferably 0.0001 to 20 parts by mass, more preferably 0.0001 to 20 parts by mass, based on 100 parts by mass of the main polymer of the adhesive. 01 to 15 parts by mass, more preferably 1 to 10 parts by mass.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is preferably 1 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, still more preferably 10 to 30 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is at least the above lower limit, it tends to be easy to form a pressure-sensitive adhesive layer with a uniform thickness and to obtain stable adhesive strength.
  • productivity and economy tend to be excellent.
  • the peel force between layers that are releasably adhered is preferably 100 to 1,000 mN/50 mm, more preferably 200 ⁇ 850 mN/50 mm, more preferably 250 to 700 mN/50 mm, even more preferably 300 to 650 mN/50 mm.
  • the peel force between the layers that are releasably adhered is equal to or higher than the above lower limit, there is a tendency that unintentional delamination of the pseudo adhesive layer can be suppressed.
  • the peel strength between the layers that are releasably adhered is equal to or less than the above upper limit, it becomes easier to peel off by hand, and when the separation base material is peeled off, it tends to be possible to suppress the breakage of the separation base material. be.
  • the peel strength between layers that are releasably adhered is a value measured in accordance with JIS Z 0237: 2000 "180° peeling adhesive strength to test plate". It can be measured by the method described in .
  • the multilayer label according to this embodiment may or may not have layers other than the substrate, one or more resin layers, and the pressure-sensitive adhesive layer.
  • the positions of the other layers are not particularly limited.
  • they may have the same composition or may have different compositions.
  • Other layers include, for example, the heat-sensitive coloring layer described above and a release sheet provided on the surface of the pressure-sensitive adhesive layer opposite to the resin layer.
  • Base materials for release sheets include, for example, papers such as woodfree paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; plastic films such as olefin resin films; and the like.
  • release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and the like.
  • rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and the like.
  • the thickness of the release sheet is not particularly limited, it is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, still more preferably 30 to 150 ⁇ m from the viewpoint of economy and handling.
  • Total thickness of multilayer label is not particularly limited, it is preferably 50 to 300 ⁇ m, more preferably 70 to 200 ⁇ m, still more preferably 90 to 150 ⁇ m.
  • the thickness of the release sheet is not included in the total thickness of the multilayer label.
  • the shape of the multilayer label when viewed from above is not particularly limited, and examples thereof include polygons such as rectangles and triangles; circles, ellipses, irregular shapes; and the like.
  • the multilayer label according to this embodiment can be manufactured, for example, by a manufacturing method including the following steps P1 and P2.
  • Step P1 Step of forming one or more resin layers on one surface of the substrate to obtain a resin layer-attached substrate
  • Step P2 Forming an adhesive layer on the resin layer of the resin layer-attached substrate obtained in Step P1 lamination process
  • Step P1 is a step of forming one or more resin layers on one surface of a substrate to obtain a substrate with a resin layer. At least one of the one or more resin layers is the resin layer (X).
  • the method for forming one or more resin layers on one surface of the substrate is not particularly limited, and examples include a method of melt extruding a resin layer-forming material onto the substrate, and a method of extruding a resin layer-forming material onto the substrate. and the like. Among these, the method of melt extruding the resin layer-forming material is preferable from the viewpoint of productivity.
  • Examples of the method of melt extruding the resin layer-forming material onto the substrate include a method of extruding a melted resin layer-forming material onto the substrate to form a layer using an extruder and a T-die. .
  • the resin for the second and subsequent layers is placed on the first resin layer. It may be a method of sequentially forming by extruding the layer-forming materials sequentially, or a co-extrusion method of simultaneously forming a plurality of resin layers by simultaneously melt-extruding a plurality of resin layer-forming materials from a plurality of extruders. good too.
  • the melt extrusion temperature of the resin layer-forming material is not particularly limited, and may be appropriately set according to the type of resin constituting the resin layer. is 180-220°C. After the resin layer-forming material is melt-extruded, the formed resin layer may be cooled and solidified.
  • a coating liquid of the resin layer-forming material obtained by dissolving and dispersing the biodegradable resin (A) and the filler (B) in a solvent is applied to the substrate.
  • a method of forming a resin layer by coating on the surface and then drying may be mentioned.
  • the one or more resin layers are a plurality of resin layers, after forming a coating film by applying the coating liquid of the resin layer forming material for the first layer on the substrate, the second layer is formed on the coating film. It may be a method of successively applying coating liquids of subsequent resin layer forming materials, or a method of simultaneously forming a plurality of resin layers by simultaneously applying coating liquids of a plurality of resin layer forming materials. may
  • Examples of methods for applying the coating liquid of the resin layer-forming material include roll coating, spin coating, spray coating, bar coating, knife coating, roll knife coating, blade coating, die coating, and gravure coating. law, etc.
