WO2012002510A1 - 易剥離性フィルム、インモールド成形用ラベル、ラベル付き樹脂成形品、壁紙、グルーラベルおよびラベル付き容器 - Google Patents
易剥離性フィルム、インモールド成形用ラベル、ラベル付き樹脂成形品、壁紙、グルーラベルおよびラベル付き容器 Download PDFInfo
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- WO2012002510A1 WO2012002510A1 PCT/JP2011/065098 JP2011065098W WO2012002510A1 WO 2012002510 A1 WO2012002510 A1 WO 2012002510A1 JP 2011065098 W JP2011065098 W JP 2011065098W WO 2012002510 A1 WO2012002510 A1 WO 2012002510A1
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- WIPO (PCT)
- Prior art keywords
- resin
- label
- layer
- easily peelable
- peeling
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered 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
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/002—Coverings or linings, e.g. for walls or ceilings made of webs, e.g. of fabrics, or wallpaper, used as coverings or linings
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
- C09J2425/006—Presence of styrenic polymer in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F2003/0257—Multilayer
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/08—Fastening or securing by means not forming part of the material of the label itself
- G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
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- Y10T428/24331—Composite web or sheet including nonapertured component
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- Y—GENERAL 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
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- Y—GENERAL 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
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- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Y—GENERAL 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
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- Y—GENERAL 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
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- Y—GENERAL 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
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- Y—GENERAL 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
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- Y—GENERAL 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
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Definitions
- the present invention relates to an easily peelable film, and more particularly to an easily peelable film useful as a wallpaper that can be adhered to a building material, or a label that can be adhered to a glass or resin bottle.
- the easy-release film of the present invention is particularly easy to apply to a building material and the like directly through an adhesive without using a natural paper backing material, and to a bottle or the like.
- the easy peel layer remains in a uniform surface on the adherend side, so the adherend after peeling does not leave large irregularities on the surface, and the surface can absorb liquid Therefore, re-pasting is easy.
- the film itself can be easily peeled in a recyclable state, which is useful for reducing waste.
- the present invention also relates to an in-mold label made of an easily peelable film. More specifically, hollow molding in which a molten thermoplastic resin parison is introduced into a mold and shaped using compressed air, or injection molding in which a molten thermoplastic resin is introduced into a mold and shaped with the resin pressure. Alternatively, in pressure reduction molding or pressure molding in which a molten thermoplastic resin sheet is guided onto a mold and shaped by decompression or pressurization, the label is placed in contact with the inner wall surface of the mold in advance, and then melted thermoplastic resin
- the present invention relates to an in-mold molding label capable of producing a resin-molded product with a label in which the label and the resin-molded product are integrated when the resin is molded into a mold.
- a base material for a wallpaper or a bottle or a container label such as a resin bottle as a building decoration material
- a film using polyolefin or a calendered film mainly composed of vinyl chloride (PVC) resin has been used as a base material for a wallpaper or a bottle or a container label such as a resin bottle as a building decoration material.
- PVC vinyl chloride
- these resin films alone are difficult to absorb the adhesive, and therefore, a water-absorbing resin layer is laminated on the bonding side (for example, Patent Document 1) or other materials are lined.
- a film on which these water-absorbing layers are laminated can be attached to an adherend with a solvent-based or water-based adhesive.
- the peeled-off surface is uniform because part of the water-absorbing layer left on the adherend side remains or peels off the adherend side when peeled off from the adherend.
- the wallpaper and the label are reapplied on the adherend side, the unevenness of the foundation is raised on the surface, and the appearance is deteriorated, so that there is a problem that the reattachment cannot be performed.
- the film peeled off when the wallpaper and the label are replaced cannot be recycled as a material.
- the film and the adhesive In order to recycle the peeled film, the film and the adhesive must be separated or the film and the backing material must be separated, but these are usually difficult to implement because they are firmly bonded.
- a wallpaper and a label that have been devised so that the resin material and the backing material can be separated have been proposed.
- a PVC and backing material that can be separated by stirring for example, Patent Document 2
- a PET film or a PP film laminated between the backing material and a foamed PVC base material for example, a patent
- a printable surface layer containing a thermoplastic resin, an inorganic fine powder and / or an organic filler as one that can be attached to an adherend such as a wall or board via an adhesive without using a backing material A back surface layer (B) containing a thermoplastic resin containing a hydrophilic thermoplastic resin and a surface-treated inorganic fine powder is laminated on the back surface of A), and the peel strength of the back surface layer (B) is 10 to 200 g.
- An easily peelable multilayer resin stretched film characterized by / cm is proposed (Patent Document 4).
- the back surface layer (B) was subjected to a hydrophilic treatment on the surface by 10 to 30% by weight of a crystalline polypropylene resin, 2 to 10% by weight of a hydrophilic resin, 13 to 25% by weight of a thermoplastic elastomer.
- a layer containing 45 to 65% by weight of inorganic fine powder is laminated on the base layer is specifically described.
- a blank or label is inserted into a mold in advance, and then a resin molded product such as a container is molded in the mold by injection molding, hollow molding, differential pressure molding, foam molding, etc.
- An integrated resin molded product is molded (see, for example, Patent Document 5 and Patent Document 6).
- Such a label is called an in-mold label, and is a gravure-printed resin film, offset-printed synthetic paper (see, for example, Patent Document 7 and Patent Document 8), flexographic-printed synthetic paper, or aluminum.
- An aluminum label or the like obtained by laminating a high-pressure low-density polyethylene and an ethylene / vinyl acetate copolymer on the back surface of the foil and gravure printing on the surface of the foil is known and put into practical use.
- a conventional low-melting-point resin is used to form a heat seal layer and not adhere by thermal fusion, but a resin film having a porous surface with an open surface.
- the molded product resin has an anchoring effect that enters the opening on the surface of the adhesive layer with pressure during molding, and the adhesion between the label and the molded product is strong regardless of the material of the molded product, and a wide range of molded products
- the thing which can bond a label on molding conditions was proposed (for example, refer patent document 11).
- this in-mold molding label adheres firmly (at 400 g / 15 mm or more) to the resin molded product, and it is difficult to easily peel off and separate the label from the resin molded product with label. It was.
- the label can be easily separated from the resin container with the label using the in-mold molding label applicable to various resin molded products, not only the collection and use of the resin container but also the adhesive layer as in Patent Document 10
- printing can be confirmed after peeling, and additional functions such as prevention of counterfeiting and reuse of labeled resin containers, and secondary use of peeled labels for coupons, etc. are added. It was possible and further improvements were sought.
- An object of the present invention is to solve the above-mentioned problems of the prior art. That is, the present invention does not require a backing material, and has excellent workability to building materials such as walls and boards or excellent applicability to bottles and bottles via an adhesive. Providing an easy-to-removable film that does not leave irregularities on the surface of the adherend when it is peeled off, and can be easily re-attached, and the peeled wallpaper and labels can be easily recovered in a material-recyclable state. The task was to do.
- the present invention has a strong adhesion between the label and the resin molded product regardless of the material of the resin molded product, can be attached to the label under a wide range of molded product molding conditions, and is an in-mold molded label.
- Another object of the present invention is to provide an in-mold molding label capable of easily separating a base layer of a label from a resin molded product with a mark.
- Another object of the present invention is to provide a labeled resin molded product capable of visually recognizing at least one of the resin molded product and the label when the label base layer (A) is separated from the labeled resin molded product.
