TW202302362A - Multilayer label - Google Patents

Abstract

The present invention pertains to a multilayer label having a base material, a resin layer, and an adhesive layer in the stated order. The base material and the resin layer are detachably adhered. The resin layer contains a biodegradable resin (A) and a filler (B).

Description

multi-layer label

This invention relates to multi-layer labels.

Traditionally, multi-layer labels with a multi-layer structure are widely used for consignment notes for distribution goods. This multi-layer label usually includes a substrate for printing information such as thermal paper, a resin layer (hereinafter also referred to as "intermediate resin layer") attached to the substrate in a detachable manner, and an adhesive for attaching to the goods. layer, the base material and the intermediate resin layer used are those that are difficult to adhere to each other after peeling off once. In addition, among the layers bonded under such specific conditions, the bond can be peeled by the peeling between the layers, and the state of not showing re-adhesiveness and adhesiveness after peeling is sometimes called "false bonding".

The base material and the intermediate resin layer of the multi-layer label need to have good pseudo-adhesiveness, that is, adhesiveness to the extent that it cannot be accidentally peeled off, and peelability to the extent that it can be easily removed by hand. In addition, when the peeled base material is managed as a receipt, the handleability of the peeled base material, the ease of disposal of the base material and the remaining parts after peeling the base material, etc. are required, and even after the peeling, it may be Various properties are required.

Patent Document 1 discloses a pseudo-adhesive laminate. As a pseudo-adhesive laminate having good pseudo-adhesive properties, a pseudo-adhesive layer is provided with a substrate and a pseudo-adhesive layer laminated on one side of the substrate. The dummy adhesive layer contains an olefin resin, an emulsifier with a melting point of 25°C or higher, and a release agent. Prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2019-147898

The problem to be solved by the invention

In addition, in recent years, due to increasing awareness of environmental issues, environmental pollution when discarding plastic materials derived from petroleum has been recognized as a problem. The olefin-based resin used in the pseudo-adhesive laminate of Patent Document 1 may affect the environment due to disposal such as incineration or landfill. Therefore, it is desired to form the intermediate resin layer using a material with a small environmental load while maintaining the peeling force between the base material and the resin layer within a good range.

In addition, the consignment note may be attached to a position laminated on both the packaging material such as corrugated cardboard and the tape for sealing the packaging material. In this case, after the base material is peeled off, the intermediate resin layer remains in a state straddling the packaging material and the adhesive tape. If an attempt is made to peel off the tape from the packaging material in this state, the intermediate resin layer may become an obstacle, and the tape may not be easily peeled off. In order to easily open the packaging material even when the consignment note is attached as described above, it is desirable that the portion of the intermediate resin layer itself attached to the tape and the portion attached to the packaging material be torn when the tape is peeled off. However, since a resin having an appropriate peeling force in a practical temperature range tends to have a high initial tear strength to initiate tearing, it is desired to achieve both an appropriate peeling force and excellent tearability.

The present invention is made in view of the above problems. The multilayer label has a base material, a resin layer, and an adhesive layer in sequence, and the base material and the resin layer are bonded in a detachable manner. The purpose is to provide an environment for the material forming the resin layer. A multi-layer label with light load, moderate peeling force between base material and resin layer, and excellent tearability. means to solve problems

The inventors of the present invention found that the above-mentioned problems can be solved by using a biodegradable resin and a filler as materials for forming a resin layer, and completed the present invention.

In other words, the present invention relates to the following [1] to [12]. [1] A multi-layer label that sequentially has a base material, a resin layer, and an adhesive layer, wherein the aforementioned substrate and the aforementioned resin layer are bonded in a detachable manner, and The aforementioned resin layer contains a biodegradable resin (A) and a filler (B). [2] The multilayer label according to the above [1], wherein the biodegradable resin (A) has crystallinity. [3] The multilayer label according to the above [1] or [2], wherein the biodegradable resin (A) has a glass transition temperature of 0°C or lower and a melting point of 40°C or higher. [4] The multilayer label according to any one of the above [1] to [3], wherein the biodegradable resin (A) is a polybutylene succinate-based resin. [5] The multilayer label according to any one of the above [1] to [4], wherein the filler (B) is an inorganic filler. [6] The multilayer label according to the above [5], wherein the inorganic filler is calcium carbonate. [7] The multilayer label according to any one of the above [1] to [6], wherein the filler (B) is non-spherical in shape. [8] The multilayer label according to any one of the above [1] to [7], wherein the filler (B) is not subjected to a surface modification treatment with an organic component. [9] The multilayer label according to any one of [1] to [8] above, wherein the content of the filler (B) in the resin layer is 1 to 50 vol. with respect to the volume (100 vol %) of the resin layer %. [10] The multilayer label according to any one of the above [1] to [9], wherein the base material is a paper base material. [11] The multilayer label according to any one of [1] to [10] above, wherein the peeling force between the base material and the resin layer is 100 to 1,000 mN/50 mm. [12] The multilayer label according to any one of [1] to [11] above, which is used for a consignment note. Invention effect

According to the present invention, the multilayer label sequentially has a base material, a resin layer, and an adhesive layer, and the base material and the resin layer are bonded in a detachable manner, so that the environmental load of the material forming the resin layer is small, and the base material and the resin layer can be provided. A multi-layer label with moderate peel force and excellent tearability.