  • Step P2 is a step of laminating an adhesive layer on the resin layer of the substrate with a resin layer obtained in step P1.
  • an adhesive layer is formed by coating a release sheet with an adhesive composition containing a material constituting the adhesive layer and then drying it as necessary. and sticking the pressure-sensitive adhesive layer to the resin layer of the base material with the resin layer.
  • the resin layer A method of forming a pressure-sensitive adhesive layer on the surface of After that, if necessary, a release sheet may be attached to the surface of the pressure-sensitive adhesive layer.
  • the method of applying the pressure-sensitive adhesive composition includes the same method as the method of applying the coating liquid of the resin layer-forming material.
  • the adhesive layer may be formed after surface treatment or the like is applied to the surface of the resin layer on which the adhesive layer is laminated.
  • surface treatment methods include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, ozone irradiation treatment, ultraviolet irradiation treatment, and ultraviolet-ozone treatment. oxidizing method; roughening method such as sandblasting method and solvent treatment method; and the like.
  • the multilayer label may be punched as appropriate.
  • the release sheet may be punched using a punching blade along the outline of a predetermined multilayer label, or the base material and the adhesive layer may be cut so as not to punch the release sheet, and then peeled off.
  • a plurality of multilayer labels may be arranged on the sheet. Moreover, if necessary, unnecessary portions around the outer contour of each multilayer label may be removed from the release sheet as waste.
  • the multilayer label according to this embodiment is preferably a multilayer label for delivery slips.
  • a half-cut line is provided in the base material of the multilayer label so that the base material can be separated into a plurality of pieces and peeled off.
  • One piece of base material separated by the half-cut line is used as a delivery slip, and the other piece of base material is used as a receipt slip.
  • the receipt is usually stamped or signed by the recipient, then peeled off, taken home by the delivery company, and used for sorting slips and the like.
  • the multilayer label according to the present embodiment has a small environmental load and is easy to dispose of, it is suitable for applications other than delivery slips, such as postcards and tamper-proof labels.
  • the melting point of the resin was measured according to JIS K 7121:1987 by the following procedure. About 5 mg of the sample is put into an aluminum pan, and a differential scanning calorimeter (DSC) (manufactured by TA Instruments, product name "Q2000") is used to measure the temperature range from -120 to 200 ° C. under a nitrogen atmosphere. , and a temperature increase rate of 10° C./min. The melting point of the resin was obtained by analyzing the obtained DSC curve according to JIS K 7121:1987. The presence or absence of crystallinity of the resin was determined by the presence of a melting point peak, and all the resins used in Examples and Comparative Examples described later had crystallinity.
  • DSC differential scanning calorimeter
  • the glass transition temperature (Tg) of the resin was measured according to JIS K 7121:1987 by the following procedure. About 5 mg of the sample is put into an aluminum pan, and a differential scanning calorimeter (DSC) (manufactured by TA Instruments, product name "Q2000") is used to measure the temperature range from -120 to 200 ° C. under a nitrogen atmosphere. , and a temperature increase rate of 10° C./min. The glass transition temperature of the resin was obtained by analyzing the obtained DSC curve according to JIS K 7121:1987.
  • DSC differential scanning calorimeter
  • a pressure-sensitive adhesive composition 100 parts by mass of acrylic pressure-sensitive adhesive and 7.5 parts by mass of rosin-based tackifier were mixed to prepare a pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition is applied onto a release sheet (manufactured by Lintec Corporation, trade name "8K Blue") using a roll coater, and then dried to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m on the release sheet. formed.
  • a release sheet manufactured by Lintec Corporation, trade name "8K Blue
  • the adhesive layer, the release sheet in this order to obtain a multilayer label in which the paper substrate and the resin layer are releasably adhered.
  • Comparative example 2 A multilayer label was obtained in the same manner as in Example 1, except that no filler was added to the resin layer-forming material.
  • the peel strength between the base material and the resin layer was measured according to the following procedure according to JIS Z 0237:2000 "180° peeling adhesive strength to test plate".
  • the multi-layer label produced in each example was cut into a size of 50 mm in width and 150 mm in length, and the release sheet was removed to prepare a multi-layer label for evaluation. Then, the multi-layer label for evaluation was attached and fixed to the surface of the SUS plate with the pressure-sensitive adhesive layer as the attachment surface. Subsequently, at one end of the multi-layer label for evaluation on the SUS plate, the paper substrate was peeled off from the resin layer by 40 mm.