- An easily peelable film including a laminated resin film of a base layer (A) and an easily peelable layer (B),
- the base layer (A) contains a thermoplastic resin
- the easily peelable layer (B) has a crystalline polypropylene resin having a crystallinity of 65% or more, a blend of 30 to 60% by weight of a thermoplastic resin incompatible with the crystalline polypropylene resin, and a fine powder of 40 to 70.
- thermoplastic resin that is incompatible with the crystalline polypropylene resin at a ratio of 105 to 300 parts by weight with respect to 100 parts by weight of the crystalline polypropylene resin in the blend, and The easily peelable film, wherein the easily peelable layer (B) is stretched in at least one axial direction.
- the surface treatment agent is at least one surfactant selected from the group consisting of a water-soluble anionic surfactant, a water-soluble cationic surfactant, and a water-soluble nonionic surfactant.
- the fine powder is 50 to 99.9% by weight of inorganic fine powder whose surface is hydrophilized and at least one of inorganic fine powder and organic fine powder whose surface is not hydrophilized is 0.00.
- thermoplastic resin incompatible with the crystalline polypropylene resin is a group consisting of polyethylene resin, styrene resin, cyclic polyolefin resin, ethylene-cyclic olefin copolymer resin, polyamide resin, polyester resin, and polycarbonate.
- the easily peelable film according to any one of [1] to [5], which is at least one resin selected from the above. [7] Any one of [1] to [6], wherein the easily peelable layer (B) further contains 0.5 to 30 parts by weight of a fine powder dispersant with respect to 100 parts by weight of the fine powder.
- the easily peelable film according to one item.
- the masking layer (C) comprises black printing or gray printing on the surface of the easily peelable layer (B), addition of masking pigment to the base layer (A), and black printing insertion between the base layers (A).
- the easily peelable film according to [14] comprising at least one method selected from the above.
- Printing is performed on the surface of the easily peelable layer (B) of the label for in-mold molding, and when the label for in-mold molding is peeled off from the resin-molded product with label, the printing is performed on the label.
- the easily peelable film of the present invention can be easily attached to an adherend such as a building material or a container via an adhesive without requiring a backing material. Moreover, since it does not leave an unevenness
- the label base layer can be easily separated from the molded resin molded product with a label. Furthermore, the resin-molded article with a label of the present invention is easy to collect and use the resin-molded article, and has a label by printing in advance on the surface of the in-mold molding label on the easy-release layer (B) side. When the base layer (A) of the label is separated from the resin molded product, the print can be visually recognized at least one of the resin molded product and the base layer (A).
- FIG. 10 is a cross-sectional view of an in-mold molding label of Comparative Example 107.
- FIG. 10 is a cross-sectional view of an in-mold molding label of Comparative Example 108.
- FIG. 10 is a cross-sectional view of an in-mold molding label of Comparative Example 108.
- the easily peelable film of the present invention includes a laminated resin film of a base layer (A) and an easily peelable layer (B) (see FIG. 1).
- the label for in-mold molding of the present invention is also composed of an easily peelable film having the same configuration.
- the base layer (A) contains a thermoplastic resin, and its own strength is higher than the strength of an easily peelable layer (B) described later. When the label is peeled off with the (A) layer, the inside itself is broken. It has the strength that does not. More specifically, the cohesive strength (peeling strength or tensile breaking strength) of the base layer (A) itself is preferably 200 gf / 15 mm or more.
- the base layer (A) may be transparent, translucent, or opaque.
- thermoplastic resin used for the base layer (A) is not particularly limited.
- polyolefin resins such as high density polyethylene, medium density polyethylene, low density polyethylene, propylene resin, polymethyl-1-pentene, ethylene-cyclic olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer Polymers, functional group-containing polyolefin resins such as maleic acid-modified polyethylene and maleic acid-modified polypropylene, polyamide resins such as nylon-6 and nylon-6,6, polyethylene terephthalate and copolymers thereof, polybutylene terephthalate, polybutylene
- Thermoplastic polyester resins such as succinate, polylactic acid and aliphatic polyester, polycarbonate, atactic polystyrene, syndiotactic polystyrene and the like can be used.
- thermoplastic resins it is preferable to use a polyolefin resin excellent in processability and a functional group-containing polyolefin resin.
- polyolefin resins include homopolymers of olefins such as ethylene, propylene, butylene, butadiene, isoprene, chloroprene, methyl-1-pentene, cyclic olefin, and two or more of these olefins. And a copolymer.
- the functional group-containing polyolefin resin include a copolymer of a functional group-containing monomer copolymerizable with the olefin.
- Such functional group-containing monomers include styrenes such as styrene and ⁇ -methylstyrene, vinyl acetate, vinyl alcohol, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl benzoate.
- Vinyl esters of carboxylic acid such as vinyl butylbenzoate and vinyl cyclohexanecarboxylate, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclope (Meth) acrylic acid esters such as Tanyl (meth) acrylate, (Meth) acrylamide, N-Metallol (meth) acrylamide ((Meth) acrylic acid ester refers to acrylic acid ester and methacrylic acid ester), methyl vinyl ether, Particularly representative are vinyl acryl
- polystyrene resins From these functional group-containing monomers, one or two or more types appropriately selected and polymerized can be used as necessary. Furthermore, these polyolefin resins and functional group-containing polyolefin resins can be used after being graft-modified if necessary.
- a known method can be used for graft modification.
- Specific examples include graft modification with an unsaturated carboxylic acid or a derivative thereof.
- the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like.
- unsaturated carboxylic acid derivative acid anhydrides, esters, amides, imides, metal salts and the like can also be used.
- maleic anhydride, itaconic anhydride, citraconic anhydride methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, malee Acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethyl Amides, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoe
- the graft-modified product is preferably obtained by graft-modifying the graft monomer with respect to the polyolefin resin and the functional group-containing polyolefin resin generally in an amount of 0.005 to 10% by weight, preferably 0.01 to 5% by weight.
- thermoplastic resin of the base layer (A) one kind selected from the above thermoplastic resins may be used alone, or two or more kinds may be selected and used in combination. Furthermore, among these polyolefin resins and functional group-containing polyolefin resins, propylene resins are preferred from the standpoints of chemical resistance and cost.
- the propylene-based resin is a propylene homopolymer which is mainly composed of polypropylene, propylene having isotactic or syndiotactic and various degrees of stereoregularity, and ethylene, 1-butene, 1-hexene, It is desirable to use as a main component a copolymer obtained by copolymerization with an ⁇ -olefin such as 1-heptene or 4-methyl-1-pentene.
- This copolymer may be a binary system or a ternary system or may be a random copolymer or a block copolymer.
- the propylene resin is preferably used by blending 2 to 25% by weight of a resin having a melting point lower than that of the propylene homopolymer.
- a resin having a low melting point include high-density or low-density polyethylene.
- an inorganic fine powder In addition to the thermoplastic resin, an inorganic fine powder, an organic filler, a heat stabilizer (antioxidant), a light stabilizer, a dispersant, a lubricant, and the like can be added to the base layer (A) as necessary.
- an inorganic fine powder one having an average particle size of usually 0.01 to 15 ⁇ m, preferably 0.1 to 5 ⁇ m is used.
- calcium carbonate, calcined clay, silica, diatomaceous earth, white clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, dolomite, wollastonite, glass fiber, etc. Can be used.