Hereinafter, the present invention will be described in detail using embodiments.

In the present specification, regarding preferable numerical ranges (for example, ranges of content, etc.), the lower limit and upper limit described in paragraphs can be combined independently of each other. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", it can be obtained by combining "preferable lower limit (10)" and "more preferable upper limit (60)" "10~60". Within the numerical range described in this specification, the upper limit or lower limit of this numerical range may be replaced with the value shown in the Example. The mechanism of action described in this specification is speculative and does not limit the mechanism for achieving the effects of the present invention.

[multi-layer label] The multi-layer label of this implementation type is Sequentially have a base material, a resin layer and an adhesive layer, The aforementioned substrate and the aforementioned resin layer are bonded in a detachable manner, and The aforementioned resin layer contains biodegradable resin (A) and filler (B) multi-layer labels.

Hereinafter, the structure of the multilayer label of this embodiment will be described more concretely with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a multilayer label 1 according to this embodiment. The multilayer label 1 has a structure in which a substrate 10 , a resin layer 20 , and an adhesive layer 30 are directly laminated in this order. In the multilayer label 1 , the interlayer S between the base material 10 and the resin layer 20 is bonded in a peelable manner. The bonding between the base material 10 and the resin layer 20 does not exhibit re-adhesiveness and adhesiveness after peeling, and corresponds to pseudo bonding. In addition, FIG. 2 is a schematic cross-sectional view showing another example of a multilayer label 2 of the present embodiment. The multilayer label 2 has a configuration in which a release sheet 40 is attached to the surface of the adhesive layer 30 of the multilayer label 1 shown in FIG. 1 . Each constituent member of the multilayer label of this embodiment will be described in detail below.

＜Substrate＞ The base material of the multilayer structure according to this embodiment is not particularly limited, and can be appropriately selected according to the purpose of use of the multilayer label. As the base material, for example, paper base materials such as wood paper, kraft paper, cellophane, parchment paper, rayon (rayon) paper, gravure paper, coated paper, coated paper, recycled paper, synthetic paper, etc.; Resin films of vinyl chloride-based resins, polyvinylidene chloride-based resins, polyolefin-based resins, etc.; laminated sheets in which two or more layers are laminated; etc. Among them, the base material is preferably a paper base material, more preferably thermal paper, kraft paper, Dowling paper, cellophane, and even more preferably thermal paper.

In the multilayer label according to this embodiment, the substrate is preferably an information display substrate for displaying information on an adherend. As the information on the adherend, for example, when the adherend is a consignment, the name of the sender, destination, shipper, address, telephone number, contents of the cargo, two-dimensional bar code, etc. are listed.

From the viewpoint of use as a substrate for information display, the substrate having the multilayer label according to the present embodiment preferably has thermochromic properties. Since the base material has heat-sensitive color rendering property, it can be printed and printed by heat-sensitive printers, etc. The substrate having thermochromic properties is preferably one in which a thermochromic layer is provided on the surface of the substrate opposite to the resin layer. As a thermosensitive color-developing layer, the thing containing a leuco dye and the color developer which reacts with a leuco dye is mentioned, for example. The heat-sensitive color developer, for example, in addition to the above-mentioned invisible dye and color developer, can also be obtained by appropriately applying a coating liquid containing a binder (binder), wax, solvent, etc. to the surface of the substrate opposite to the resin layer. formed on top.

(Basis Weight of Substrate) When a paper substrate is used as the substrate, the basis weight of the paper substrate is not particularly limited, but is preferably 10 to 100 g/m ² , more preferably 20 to 90 g/m ² , and More preferably, it is 40 to 80 g/m ² . When the basis weight of the paper base material is within the above range, the strength of the base material and the peeling force between the base material and the resin layer tend to be improved.