  • the part of the peeled paper substrate was fixed to a chuck of a tensile tester, and the paper substrate was peeled off from the resin layer using the tensile tester under the conditions of a peeling speed of 0.3 m/min and a peeling angle of 180°. , 4-point peel force was measured at 20 mm intervals. Three multilayer labels for evaluation were tested, and the peel force was calculated as the average value of the 12 measured points.
  • a multi-layer label 1 for evaluation was prepared by cutting the multi-layer label prepared in each example into a size of 80 mm long ⁇ 40 mm wide and removing the release sheet.
  • a cloth tape (No. 111, manufactured by Okamoto Co., Ltd.) 60 having a length of 160 mm and a width of 50 mm was attached to the surface of the cardboard 50 .
  • one end of the cloth tape 60 attached to the cardboard 50 is peeled off by about 20 mm, and the peeled portion is grasped with fingers, and the cloth tape 60 is peeled from one longitudinal end to the other end (Fig. 4) at a peeling angle of about 135°. (Z direction)), thereby tearing the resin layer.
  • the longest distance from the boundary between the corrugated board 50 and the fabric tape 60 to the edge of the torn resin layer was measured and evaluated according to the following criteria.
  • the evaluation was based on a test (i) in which the flow direction when the resin layer was extruded and formed was parallel to the direction in which the cloth tape 60 was peeled off, and a test (i) in which the flow direction was the direction in which the cloth tape 60 was peeled off.
  • Both tests (ii) of application perpendicular to the [Evaluation Criteria for Tearability] A: The longest distance of the resin layer was less than 5 mm in both tests (i) and (ii).
  • B Among tests (i) and (ii), the longest distance of the resin layer was 5 mm or more and less than 10 mm.
  • C Among Tests (i) and (ii), the longest distance of the resin layer was 10 mm or more and less than 20 mm.
  • D Among tests (i) and (ii), the longest distance of the resin layer was 20 mm or more.
  • F In tests (i) and (ii), at least one of the resin layers was peeled off from the cardboard 50 without being torn.
  • the multilayer labels of Examples 1 to 8 of the present embodiment have the same peel strength as the multilayer label of Comparative Example 1 using conventional low-density polyethylene for the resin layer, but they are biodegradable. It can be seen that the use of the flexible resin (A) has a small environmental load and is excellent in tearability. On the other hand, the multilayer label of Comparative Example 2, in which no filler was added to the resin layer, was inferior in tearability.
  • the multilayer label of Comparative Example 3 in which the filler had an average particle diameter (D 50 ) of less than 0.1 ⁇ m, was inferior in tearability to the multilayer labels of Examples 1 to 8, and the average filler particle diameter (D 50 ) of more than 20 ⁇ m, the multilayer label of Comparative Example 4 had a small peeling force between the substrate and the resin layer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une étiquette multicouche comportant un substrat, une ou plusieurs couches de résine et une couche adhésive dans l'ordre indiqué. Toute couche intermédiaire dans une structure stratifiée composée du substrat et de la ou des couches de résine est liée de manière détachable et au moins une couche de résine parmi la ou les couches de résine est une couche de résine (X) comprenant une résine biodégradable (A) et une charge (B), dont le diamètre de particule moyen (D50) est de 1 à 20 µm.
PCT/JP2022/013336 2021-03-25 2022-03-23 Étiquette multicouche WO2022202856A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH079642A (ja) * 1993-06-25 1995-01-13 Sekisui Chem Co Ltd 表面保護フイルム
JP2005140939A (ja) * 2003-11-06 2005-06-02 Sekisui Seikei Ltd 印刷テープ
US20090117377A1 (en) * 2007-11-07 2009-05-07 Michael Hacikyan Degradable paper with long-shelf-life adhesive backing
JP2009208392A (ja) * 2008-03-05 2009-09-17 Lintec Corp 配送用積層シート、その製造方法及び配送伝票
JP2016061929A (ja) * 2014-09-18 2016-04-25 リンテック株式会社 擬似接着ラベル及び擬似接着ラベルの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH079642A (ja) * 1993-06-25 1995-01-13 Sekisui Chem Co Ltd 表面保護フイルム
JP2005140939A (ja) * 2003-11-06 2005-06-02 Sekisui Seikei Ltd 印刷テープ
US20090117377A1 (en) * 2007-11-07 2009-05-07 Michael Hacikyan Degradable paper with long-shelf-life adhesive backing
JP2009208392A (ja) * 2008-03-05 2009-09-17 Lintec Corp 配送用積層シート、その製造方法及び配送伝票
JP2016061929A (ja) * 2014-09-18 2016-04-25 リンテック株式会社 擬似接着ラベル及び擬似接着ラベルの製造方法

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