- thermoplastic resin film is a polyolefin resin film
- examples of the organic filler include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic polyolefin, polystyrene, and polymethacrylate.
- a polymer having a melting point (for example, 170 to 300 ° C.) higher than the melting point of the polyolefin resin or a glass transition temperature (for example, 170 to 280 ° C.) and incompatible can be used.
- a heat stabilizer When adding a heat stabilizer, it is usually added within a range of 0.001 to 1% by weight. Specifically, sterically hindered phenol-based, phosphorus-based, amine-based stabilizers, and the like can be used. When a light stabilizer is used, it is usually used within a range of 0.001 to 1% by weight. Specifically, sterically hindered amines, benzotriazole-based, benzophenone-based light stabilizers, and the like can be used. A dispersant or a lubricant is used for the purpose of dispersing inorganic fine powder, for example. The amount used is usually in the range of 0.01 to 4% by weight. Specifically, silane coupling agents, higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid or salts thereof can be used.
- the thickness of the base layer (A) is usually in the range of 30 to 500 ⁇ m, preferably 70 to 300 ⁇ m. If it is 30 ⁇ m or more, for example, when sticking to an adherend as a water-absorbing easily peelable film such as wallpaper, sticking is unlikely to occur and it tends to be neatly attached to the adherend. If it is 30 ⁇ m or more, for example, it has sufficient rigidity when affixed to a resin molded product as an in-mold molding label. It tends to be difficult to break. On the other hand, if it is 500 ⁇ m or less, it has an appropriate waist and rigidity, so that it is easy to process and print, and for example, it tends to be held in a mold as an in-mold molding label.
- the base layer (A) may have a single layer structure or a multilayer structure of two or more layers. Various functions such as writability, printability, scratch resistance, and secondary processing suitability can be added by multilayering the base layer (A).
- the base layer (A) has a multilayer structure, the content of at least one of the inorganic fine powder and the organic filler in the layer (A1) which is a layer in contact with the later-described easily peelable layer (B) is more than that of the easily peelable layer (B). 5% by weight or more, preferably 10% by weight or less.
- the porosity of the easily peelable layers (B) and (A1) is that the content of at least one of the inorganic fine powder and organic filler in the (A1) layer is 5% by weight or more lower than the easily peelable layer (B). Therefore, when the easily peelable film is peeled off from the adherend, it can be propagated to only the easily peelable layer (B).
- the layer (A1) has a thermoplastic resin content of 35 to 100% by weight, preferably 40 to 100% by weight, and at least one of inorganic fine powder and organic filler is 0 to 65% by weight, preferably 0 to 60% by weight. %including.
- the number of stretching axes of this multilayer structure is, for example, in the case of a two-layer structure, as a surface layer / (A1) layer, unstretched / uniaxial, unstretched / 2-axis, 1-axis / 1-axis, 1-axis / 2-axis, 2 axis / 1 axis, 2 axis / 2 axis can be exemplified.
- the easily peelable layer (B) in the present invention is formed on the base layer (A). Peeling of the easily peelable film of the present invention is performed by breaking (cohesive failure) of the easily peelable layer (B).
- peeling of the easily peelable film of the present invention is performed by breaking (cohesive failure) of the easily peelable layer (B).
- at least two kinds of resins that are incompatible with each other are blended as a resin material and stretched in a phase-separated state so that the pores Peeling occurred not only at the interface but also at the interface between these resins, and the same layer (B) could be peeled in a uniform plane.
- the easily peelable layer (B) in the present invention can absorb liquid.
- the liquid absorbency is high.
- the same layer (B) is stretched, a large number of surface openings and internal vacancies are formed with this as a nucleus.
- the water-based adhesive is particularly applicable to the easily peelable film of the present invention, and can be adhered to the adherend via the adhesive, so that it is easy to absorb water such as wallpaper. It can be used as a peelable film.
- the same layer (B) is a layer that is more brittle and weaker than the base layer (A), and the film can be easily peeled in such a manner that no adhesive is contained due to the destruction of the same layer (B).
- the same layer (B) can be peeled in a uniform surface as compared with a conventionally known water-absorbing layer, coarse irregularities derived from the same layer (B) are not left on the adherend surface. The appearance does not deteriorate the appearance even if another film is applied again.
- the easily peelable film of the present invention is a porous resin film having an open surface, for example, when used as an in-mold molding label, it is easy to melt resin with resin pressure during in-mold molding of a resin molded product. It enters into the opening on the surface of the release layer (B), and the label can be attached to the resin molded product by the anchoring effect. Therefore, the label can be bonded to the resin molded product regardless of the material of the resin molded product.
- the easily peelable layer (B) is a layer that is more brittle and weaker than the base layer (A), and the base layer (A) can be easily peeled off from the resin-molded article with a label by breaking the same layer (B). .
- the easily peelable layer (B) has a large number of communicating pores therein, even when air remains between the label and the resin molded product when the label is attached to the resin molded product, Since it is pushed out to the resin through the communication hole and discharged to the outside, the label does not bulge and remain between the two. Furthermore, the easy-peeling layer (B) has a smooth surface, and preferably uses an inorganic fine powder whose surface has been hydrophilized, so that the printability is good. Will not be disturbed.
- the easy-release layer (B) of the present invention comprises 30 to 60% by weight, preferably 35 to 50% by weight of a crystalline polypropylene resin and a blend of thermoplastic resin incompatible with the crystalline polypropylene resin, and 40 to
- the easily peelable layer (B) contains 70% by weight, preferably 50 to 65% by weight, and is characterized in that it is stretched in at least one axial direction. If the content of the fine powder in the easily peelable layer (B) is less than 40% by weight, sufficient peelability cannot be obtained. Conversely, if it exceeds 70% by weight, the molding stability is impaired.
- thermoplastic resin incompatible with the crystalline polypropylene resin with respect to 100 parts by weight of the crystalline polypropylene resin. It is blended at a blending ratio of parts.
- the crystalline polypropylene resin is the above-mentioned propylene-based resin, and its crystallinity is 65% or more, preferably 66% or more, and particularly preferably 67 to 80%. If the degree of crystallinity is 65% or more, the compatibility between the amorphous part of the crystalline polypropylene resin and the thermoplastic resin is difficult to proceed, and the desired interfacial peeling effect can be easily obtained, and the stress required for peeling (peeling strength) ) Can be made reasonably small. Moreover, if the degree of crystallinity is 80% or less, it is easy to obtain commercially.
- the crystallinity of the crystalline polypropylene resin is determined by subjecting the resin sample to an annealing treatment for 90 minutes in an oven set at 105 ° C., and then at a temperature of 23 ° C., a density gradient tube method or an underwater substitution method. It was calculated using the following formula (1) from the density of the crystalline polypropylene resin obtained by (both can be mutually corrected by a conversion formula).
- ⁇ S is the density of the crystalline polypropylene resin
- ⁇ C is the theoretically determined density (0.938 g / cm 3 ) of the crystal part of the polypropylene resin
- ⁇ A is logically (The density of the amorphous part of the obtained polypropylene resin (0.852 g / cm 3 ).) Therefore in order to achieve the above crystallinity is preferably the density of the crystalline polypropylene resin used in the easily-peelable layer (B) is 0.906 g / cm 3 or more, is 0.907 g / cm 3 or more Is more preferable, and 0.908 g / cm 3 or more is particularly preferable.