(thickness of substrate) The thickness of the substrate is not particularly limited, but is preferably 10-250 μm, more preferably 20-200 μm, and still more preferably 30-150 μm. When the thickness of the base material is more than the aforementioned lower limit, it tends to be possible to suppress the occurrence of wrinkles, cracks, and the like of the base material. In addition, when the thickness of the base material is not more than the above upper limit, economical efficiency tends to be excellent, rigidity does not become too high, and transportability and operability at the time of printing and printing with a printer or the like tend to be excellent. In addition, the "thickness of the substrate" refers to the thickness of the entire substrate, and when the substrate is composed of a plurality of layers, it refers to the total thickness of all the layers constituting the substrate.

＜Resin layer＞ The resin layer of the multilayer label according to this embodiment contains a biodegradable resin (A) and a filler (B).

(Biodegradable resin (A)) The biodegradable resin (A) is not particularly limited as long as it is a biodegradable resin, and may be a biodegradable resin derived from organisms or a biodegradable resin derived from petroleum. Since the multilayer label according to this embodiment uses the biodegradable resin (A) for the resin layer, there is no need to worry about environmental pollution when discarded like conventional polyethylene resins, and the environmental load is small. In addition, in the present embodiment, "biodegradability" refers to the property of being chemically decomposed by, for example, hydrolysis, enzymatic decomposition, microbial decomposition, and the like. Biodegradable resins (A) may be used alone or in combination of two or more.

The biodegradable resin (A) is preferably a crystalline resin. Since the biodegradable resin (A) has crystallinity, the generation of tack on the surface of the resin layer can be suppressed within the temperature range of use, and the workability tends to be improved. At the same time, the peeling force between the base material and the resin layer can be suppressed. too big. Furthermore, since the biodegradable resin (A) has crystallinity, the resin layer tends to have more excellent tearability. Whether or not the biodegradable resin (A) has crystallinity can be confirmed by a differential scanning calorimeter (DSC), specifically, by the method described in Examples.

Examples of the biodegradable resin (A) include polyesters such as aliphatic polyester, aliphatic polyester carbonate, aliphatic polyester amide, and aliphatic polyester ether; polyvinyl alcohol; polyamino acid ; Polysaccharides such as cellulose, cellulose acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, chitin, chitosan, mannan, etc.; thermoplastic resins such as. Among these, polyesters are preferred, and aliphatic polyesters and derivatives thereof are more preferred.

Examples of aliphatic polyesters and derivatives thereof include polybutylene succinate resins, polycaprolactone, polybutylene adipate terephthalate, polylactic acid, A polyester in which oxyalkanoic acid is a monomer unit. Among them, polybutylene succinate-based resins are preferable from the viewpoint of moldability and biodegradability.

Examples of the polybutylene succinate-based resin include polybutylene succinate, polybutylene succinate adipate, and polybutylene succinate lactate.

[Melting point of biodegradable resin (A)] The melting point of the biodegradable resin (A) is not particularly limited, but is preferably 40°C or higher, more preferably 50°C or higher, and still more preferably 80°C or higher. When the melting point of the biodegradable resin (A) is equal to or higher than the above-mentioned lower limit, the resin layer can be prevented from melting under the general use environment of the multilayer label according to the present embodiment. As a result, unintentional peeling of the base material and the resin layer due to melting of the resin layer can be suppressed. The upper limit of the melting point of the biodegradable resin (A) is not particularly limited, but is preferably at most 200°C, more preferably at most 150°C, and even more preferably at most 130°C. When the melting point of the biodegradable resin (A) is not more than the above-mentioned upper limit, the processing of the biodegradable resin (A) becomes easy, and the productivity of a multilayer label tends to be excellent. The melting point of the biodegradable resin (A) can be measured by the method described in Examples.

[Glass transition temperature (Tg) of biodegradable resin (A)] The glass transition temperature (Tg) of the biodegradable resin (A) is not particularly limited, but is preferably at most 0°C, more preferably at most -10°C, and even more preferably at most -20°C. When the glass transition temperature (Tg) of the biodegradable resin (A) is below the above-mentioned upper limit, the resin layer will have appropriate flexibility under the general use environment of the multilayer label related to this embodiment. As a result, unintentional peeling of the base material and the resin 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 may be -150°C or higher, -100°C or higher, or -100°C or higher in consideration of the balance with other physical properties. above -50°C. The glass transition temperature of the biodegradable resin (A) can be measured by the method described in Examples.

From the same viewpoint as above, the biodegradable resin (A) preferably has a glass transition temperature of 0°C or lower and a melting point of 40°C or higher. When the glass transition temperature and the melting point of the biodegradable resin (A) are within the above-mentioned ranges, the effects obtained from the physical properties of both can be highly combined.

〔Content of biodegradable resin (A)〕 The content of the biodegradable resin (A) in the resin layer is not particularly limited, but is preferably 50 to 99 volume %, more preferably 55 to 98 volume %, and still more preferably 60-97% by volume. When content of the biodegradable resin (A) in a resin layer is more than the said lower limit, the peeling force of a base material and a resin layer tends to become favorable. Moreover, when content of the biodegradable resin (A) in a resin layer is below the said upper limit, tearability tends to become favorable.