- Thermoplastic resin incompatible with crystalline polypropylene resin include polyethylene resins, styrene resins, cyclic polyolefin resins, ethylene-cyclic olefin copolymer resins, nylon-6, nylon-6,6, nylon-6,10, Polyamide resins such as nylon-6,12, polyethylene terephthalate and copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, polybutylene succinate, polylactic acid, thermoplastic polyester resins such as aliphatic polyester, polycarbonate, etc. It is done. These may be used in combination of two or more.
- thermoplastic resin from the viewpoint of chemical resistance and production cost. Due to the presence of the incompatible thermoplastic resin, interfacial peeling occurs between the crystalline polypropylene resin and the polypropylene resin incompatible with the crystalline polypropylene resin and the polypropylene resin when the stretched film is produced, thereby improving the peelability. If the thermoplastic resin incompatible with the polypropylene resin is less than 105 parts by weight or more than 300 parts by weight, sufficient peelability cannot be obtained.
- incompatible means that when a blend of a crystalline polypropylene resin and an incompatible thermoplastic resin is observed with an electron microscope, it has a morphology of a sea-island structure, and the size of the structure is It means 0.3 to 10 ⁇ m.
- an inorganic fine powder that has been hydrophilized an inorganic fine powder that has not been hydrophilized, or an organic fine powder can be used.
- the fine powder only an inorganic fine powder that has been hydrophilized may be used, or only an inorganic fine powder or an organic fine powder that has not been hydrophilized, or an inorganic fine powder that has been hydrophilized. You may use combining powder and the inorganic fine powder and / or organic fine powder which are not hydrophilized.
- the inorganic fine powder examples include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, silicon oxide, and other inorganic fine powders, around the core of the inorganic fine powder
- examples thereof include composite inorganic fine powders having aluminum oxide or hydroxide, and hollow glass beads.
- heavy calcium carbonate, calcined clay, and diatomaceous earth are preferable because they are inexpensive and can form many pores during stretching.
- the organic fine powder it is preferable to select a resin of a different type from the polypropylene resin used for the easily peelable layer (B).
- a polymer such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic polyolefin, polystyrene, polymethacrylate, etc., which has a melting point higher than that of polypropylene resin (for example, 170 to 300 ° C. ) Or glass transition temperature (for example, 170 to 280 ° C.) and incompatible materials can be used.
- the fine powder in the present invention it is preferable to use at least the above-described inorganic fine powder whose surface is hydrophilized with a surface treatment agent. If the easily peelable layer (B) is formed using inorganic fine powder whose surface has been hydrophilized, the printability of the surface of the easily peelable layer (B) is improved, and a beautiful film or label can be provided. In particular, when used as a label for in-mold molding, a beautiful molded product with a label is obtained, and at the same time, the easy peeling layer (B) formed by these causes more interfacial peeling between the inorganic fine powder and crystalline polypropylene. Since it is easy, it can be separated from the molded product more easily.
- the surface treatment agent examples include water-soluble anionic surfactants, water-soluble cationic surfactants, and water-soluble nonionic surfactants.
- surfactants include, for example, water-soluble anionic surfactants, sulfonates having a hydrocarbon group having 4 to 40 carbon atoms, and hydrocarbon groups having 4 to 40 carbon atoms. Examples thereof include phosphate ester salts, salts of mono- or diesters of higher alcohols having 4 to 40 carbon atoms, and alkylbetaines and alkylsulfobetaines having hydrocarbon groups having 4 to 40 carbon atoms.
- water-soluble cationic surfactants include diallylamine salts, alkyl diallylamine salts and dialkyldiallylamine salts having 1 to 4 carbon atoms, that is, methyldiallylamine salts, ethyldiallylamine salts, dimethyldiallylamine salts, methacryloyloxyethyltrimethylammonium, acryloyl.
- diallylamine salt methyldiallylamine salt and dimethyldiallylamine salt.
- water-soluble nonionic surfactants include acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrodoline, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy (meta ) Acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid butyl ester.
- acrylamide and methacrylamide are preferable.
- the surface treating agent those having an average molecular weight of 1,000 to 15,000 can be preferably used.
- a desired particle size is obtained by wet-grinding in an aqueous medium in the presence of a necessary amount of a surface treatment agent with respect to 100 parts by weight of calcium carbonate coarse particles having a particle size of 10 to 50 ⁇ m.
- the method of doing can be mentioned.
- water is added to calcium carbonate so that the weight ratio of calcium carbonate / aqueous medium (specifically water) is in the range of 70/30 to 30/70, preferably 60/40 to 40/60.
- the surface treating agent is added to 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight per 100 parts by weight of calcium carbonate, and wet pulverized by a conventional method.
- an aqueous medium in which a surface treatment agent having an amount in the above range is dissolved in advance may be prepared, the aqueous medium may be mixed with calcium carbonate, and wet pulverized by a conventional method.
- the wet pulverization may be a batch type or a continuous type, and a mill using a pulverizer such as a sand mill, an attritor, or a ball mill can be used.
- Specific examples of the inorganic fine powder that has been surface-treated with these surface treatment agents include, for example, trade name “AFF” manufactured by Phymatech.
- the easily peelable layer (B) of the present invention may be combined with an inorganic fine powder or organic fine powder whose surface is not hydrophilized.
- the blending ratio is 50 to 99.9% by weight of the inorganic fine powder whose surface is hydrophilized when the fine powder used is 100% by weight, and the inorganic fine powder and organic fine powder whose surface is not hydrophilized
- the inorganic fine powder whose surface is hydrophilized is 55 to 80% by weight, and the inorganic fine powder and organic fine powder whose surface is not hydrophilized. More preferably, at least one of these is 20 to 45% by weight.
- the content of the inorganic fine powder and the organic fine powder whose surface is not hydrophilized in the easily peelable layer (B) is preferably 0.1 to 30% by weight.
- the “inorganic fine powder whose surface is not hydrophilized” refers to an inorganic fine powder that is not intentionally hydrophilized by the surface treatment agent, and includes processes such as normal pulverization, classification, and sedimentation. It refers to the inorganic fine powder obtained through the process.
- the amount of eluate from the easily peelable layer (B) can be adjusted by mixing a hydrophilic calcium carbonate fine powder and a normal heavy calcium carbonate fine powder.
- the hydrophilic calcium carbonate The water absorption can be adjusted by combining the fine powder and the organic fine powder.
- the easily peelable layer (B) of the present invention preferably contains a dispersant in order to uniformly finely disperse the inorganic fine powder.
- the inorganic fine powder dispersant include acid-modified polyolefin and silanol-modified polyolefin.
- the acid-modified polyolefin includes a hydroxyl-free polyolefin obtained by random copolymerization or graft copolymerization of maleic anhydride, or a carboxylic acid group-containing polyolefin obtained by random copolymerization or graft copolymerization of an unsaturated carboxylic acid such as methacrylic acid or acrylic acid. And epoxy group-containing polyolefin obtained by random copolymerization or graft copolymerization of glycidyl methacrylate.
- maleic anhydride-modified polypropylene maleic anhydride-modified polyethylene, acrylic acid-modified polypropylene, ethylene / methacrylic acid random copolymer, ethylene / glycidyl methacrylate random copolymer, ethylene / glycidyl methacrylate graft copolymer, glycidyl.
- methacrylate-modified polypropylene examples include methacrylate-modified polypropylene.
- maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene are particularly preferable.
- maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene include Modic AP manufactured by Mitsubishi Chemical Corporation, trade name “P513V”, trade name “M513”, trade name “P928”, Sanyo Chemical Industries, Ltd.
- the acid modification rate of the acid-modified polyolefin is preferably 0.01 to 20%, more preferably 0.05 to 15%. If the acid modification rate is 0.01% or more, the effect of dispersing the inorganic fine powder in the resin blend can be sufficiently obtained. When the acid modification rate is 20% or less, since the softening point of the acid-modified polyolefin does not become too low, compounding with a thermoplastic resin is relatively easy.
- the content of the dispersant when blending the dispersant into the easy release layer (B) is usually 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, with respect to 100 parts by weight of the inorganic fine powder.
- the content of the dispersant is 0.5 parts by weight or more, the inorganic fine powder is sufficiently dispersed, so that a desired surface opening ratio can be easily obtained and the liquid absorption volume can be easily improved.
- a drawability is favorable and it can suppress the draw break at the time of shaping
- the thickness of the easy release layer (B) is preferably 0.1 to 30 ⁇ m. A more preferable range varies depending on the use of the easily peelable film of the present invention. For example, when the easily peelable film of the present invention is used as a water-absorbing easily peelable film such as wallpaper, the thickness of the easily peelable layer (B) is more preferably 1 to 30 ⁇ m, and more preferably 1.5 to 15 ⁇ m. More preferably. If it is 1 ⁇ m or more, sufficient peelability and liquid absorption volume tend to be obtained.
- the thickness of the easily peelable layer (B) is more preferably 0.1 to 20 ⁇ m, and further preferably 3 to 18 ⁇ m. It is preferably 6 to 15 ⁇ m, more preferably 7 to 12 ⁇ m.
- the resin melt constituting the molded product enters the base layer (A) through the easily peelable layer (B), and the adhesive strength is improved, but the label is attached. Even if the label is peeled off from the resin molded product, it is difficult to stably perform the cohesive failure in the easily peelable layer (B), and there is a tendency that peeling is difficult.
- the thickness of the same layer (B) is too thick, there is no problem with the peeling strength when peeling, but the peeling position is not stable and the peeling surface is not uniform, so the stress required for peeling is not stable.
- irregularities remain on both the surface of the resin molded product and the peeled film, and even when printing is performed on the easy peelable layer (B) side, there is a tendency that the surface is not clearly visible.
- the easy release layer (B) is a stretched resin film layer that is stretched in at least one axial direction. By forming surface openings and internal vacancies by stretch molding, it is possible to obtain an easily peelable layer (B) with uniform thickness at the same time as obtaining a layer (B) that is easily peeled off by orientation of the resin. Become.
- the surface opening ratio of the easy-peeling layer (B) is preferably 7% or more, more preferably 7 to 60%, more preferably 12 to 50%, and more preferably 15 to 40%. Particularly preferred. If the surface opening ratio is 7% or more, sufficient liquid absorbability and adhesion tend to be obtained. If the surface opening ratio is 60% or less, the easily peelable layer (B) is less likely to break during stretch molding described later, and the laminated resin film tends to be stably molded.
- the “surface aperture ratio” in the present invention indicates an area ratio occupied by pores in the observation region when the surface on the easily peelable layer (B) side is observed with an electron microscope.
- an arbitrary part of the laminated resin film sample is cut out and attached to an observation sample stage, and gold or gold-palladium is deposited on the observation surface to scan an electron microscope (for example, manufactured by Hitachi, Ltd.). It can be determined by observing surface vacancies at an arbitrary magnification (for example, magnification of 500 to 3000 times) that is easy to observe using a scanning microscope S-2400). Further, the observed area was photographed, and the holes were traced on the tracing film, and the image filled with the image was processed with an image analysis device (manufactured by Nireco Corporation: model Luzex IID). It was set as the aperture ratio of the surface of an easy peeling layer (B).
- an image analysis device manufactured by Nireco Corporation: model Luzex IID
- the porosity of the easily peelable layer (B) is preferably 20 to 60%, more preferably 30 to 55%, and particularly preferably 35 to 50%. If the porosity is 20% or more, sufficient adhesion tends to be obtained. If the porosity is 60% or less, the easily peelable layer (B) is hardly broken during the stretch molding described later, and a stable laminated resin film can be molded.
- the “porosity” in the present invention is obtained by taking an electron micrograph of the cross section of the easily peelable layer (B) and determining the area ratio (%) of the occupancy in the cross-sectional area taken in the photograph. .
- a cut surface parallel to the thickness direction of the film (that is, perpendicular to the surface direction) is prepared using a microtome, for example.
- a microtome for example.
- the arithmetic average roughness Ra of the surface of the easily peelable layer (B) is preferably 0.3 to 1.8 ⁇ m, more preferably 0.5 to 1.6 ⁇ m, and 0.7 to 1.4 ⁇ m. It is particularly preferred. If the arithmetic average roughness is 0.3 ⁇ m or more, it is possible to obtain a fitting effect that enters the irregularities on the surface of the easily peelable layer with the resin pressure at the time of molding the molded product resin, thereby contributing to an improvement in adhesion. When the arithmetic average roughness is 1.8 ⁇ m or less, there is no possibility of image quality degradation due to missing dots due to unevenness when printing is performed.
- the “arithmetic average roughness” in the present invention was measured using a surface roughness meter (trade name: Surfcoder SE30, manufactured by Kosaka Laboratory Ltd.) based on JIS-B0601.
- the base layer (A) and the easily peelable layer (B) are preferably stretched in at least a uniaxial direction after lamination. Since the easily peelable layer (B) of the present invention has a low strength and a thin wall thickness, it is extremely difficult to stretch-mold the single easily peelable layer (B). By stretching after laminating the base layer (A) and the easily peelable layer (B), the easily peelable layer (B) can be easily stretched. Therefore, the base layer (A) is also useful as a carrier for stretching the easy-release layer (B). Various known methods can be used for such a lamination method.
- extrusion lamination methods There are extrusion lamination methods. It is also possible to use a combination of a multilayer die method and an extrusion lamination method.
- the stretching temperature can be carried out within a known temperature range suitable for a thermoplastic resin having a temperature not lower than the glass transition temperature of the thermoplastic resin mainly used for the base layer (A) and not higher than the melting point of the crystal part.
- a thermoplastic resin having a temperature not lower than the glass transition temperature of the thermoplastic resin mainly used for the base layer (A) and not higher than the melting point of the crystal part.
- the thermoplastic resin of the base layer (A) is a propylene homopolymer (melting point 155 to 167 ° C.)
- it is 100 to 166 ° C.
- it is a high density polyethylene (melting point 121 to 136 ° C.)
- it is 70 to 135 ° C.
- the temperature is 1 to 70 ° C. lower than the melting point.
- stretching examples include stretching between rolls utilizing the peripheral speed difference of the roll group, clip stretching using a tenter oven, and the like.
- the draw ratio is not particularly limited, and is determined in consideration of the purpose of use of the easily peelable film of the present invention and the characteristics of the resin used.
- the stretching ratio is usually 2 to 11 times, preferably 3 to 10 times.
- the draw ratio is more preferably 4 to 7 times.
- stretching is preferably performed 4 to 11 times.