The content of the biodegradable resin (A) is not particularly limited with respect to the total amount of resin contained in the resin layer (100 parts by mass), but from the viewpoint of further reducing the environmental load, it is preferably 80 to 100 mass %, more preferably 90 to 100% by mass, more preferably 95 to 100% by mass, still more preferably 99 to 100% by mass.

(Filler (B)) The filler (B) is not particularly limited, and known materials can be used. Since the resin layer contains the filler (B), the multilayer label according to the present embodiment has excellent tearability and is less likely to be an obstacle when opening the packaging material. In addition, since the filler (B) promotes the biodegradability of the biodegradable resin (A), the environmental load of the multilayer label related to the present embodiment becomes smaller. The filler (B) may be used alone or in combination of two or more.

The filler (B) may be an inorganic filler or an organic filler, but from the viewpoint of suppressing the melting and deformation of the filler caused by heating during the manufacture of the multilayer label, and having an appropriate water content to promote the hydrolysis of the biodegradable resin (A) From a viewpoint, an inorganic filler is preferable. Examples of inorganic fillers include silica, alumina, glass, metal oxides, sodium carbonate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, magnesium silicate, calcium silicate, silicon Zirconium acid, barium titanate, potassium titanate, calcium titanate, mica, vermiculite, zeolite, barium sulfate, silicon carbide, silicon nitride, etc. Among them, calcium carbonate is preferable.

The filler (B) can also be subjected to surface modification treatment, but it is preferably one that is not subjected to surface modification treatment with an organic component. When the filler (B) is not surface-modified with an organic component, excessive adhesion between the biodegradable resin (A) and the filler (B) tends to be suppressed, and the tear property tends to be improved.

[Average particle diameter (D ₅₀ ) of filler (B)] The average particle diameter (D ₅₀ ) of filler (B) is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and still more preferably 0.8 to 20 μm. 10 μm. When the average particle diameter ( _D50 ) of a filler (B) is more than the said lower limit, the tearability of a resin layer will tend to become favorable. Moreover, when the average particle diameter ( _D50 ) of a filler (B) is below the said lower limit, it exists in the tendency for the peeling force of a base material and a resin layer to be suppressed to become too small by the unevenness|corrugation of a filler (B). The average particle size (D ₅₀ ) of the filler (B) in this embodiment has a volume median particle size (D ₅₀ ), which can be measured by the method described in the examples.

[Shape of filler (B)] The shape of the filler (B) is not particularly limited, but is preferably non-spherical. Since the shape of the filler (B) is non-spherical, the tearability of the resin layer tends to be improved. In addition, "non-spherical shape" in this embodiment means a three-dimensional shape other than a spherical shape, for example, a polygonal shape, a plate shape, a sheet shape, a square shape, a needle shape, a rod shape, or the like. In addition, "spherical" in this embodiment refers to a true sphere or an ellipsoid, and an ellipsoid with an aspect ratio (major axis diameter/short axis diameter) of 1.2 or more is classified as "non-spherical". Among them, the filler (B) preferably has a polygonal shape. In addition, the filler (B) having a polygonal shape preferably has an irregular shape, more preferably a crushed shape. The shape of the filler (B) can be confirmed by a scanning electron microscope (SEM) etc., for example.

[Content of filler (B)] The content of the filler (B) in the resin layer is not particularly limited, but is preferably 1 to 50% by volume, more preferably 4 to 45% by volume, and even more preferably 7 to 40% by volume relative to the volume of the resin layer (100% by volume). volume%. When content of the filler (B) in a resin layer is more than the said lower limit, tear property tends to become favorable. Moreover, when content of a filler (B) in a resin layer is below the said upper limit, it exists in the tendency for the peeling force of a base material and a resin layer to be suppressed to become too small by the unevenness|corrugation of a filler (B).

[Contents of biodegradable resin (A) and filler (B)] The total content of the biodegradable resin (A) and the filler (B) in the resin layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass based on the mass (100% by mass) of the resin layer. % by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass. When the total content of the biodegradable resin (A) and the filler (B) is within the above range, the environmental load of the material that tends to form the resin layer is sufficiently small, and excellent tearability is obtained.