- the area magnification is usually 2 to 80 times, preferably 3 to 60 times, more preferably 4 to 50 times. If the area magnification is 2 times or more, a desired aperture ratio is easily obtained on the surface of the film, and sufficient adhesiveness tends to be easily obtained. Moreover, if it is 80 times or less, there exists a tendency which becomes easy to prevent extending
- the temperature of the heat treatment is preferably selected within the range of a temperature 30 ° C. higher than the stretching temperature from the stretching temperature.
- the heat treatment is generally performed by a roll and a heat oven, but these may be combined. In these treatments, it is preferable to heat-treat the stretched film in a state where the stretched film is held under tension because a higher treatment effect can be obtained.
- the laminated resin film surface it is preferable to subject the laminated resin film surface to an oxidation treatment such as corona discharge treatment or plasma treatment after the heat treatment.
- an oxidation treatment such as corona discharge treatment or plasma treatment after the heat treatment.
- the surface wettability is further improved by subjecting the surface to oxidation treatment such as corona discharge treatment or plasma treatment, and an aqueous adhesive.
- the solvent absorption rate of the water-based adhesive is improved, and the adhesive component has an advantage that the adhesive component enters faster and more into the opening on the surface of the easily peelable layer (B).
- the easy absorption layer (B) thus produced preferably has a liquid absorption volume of 1 to 20 ml / m 2 .
- liquid absorption volume refers to JAPAN TAPPI No. Measured by a Bristow liquid absorbency test in accordance with 51: 2000, using a Bristow tester type II manufactured by Kumagai Riki Kogyo Co., Ltd. in a non-pressurized state with red water. 20 ⁇ l of a mixture containing ink at a ratio of 20: 1 was dropped and the liquid transfer amount at 50 ms was determined.
- the easily peelable film of the present invention can be made opaque so that the base is not seen through.
- the easily peelable film preferably has a concealing layer (C).
- Specific examples of the hiding layer (C) include colored printing such as black printing or gray printing on the surface of the easy peeling layer (B). These can be easily applied to an easily peelable film, but it is preferable to carry out such an amount that does not hinder the application of the adhesive described later.
- Another specific example of the masking layer (C) is one that improves the opacity of the base layer (A).
- a method of inserting black printing is mentioned.
- the method of inserting black printing between the layers is to perform black printing on one or both surfaces of the layers constituting the layer in advance, and stack them so that the black printing is sandwiched by a method such as dry lamination using an adhesive. Good.
- the easily peelable film of the present invention can be added with various functions such as writability, printability, scratch resistance and suitability for secondary processing by forming the base layer (A) into a multilayer.
- printability is particularly required.
- a conventionally known method such as lamination of a coat layer can be used.
- the easily peelable layer (B) side surface also has good printability.
- the surface of the easy-peeling layer (B) is smooth as described above, and preferably the inorganic fine powder whose surface is hydrophilized is used. Since the surface has few irregularities, dot gain (dot thickening) is small, and high-definition printing is possible.
- the use of inorganic fine powder whose surface is hydrophilized improves the wettability (affinity) of the ink and the like, and exhibits excellent ink transferability in combination with capillary action due to openings.
- the easily peelable film of the present invention When used as a water-absorbing easily peelable film such as wallpaper, it is preferable to use the film as a long winding (roll) form. It is preferable to employ flexographic printing or inkjet printing using a plotter. In the case of using an easily peelable film as a label, it is preferable that higher-definition printing can be performed, and offset printing or the like is preferable as a printing mode.
- a coating layer (D) that matches the printing technique is provided in order to fix the coloring material on the surface on the base layer (A) side that becomes the printing surface. It is preferable.
- a suitable coating layer (D) can be applied to inkjet printing including water-based inkjet, solvent-based inkjet, UV inkjet, latex-type inkjet, and the like.
- a coating layer (D) containing polyether urethane to which silica is added is preferable.
- the surface of the easy peelable film of the present invention is printed on the side of the easy peelable layer (B) and used as a label, for example, if the base layer (A) is opaque, the easy peelable layer (B) is peeled off. It is possible to recognize information such as a pattern and characters below and a barcode such as a QR code from the resin molded product or the label. Therefore, not only printing on the surface of the base layer (A) where the content and state of the resin-molded product with label can be described, but also printing on the surface of the easily peelable layer (B) can prevent counterfeiting and re-use of the resin container with label. Additional functions such as prevention of use and secondary use of coupons with peeled labels can be added.
- the printing provided on the easily peelable layer (B) can be visually confirmed only by emitting light by applying a black light even if it can be visually confirmed by using a normal process four-color ink, special color ink, metallic ink or the like. A thing using fluorescent ink etc. may be used. If the latter, better anti-counterfeiting is possible.
- the easy-peelable film of the present invention is obtained by applying an adhesive directly to the back side of the easy-peelable layer (B), to make a wood wall material, gypsum board, various composite materials (resin decorative board, wood plywood, etc.) and iron plate. Suitable for adherends made of aluminum plate, glass, earthenware, and resin, and can be used by directly bonding together. For this reason, when using the easily peelable film of this invention for wallpaper, a label, etc., it is not necessary to lining the back material (natural paper etc.) on the back surface.
- the adhesive used for laminating the easily peelable film of the present invention is not particularly limited, and protein-based adhesives, water-containing carbon-based adhesives, synthetic resin-based adhesives, solvent-based adhesives, and the like can be used.
- adhesives that use water as a medium such as protein adhesives, water-containing carbon adhesives, and synthetic resin adhesives, are collectively referred to as aqueous adhesives.
- the adhesive may be either water-based or solvent-based, but it is preferable to use a water-based adhesive from the viewpoint of workability and safety (poisoning due to solvent scattering, fire, etc.).
- a water-based adhesive has a property of dissolving or swelling in water.
- protein-based adhesives include gelatin, glue, and casein.
- water-containing carbon adhesive include starch and derivatives thereof, and examples of the cellulose derivative include hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose (CMC), and viscose.
- CMC carboxymethyl cellulose
- Other examples include arabic rubber and tragacanth rubber.
- the synthetic resin adhesive examples include polyvinyl alcohol, polyvinyl ether, and polyvinyl pyrrolidone.
- polyacrylamide, polyethylene oxide, polyvinyl amide, water-soluble polyurethane, polyacrylic acid resin and salts thereof, and the like can be given.
- the adhesive agent using the emulsion obtained by emulsion polymerization etc. such as vinyl acetate, acrylic acid ester, ethylene vinyl acetate, vinyl chloride, is also mentioned.
- aqueous adhesive used for laminating the easily peelable film of the present invention to an adherend
- starch and its derivatives polyacrylic acid, polyacrylamide, polyethylene oxide, polyvinyl alcohol, workability, adhesiveness, etc.
- Carboxymethyl cellulose (CMC), vinyl acetate and polyvinyl amide are preferred, and starch and derivatives thereof are more preferably used.
- the peel strength of the easily peelable layer (B) is preferably in the range of 50 to 180 gf / 18 mm. It is preferable to proceed in a uniform plane by cohesive failure in B).
- the peel strength indicates the strength required when the film is peeled off after being attached to the adherend, but the peeling itself proceeds by breaking the easy peelable layer (B) where there is no penetration of the adhesive.
- a pressure-sensitive adhesive tape is affixed to the easy-peeling layer (B) in a pseudo manner, and the measurement is performed with the strength required when the adhesive tape is peeled off.
- peel strength means that an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd., trade name “Cellotape”, brand name “CT-18”) is attached to the surface of the easy peelable layer (B).