(other ingredients) The resin layer may contain components other than the biodegradable resin (A) and the filler (B) within the range that does not impair the effects of the present invention. Examples of other components include resins other than the biodegradable resin (A); additives such as antioxidants, lubricants, ultraviolet absorbers, colorants, and anti-blocking agents; and the like. Each of the other components may be used alone or in combination of two or more. When the resin layer contains other components, the content of the other components is not particularly limited, but is preferably 0.0001 to 20% by mass, more preferably 0.0005 to 15% by mass, and more preferably 0.0005 to 15% by mass relative to the mass of the resin layer (100% by mass). Preferably, it is 0.001 to 10% by mass.

(thickness of resin layer) The thickness of the resin layer is not particularly limited, but is preferably 5-50 μm, more preferably 10-40 μm, and still more preferably 15-30 μm. When the thickness of the resin layer is more than the above lower limit, it tends to be easy to form a resin layer with a uniform thickness, and to easily adjust the peeling force between the base material and the resin layer within an appropriate range. Moreover, when the thickness of a resin layer is below the said upper limit, environmental load can be further reduced, and the peeling force of a base material and a resin layer tends to become favorable.

＜Adhesive layer＞ The adhesive layer included in the multilayer structure according to this embodiment is a layer for bonding the multilayer label to an adherend, and is appropriately selected according to the application of the multilayer label. The adhesive layer is formed of, for example, an adhesive such as an acrylic adhesive, a natural rubber adhesive, a synthetic rubber adhesive, or a silicone adhesive. Among them, an acrylic adhesive is preferable from the viewpoint of weather resistance and economic efficiency. As an acrylic adhesive agent, a solvent-type acrylic adhesive agent, an aqueous emulsion type acrylic adhesive agent, etc. are mentioned, for example. Adhesives may be used alone or in combination of two or more.

The adhesive preferably contains an adhesive imparting agent. Examples of tackifiers include rosin-based resins, terpene-phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, aromatic petroleum resins, hydrogenated petroleum resins, benzofuran- Indene (coumarone-indene) resins, styrene-based resins, phenol-based resins, xylene resins, and the like. These tackifiers may be used alone or in combination of two or more. When the adhesive contains an adhesion-imparting agent, its content is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and more preferably 100 parts by mass of the main polymer of the adhesive. Preferably, it is 5-10 mass parts.

The adhesive may or may not contain additives for adhesives used in general adhesives in addition to the main polymer and the adhesive imparting agent within the range that does not impair the efficacy of the present invention. Examples of additives for adhesives include fillers, softeners, thermo-optic stabilizers, antioxidants, crosslinking agents and the like. Each of these adhesive additives may be used alone or in combination of two or more. When the adhesive contains additives for the adhesive, the content thereof is not particularly limited, but is preferably 0.0001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and more preferably More preferably, it is 1-10 mass parts.

(thickness of adhesive layer) The thickness of the adhesive layer is not particularly limited, but is preferably 1-50 μm, more preferably 5-40 μm, and still more preferably 10-30 μm. When the thickness of the adhesive layer is more than the above-mentioned lower limit, it tends to be easy to form an adhesive layer with a uniform thickness and to obtain stable adhesive force. Moreover, when the thickness of an adhesive layer is below the said upper limit, productivity and economic efficiency tend to be excellent.

<Peel force between substrate and resin layer> In the multilayer label related to this embodiment, the peeling force between the base material and the resin layer is preferably 100-1,000mN/50mm, more preferably 200-850mN/50mm, even more preferably 250-700mN/50mm, and furthermore Preferably it is 300-650mN/50mm. When the peeling force of a base material and a resin layer is more than the said lower limit, it will tend to suppress that a base material peels unexpectedly from a resin layer. In addition, when the peeling force between the base material and the resin layer is below the above-mentioned upper limit, it tends to be easily peeled by hand, and when the base material is peeled from the resin layer, cracking of the base material can be suppressed. In addition, the peeling force of a base material and a resin layer is a value measured according to JIS Z 0237:2000 "180 degree peeling adhesion to a test board", Specifically, it can measure by the method described in an Example.

＜Other layers＞ The multilayer label according to this embodiment may or may not have layers other than the base material, the resin layer, and the adhesive layer. Even when the multilayer label according to the present embodiment has other layers, the base material and the resin layer have a structure in which they are directly laminated. As long as this is the case, the positions of the other layers are not particularly limited. When there are two or more other layers, each may have the same composition, or may have a different composition. As another layer, the above-mentioned thermosensitive color-developing layer, the peeling sheet provided on the surface of the adhesive layer opposite to a resin layer, etc. are mentioned, for example.

As the release sheet, a release sheet after double-side release treatment, a release sheet after single-side release treatment, etc., or one in which a release agent is applied to a base material for a release material, etc. are exemplified. As the base material for the release sheet, papers such as Dowling paper, cellophane, kraft paper, etc.; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, etc. Polyester resin films such as glycol ester resins, plastic films such as olefin resin films such as polypropylene resins and polyethylene resins; etc. Examples of the release agent 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 resin etc.

The thickness of the release sheet is not particularly limited, but is preferably from 10 to 200 μm, more preferably from 25 to 170 μm, and still more preferably from 30 to 150 μm, from the viewpoint of economic efficiency and workability.

＜Total thickness of multi-layer label＞ The total thickness of the multilayer label in this embodiment is not particularly limited, but is preferably 50-300 μm, more preferably 70-200 μm, and still more preferably 90-150 μm. Furthermore, where the multilayer label has a release sheet, the thickness of the release sheet is not included in the total thickness of the multilayer label.

＜Shape of multi-layer label＞ Viewed from a plane, the shape of the multilayer label is not particularly limited, and examples thereof include polygonal shapes such as rectangles and triangles; circles, ellipses, and indeterminate shapes; and the like.

＜Manufacturing method of multi-layer label＞ The multilayer label related to this embodiment can be manufactured by the manufacturing method including the following steps P1 and P2, for example. Step P1: Step of forming a resin layer on one side of the base material to obtain a base material with a resin layer Step P2: A step of laminating an adhesive layer on the resin layer of the substrate with a resin layer obtained in Step P1

(step P1) Step P1 is a step of forming a resin layer on one side of a substrate to obtain a substrate with a resin layer. The method for forming the resin layer on one side of the substrate is not particularly limited, and examples thereof include a method of melt-extruding a resin layer-forming material containing a biodegradable resin (A) and a filler (B) onto a substrate, A method of coating a resin layer forming material on a substrate, etc. Among them, the method of melt-extruding the resin layer forming material is preferable from the viewpoint of productivity.

As a method of melt-extruding the resin layer-forming material onto the base material, for example, a method of extruding the melted resin layer-forming material onto the base material using an extruder and a T-die to form a layer is exemplified. The melt extrusion temperature of the resin layer forming material is not particularly limited, and can be appropriately set according to the type of resin constituting the resin layer, and is preferably 130 to 300°C, more preferably 150 to 250°C, and still more preferably 180 to 220°C. °C. After the resin layer forming material is melt-extruded, the formed resin layer may be subjected to cooling and solidification treatment.

As a method of coating the resin layer forming material on the base material, for example, a coating solution of the resin layer forming material obtained by dissolving and dispersing the biodegradable resin (A) and the filler (B) in a solvent is mentioned. It is a method of forming a resin layer by coating it on a substrate and drying it. As the coating method of the coating liquid of the resin layer forming material, for example, a roll coating method, a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll knife coating method, Blade coating method, die coating method, gravure coating method, etc.

(step P2) 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. As a method of laminating an adhesive layer on a resin layer, for example, after coating an adhesive composition containing materials constituting the adhesive layer on a release sheet, drying to form an adhesive layer as necessary, the adhesive A method of attaching the agent layer to the resin layer of the substrate with the resin layer. In addition, as another method of laminating the adhesive layer on the resin layer, for example, after applying the adhesive composition on the surface of the resin layer of the base material with the resin layer, drying the resin layer as necessary A method of forming an adhesive layer on a surface. Thereafter, if necessary, a release sheet may be attached to the surface of the adhesive layer. As a method of coating the adhesive composition, the same method as the coating method of the coating liquid of the resin layer forming material is mentioned.

From the viewpoint of improving the adhesiveness between the resin layer and the adhesive layer, 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. Examples of surface treatment methods include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, ozone irradiation treatment, ultraviolet irradiation treatment, ultraviolet-ozone treatment Oxidation methods such as sand blasting and solvent treatment; etc.

Multi-layer labels can be properly crimped. For crimping, for example, a crimping knife can be used to cut through the peeling sheet along the periphery of the predetermined multilayer label, or it can be cut from the base material to the adhesive layer without cutting through the peeling sheet to form a plurality of multilayer label arrangements on the release sheet. In addition, waste portions around the periphery of each multilayer label can be removed as pieces from the release sheet, as desired.

＜Applications of multi-layer labels＞ The multilayer label related to this embodiment is preferably a multilayer label for a consignment note. When used as a consignment note, a half-cut line is placed on the substrate of a multi-layer label to divide the substrate into multiple sheets so that it can be peeled off. Then, one substrate separated by the half tangent is used as the delivery note, while the other substrate is used as the goods receipt. The receipt is usually torn off after being stamped or signed by the recipient, and taken back by the courier company for document sorting, etc. In addition, the multi-layer label according to this embodiment is suitable for uses other than consignment notes, such as postcards and anti-counterfeit labels, because it has little environmental impact and is easy to discard. Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. The measurement methods and evaluation methods of various physical properties are as follows.