- the easily peelable layer (B) having water absorption performance remains on the wall surface or bottle. It is sufficient if the water-based adhesive is directly applied to the easy-peeling layer (B) of another easily-peelable film, and the application is applied from above the easy-peeling layer (B) remaining on the wall surface or bottle. Adhesiveness is obtained. In other words, when applying a new wallpaper or label to the adherend, it is not necessary to work after removing the easy peeling layer (B) remaining on the wall or bottle after peeling off the previous wallpaper or label. Further, it is possible to repeatedly apply using the easily peelable layer (B) remaining on the wall surface or bottle.
- Adhesive and easy-peeling layer (B) remain and accumulate on the wall or bottle as the adherend each time the adhesive-peeling cycle of the easy-peeling film of the present invention is repeated. Since it peels thinly and uniformly, uneven unevenness does not occur and appearance deterioration hardly occurs.
- the easily peelable film of the present invention is suitable as an in-mold label for direct blow molding in which a molten resin parison is pressure-bonded to the inner wall of a mold by compressed air or stretch blow molding using a preform. It can also be suitably used as an in-mold label for injection molding in which molten resin is poured into a mold and solidified by cooling.
- a label for differential pressure molding after setting the label printing surface to be in contact with the inner surface of the lower female die of the differential pressure molding die, it is fixed to the inner wall of the mold by suction, and then used for molding product molding material
- the melt of the resin sheet can be guided above the lower female mold, and the label can be integrally fused to the outer wall of the molded product by differential pressure.
- the differential pressure forming either vacuum forming or pressure forming can be adopted, but in general, differential pressure forming using both of them and utilizing plug assist is preferable.
- the resin molded product in which the in-mold molding label of the present invention is adhered and integrated is formed without any deformation of the label because the label and the resin molded product are integrally molded after the label is fixed in the mold.
- the product and the label have an appropriate adhesive strength, have no blisters, and a molded product with a good appearance decorated with the label can be obtained.
- thermoplastic resins examples include polypropylene resin, polyethylene resin, polystyrene resin, and polyethylene terephthalate resin. These may be used alone or in combination.
- the labeled resin molded product of the present invention is a container obtained by the above-described molding technique, and is a household detergent, bathtub detergent, toilet cleaner, car wash detergent, face wash, liquid soap, shampoo, rinse, deodorant.
- the resin-molded article with a label according to the present invention can be optionally peeled off by hand as necessary.
- the adhesive strength is maintained so that it does not peel off naturally, and there is no problem. Peeling when the base layer (A) is peeled off from the resin-molded article with a label proceeds by cohesive failure in the easily peelable layer (B). Therefore, the resin molded article with a label according to the present invention can achieve a desired stress for peeling by suitably adjusting the cohesive force of the easily peelable layer (B) from the composition such as the blending surface and thickness.
- the peel strength (stress required for peeling) when peeling off the base layer (A) of the label attached to the resin molded product is preferably in the range of 40 to 160 gf / 15 mm, and preferably in the range of 100 to 160 gf / 15 mm. A range of 120 to 160 gf / 15 mm is particularly preferable.
- the peel strength indicates the strength required when the base layer (A) is peeled off after being attached to a resin molded product. Peeling preferably proceeds in a uniform plane due to cohesive failure in the easily peelable layer (B). When the peel strength is 40 gf / 15 mm or more, there is a tendency that it is difficult to peel off due to an external impact when it is attached to a resin molded product.
- peel strength is 160 gf / 15 mm or less, it will not exceed the strength of the adhesive or the surface strength of the resin molded product when affixed to the resin molded product. Tends to cause cohesive failure.
- “Peel strength” in the present invention is a stress required for peeling a label (base material layer (A)), and in a resin-molded product with a label, the label adhering portion of the molded product is 15 mm wide and 100 mm long.
- AUTOGRAPH tensile tester
- This peel strength is obtained by setting the crystallinity of the crystalline polypropylene used for the easy peelable layer (B) to 65% or more, blending a predetermined amount of incompatible thermoplastic resin or inorganic fine powder, This can be achieved by stretching the easily peelable layer (B) in at least a uniaxial direction.
- the peel strength is preferably such that the inorganic fine powder whose surface is hydrophilized is used, the stretching is performed at a temperature lower than the melting point of the crystallization site of crystalline polypropylene, and the heat It can be adjusted by selecting a resin having a relatively low viscosity as the plastic resin, or setting the porosity of the easily peelable layer (B) within a specific range.
- the peel strength is the easy-peeling layer of the laminated resin film. It is also possible to measure the strength of the laminated resin film by pseudo-determining from a value obtained by measuring the strength required when the adhesive tape is attached to (B) and peeled off.
- the peel strength of the single layer resin film is as follows: Adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd., trade name “Cellotape”, brand name “CT-18”) is attached to the easy peelable layer (B) surface, and the length is 100 mm.
- the base layer (A) and the adhesive tape can be easily peeled at an angle of 180 ° at a tensile speed of 300 mm / min.
- the stress generated when peeling was stable in the release layer (B) was measured with a load cell, and was determined from the average values in the horizontal and vertical directions.
- the peel strength obtained by this method is preferably 40 to 200 gf / 18 mm, more preferably 50 to 190 gf / 18 mm, and particularly preferably 60 to 180 gf / 18 mm. This peel strength can be adjusted by using the above-described method described as a method for adjusting the stress required for peeling the label (base material layer (A)).
- Laminated resin films (Examples 1 to 19 and Comparative Examples 1 to 7) were produced according to the following procedure.
- Table 1 shows details of the materials used. “MFR” in the table means melt flow rate.
- Tables 2 and 3 list the type and amount (% by weight) of materials used in the production of each laminated resin film, stretching conditions, total thickness and thickness of the [B] layer, and the presence or absence of the [C] layer. The material numbers listed in Tables 2 and 3 correspond to the material numbers listed in Table 1.
- Example 1 to 18 and Comparative Examples 1 to 5 the compound [A1] shown in Table 2 or 3 was melt-kneaded with an extruder set at 250 ° C. and extruded into a sheet through a die. And it cooled to 70 degreeC with the cooling device, and obtained the unstretched sheet
- the blend [B] shown in Table 2 or Table 3 was melt-kneaded with another extruder set at 250 ° C. and extruded into a sheet shape through a die, and was applied to the other surface of the longitudinally uniaxially stretched film. Laminated. The laminate was heated to 158 ° C. and stretched 9 times in the transverse direction using a tenter stretching machine to obtain a laminated resin film having a three-layer structure that was uniaxially stretched / biaxially stretched / uniaxially stretched (see FIG. 2). ).
- Example 9 gravure ink (trade name: XS-756, manufactured by DIC Graphics Co., Ltd.) and a gravure printing machine were used on the surface of the laminated resin film obtained in Example 2 on the [B] layer side. Gray printing was performed to obtain a laminated resin film provided with a concealing layer (C).
- Example 19 the blend [A2], the blend [A1] and the blend [B] shown in Table 3 were melt-kneaded with three extruders set at 250 ° C., respectively, to feed block, multi-manifold Was laminated in a die through a multi-layer die using the same, and this was coextruded into a sheet shape and cooled to 70 ° C. with a cooling device to obtain a three-layer unstretched sheet. This unstretched sheet was heated to 145 ° C., then stretched 5 times between rolls in the machine direction, then heated to 158 ° C.