[Measurement of thickness of each layer] Measured using a constant pressure thickness measuring device manufactured by TECLOCK Co., Ltd. (model: "PG-02J", conforming to standard specifications: JIS K 6783, Z1702, Z1709).

[Measuring method of average particle diameter (D ₅₀ ) of filler] The particle size distribution was measured using a laser diffraction particle size distribution measuring device (manufactured by Malvern, product name "Mastersizer 3000"), and the obtained particle size distribution was compared with Starting from small particle size, the particle size corresponding to 50% of the cumulative volume frequency was calculated as the average particle size (D ₅₀ ).

[Measurement of melting point of resin and confirmation of crystallinity] The melting point of the resin was measured according to the following procedure in accordance with JIS K 7121:1987. About 5 mg of the sample was put into an aluminum pot, and using a differential scanning calorimeter (DSC) (manufactured by TA Instruments, product name "Q2000"), the measurement temperature range was -120 to 200°C, and the heating rate was 10°C in a nitrogen atmosphere. The DSC curve was obtained under the condition of °C/min. The melting point of the resin was obtained by analyzing the obtained DSC curve according to JIS K 7121:1987. In addition, the presence or absence of crystallinity of the resin is judged by the presence of a melting point peak, and the resins used in Examples and Comparative Examples described later all have crystallinity.

[Measurement of glass transition temperature (Tg) of resin] The glass transition temperature (Tg) of resin is measured by the following procedure based on JISK7121:1987. About 5 mg of the sample was put into an aluminum pot, and using a differential scanning calorimeter (DSC) (manufactured by TA Instruments, product name "Q2000"), the measurement temperature range was -120 to 200°C, and the heating rate was 10°C in a nitrogen atmosphere. The DSC curve was obtained under the condition of °C/min. The glass transition temperature of the resin was obtained by analyzing the obtained DSC curve according to JIS K 7121:1987.

[Manufacturing of multi-layer labels] Examples 1-8, Comparative Example 1 The resin layer forming material containing the resin and fillers having the resin layer composition described in Table 1 was heated to 200°C, and extruded onto the paper base using a T-die material (Nippon Paper Co., Ltd., thermal paper, basis weight 65 g/m ² , thickness 75 μm). Thereafter, the resin layer was cooled and solidified with a water-cooled roller adjusted to 23° C. to form a resin layer with a thickness of 20 μm on the paper substrate. Then, 100 parts by mass of an acrylic adhesive and 7.5 parts by mass of a rosin-based tackifier were mixed to prepare an adhesive composition. This adhesive composition was coated on a release sheet (manufactured by Lintec Co., Ltd., trade name "8K AO") with a roll coater, and dried to form an adhesive layer with a thickness of 20 μm on the release sheet. Next, by laminating the adhesive layer on the release sheet and the resin layer on the paper substrate, there are sequentially a paper substrate, a resin layer containing a resin and a filler, an adhesive layer, and a release sheet to obtain a paper substrate and a resin layer. A multi-layer label with resin layers bonded in a peelable manner.

Comparative example 2 In Example 1, a multilayer label was obtained in the same manner as in Example 1 except that no filler was mixed with the resin layer forming material.

[Evaluation of multi-layer labels] The multilayer labels produced in each example were evaluated as follows. The evaluation results are shown in Table 1.

(Peel force between substrate and resin layer) The peeling force between the base material and the resin layer was measured in the following procedure in accordance with "180° peeling adhesion to a test plate" of JIS K 0237:2000. The multilayer label produced in each example was cut into width 50 mm x length 150 mm, and what removed the release sheet was prepared as a multilayer label for evaluation. Then, the multilayer label for evaluation was attached and fixed on the surface of the SUS plate with the adhesive layer as the attachment surface. Next, on one end of the multilayer label for evaluation on the SUS board, the paper substrate was peeled 40 mm from the resin layer. The part of the paper substrate after the peeling is fixed on the chuck of the tensile tester, and with the tensile tester, the paper substrate is peeled off from the resin layer under the conditions of a peeling speed of 0.3m/min and a peeling angle of 180°. The peel force at 4 points was measured at intervals of 20 mm. The test was performed on three multilayer labels for evaluation, and the peel force was calculated as an average value of 12 points after the measurement.

(tearing) The tearability of the multilayer labels was evaluated in the following order. In addition, a schematic diagram for explaining the evaluation method of the tear property is shown in FIG. 3 , and the procedure will be described below with reference to this diagram. First, the multilayer label produced in each example was cut into a length of 80 mm×width of 40 mm, and what removed the release sheet was prepared as a multilayer label 1 for evaluation. Then, a cloth tape (manufactured by Okamoto Co., Ltd., No. 111) 60 with a length of 160 mm×a width of 50 mm was attached to the surface of the corrugated cardboard 50 . Next, as shown in FIG. 3 , the multilayer label 1 for evaluation is attached to the lamination position of both the corrugated cardboard 50 and the cloth tape 60 attached to the corrugated cardboard 50 with the adhesive layer as the application surface, and the paper substrate is peeled off. Afterwards, the sticking position of the multilayer label 1 for evaluation is a position where the center line of the cloth tape 60 in the short direction coincides with the center line of the multilayer label 1 for evaluation in the longitudinal direction, and the longitudinal direction of the multilayer label 1 for evaluation is Half of the length of 40 mm is laminated on the cloth tape 60 , and the remaining length of 40 mm is laminated on the corrugated paper 50 . Next, peel off one end of the cloth tape 60 attached to the corrugated paper 50 for about 20mm, grasp the peeled part with your fingers, and at a peeling angle of about 135°, the cloth tape 60 is stretched from one end to the other end in the long side direction. (X direction in FIG. 3 ) was instantly peeled off, thereby tearing the resin layer. Thereafter, the longest distance from the boundary between the corrugated cardboard 50 and the cloth tape 60 to the edge of the torn resin layer was measured, and evaluated according to the following criteria. After that, the evaluation was carried out in the test (i) in which the flow direction of the resin layer was attached to the direction parallel to the direction in which the tape 60 was peeled off, and the above flow direction was attached to the tape 60 and peeled off. Test (ii) both in the direction perpendicular to the direction. [Evaluation Criteria for Tearability] A: In both tests (i) and (ii), the longest distance of the resin layer was less than 5 mm. B: In tests (i) and (ii), the maximum value of the longest distance of the resin layer is 5 mm or more and less than 10 mm. C: In tests (i) and (ii), the maximum value of the longest distance of the resin layer is 10 mm or more and less than 20 mm. F: In tests (i) and (ii), the maximum value of the longest distance of the resin layer was 20 mm or more. Alternatively, the resin layer is peeled from the corrugated paper 50 without being torn.

※填料的添加量為相對樹脂層的體積(100體積%)的添加量。 [Table 1] Table 1

※The amount of filler added is based on the volume of the resin layer (100% by volume).

As can be seen from the results in Table 1, the multilayer labels of Examples 1 to 8 of this embodiment have the same peeling force as the multilayer label of Comparative Example 1 using conventional low-density polyethylene as the resin layer, and by using biodegradable The 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.

1,2: multi-layer labels 10: Substrate 20: resin layer 30: Adhesive layer 40: Stripping sheet 50: corrugated paper 60: cloth tape S: Interlayer X: direction

[ Fig. 1] Fig. 1 is a schematic cross-sectional view showing an example of the structure of a multilayer label according to this embodiment. [ Fig. 2] Fig. 2 is a schematic cross-sectional view showing another example of the structure of the multilayer label of the present embodiment. [ Fig. 3 ] A schematic diagram for explaining a method of evaluating peelability.

1: Multi-layer label

10: Substrate

20: resin layer

30: Adhesive layer

S: Interlayer

Claims (12)

A multi-layer label sequentially has a base material, a resin layer and an adhesive layer, wherein the aforementioned substrate and the aforementioned resin layer are bonded in a detachable manner, and The aforementioned resin layer contains a biodegradable resin (A) and a filler (B). The multilayer label according to claim 1, wherein the biodegradable resin (A) has crystallinity. The multilayer label according to claim 1 or 2, wherein the biodegradable resin (A) has a glass transition temperature of 0°C or lower and a melting point of 40°C or higher. The multilayer label according to any one of claims 1 to 3, wherein the biodegradable resin (A) is a polybutylene succinate-based resin. The multi-layer label according to any one of Claims 1 to 4, wherein the aforementioned filler (B) is an inorganic filler. The multi-layer label as described in Claim 5, wherein the aforementioned inorganic filler is calcium carbonate. The multi-layer label according to any one of Claims 1 to 6, wherein the filler (B) is non-spherical in shape. The multi-layer label according to any one of Claims 1 to 7, wherein the aforementioned filler (B) is not subjected to surface modification treatment with organic components. The multilayer label according to any one of Claims 1 to 8, wherein the content of the filler (B) in the resin layer is 1 to 50% by volume relative to the volume (100% by volume) of the resin layer. The multi-layer label according to any one of Claims 1 to 9, wherein the aforementioned substrate is a paper substrate. The multilayer label according to any one of Claims 1 to 10, wherein the peeling force between the substrate and the resin layer is 100 to 1,000 mN/50mm. The multi-layer label described in any one of Claims 1 to 11, which is used for the consignment note.

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