- the blend [A2] shown in Table 3 was melt-kneaded with an extruder set at 250 ° C., extruded into a sheet through a die, and laminated on the [A1] side of the longitudinally uniaxially stretched film.
- the laminate was heated to 158 ° C. and stretched 9 times in the transverse direction using a tenter stretching machine to obtain a laminated resin film having a three-layer structure that was uniaxially stretched / biaxially stretched / biaxially stretched (see FIG. 2). ).
- Example 20 The surface of the laminated resin film obtained in Example 2 on the [A2] side is coated with a coating liquid having the following composition using a gravure coater so that the solid content is about 2.0 g / m 2. And dried to form a coat layer (D) suitable for aqueous inkjet printing.
- ⁇ Coating solution composition Synthetic silica powder 100 parts by weight (trade name “Mizukasil P-78D”, average particle size 8 ⁇ m, manufactured by Mizusawa Chemical Co., Ltd.) 30 parts by weight of polyvinyl alcohol (trade name “Kuraray Poval PVA-117”, manufactured by Kuraray Co., Ltd.) 10 parts by weight of an epichlorohydrin adduct of polyamide polyamine (trade name “WS4082”, manufactured by Seiko PMC Co., Ltd.) Polyacrylic acid soda 5 parts by weight (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1600 parts by weight of water
- Example 21 A metal foil was transferred and deposited on the surface of the laminated resin film obtained in Example 2 on the [A2] layer side, and a coating liquid containing a polyamidopolyamine resin (trade name “Topaz” was used on the surface of the metal foil using a gravure coater. 17 liquid ", manufactured by Toyo Ink Mfg. Co., Ltd., so that the solid content is about 0.5 g / m 2, and dried to be a wet electrophotographic printing machine (for example, trade name“ Indigo WS4000 ”, A coat layer (D) suitable for printing by Hewlett-Packard Co. was formed.
- a coating liquid containing a polyamidopolyamine resin trade name “Topaz”
- the ratio of the thicknesses of the [A1] layer and the [A2] layer was 1:24.
- Test Example 1 For each laminated resin film produced in Examples and Comparative Examples, printing characteristics, opacity, liquid absorption volume, peel strength, peelability to gypsum board, adhesiveness / peelability to bottles, concealability, re-sticking workability, recycling Suitability was evaluated. Details of each test are as follows.
- Adhesive tape (made by Nichiban Co., Ltd., trade name “Cerotape”, brand name “CT-18”) is pasted on the ink surface of each laminated resin film that is gravure printed on the side surface, and pressed sufficiently with fingers After that, the adhesive tape is manually peeled off at a speed of about 1000 mm / sec by pulling the non-adhered part while keeping the angle between the non-adhered part of the adhesive tape and the laminated resin film at 90 degrees, and the ink is removed.
- the manner of evaluation was evaluated according to the following criteria, and evaluated according to the following four levels.
- Liquid absorption volume JAPAN TAPPI No. It measured by the Bristow liquid absorptivity test based on 51: 2000. Specifically, 20 ⁇ l of a mixture of 20: 1 red water-based ink was added to ion-exchanged water in a non-pressurized state using a Bristow tester type II manufactured by Kumagai Riki Kogyo Co., Ltd. The amount of liquid transfer at 50 ms was determined.
- peeling startability After peeling off one side of the four sides of each laminated resin film with a nail from the gypsum board by 1 cm from the end, hold the peeled side by hand, peel off from the gypsum board, and easily peel off The state until peeling due to cohesive failure of the layer (B) was observed from the distance, and evaluated in the following four stages.
- peeling off from a gypsum board by hand it peeled off by pulling the peeling part of a laminated resin film, maintaining the angle which the gypsum board surface and the peeling part of a base layer (A) make about 135 degrees.
- Adhesive tape (made by Nichiban Co., Ltd., trade name “Cerotape”, brand name “CT-18”) is applied to one side of the four sides of each laminated resin film along the side. Put the base layer (A) on the gypsum board by pulling the peeled part of the base layer (A) while keeping the angle between the plaster board surface and the peeled part of the base layer (A) at about 135 °. I peeled off more.
- the peeling propagation state and peeling force of the easy peeling layer (B) at this time were evaluated in the following four stages.
- each laminated resin film was peeled off from the gypsum board in the same manner as the peel initiation test for the gypsum board.
- the same water-based adhesive was applied to the peeled surface of each laminated resin film with an automatic wallpaper pasting machine (manufactured by Kyokuto Sangyo Co., Ltd.) so that the solid content was 8 g / m 2. It was made to re-adhere on the plaster board which has not been affixed, and the external appearance was evaluated.
- ⁇ The laminated resin film after re-adhesion does not show irregular appearance of irregularities, and when peeled, it peels off again from the easy-release layer (B) part of the film.
- ⁇ Irregularities on the laminated resin film after re-adhesion
- the easy peeling layer (B) peeled off from the rebonding surface was uneven and had practical problems.
- X The uneven appearance of the unevenness was seen in the laminated resin film after reattachment. In addition, peeling from the rebonding surface occurs from both the film side and the adherend side, so it is very uneven and cannot be used practically.
- Table 4 summarizes the test results of the above evaluation items.
- Examples 101 to 116, Comparative examples 101 to 105 The compound [A1] described in Table 5 or 6 is melt-kneaded with an extruder set at 250 ° C., extruded into a sheet shape through a die, and cooled to 70 ° C. with a cooling device to form a single layer. An unstretched sheet was obtained. This non-stretched sheet was reheated to 145 ° C., and then stretched 5 times in the longitudinal direction using the peripheral speed difference between a number of rolls to obtain a longitudinally uniaxially stretched film.
- the compound [A2] and the compound [B] described in Table 5 or 6 are melt-kneaded with an extruder set individually at 250 ° C., extruded into a sheet through a die, and the longitudinally uniaxially stretched film.
- the compound [A2] was laminated on one side of the film, and the compound [B] was laminated on the other side to obtain a laminate having a three-layer structure of [A2] / [A1] / [B].
- the laminate was reheated to 158 ° C.
- Example 117 A multi-layer die using a feed block and a multi-manifold by melt-kneading each of the compound [A2], the compound [A1] and the compound [B] shown in Table 6 with three extruders set at 250 ° C. Were laminated in a die, coextruded into a sheet, and cooled to 70 ° C. with a cooling device to obtain a three-layer unstretched sheet. This unstretched sheet was heated to 145 ° C., then stretched 5 times between rolls in the machine direction, then heated to 158 ° C.
- Example 107 A multilayer film of Example 101 of JP-A No. 2003-295767 was obtained and used as an in-mold label (see FIG. 3).
- a layer (Y) and a layer (B) capable of delamination are individually provided via an intermediate layer (C), and the total thickness of the multilayer film is 100 ⁇ m, and a layer capable of delamination
- the thickness of (Y) is 5 ⁇ m
- the thickness of layer (B) is 5 ⁇ m.
- the layer (B) was a heat seal layer composed only of an ethylene / 1-hexene copolymer, and the surface opening ratio of this layer was 0%.
- Example 101 of JP-A-2006-309175 was obtained and used as an in-mold label (see FIG. 4).
- the propylene homopolymer (trade name: FY4, manufactured by Nippon Polypro Co., Ltd.) used for this layer (B) has a melting point of 164 ° C., a density of 0.9055 g / cm 3 , and a crystallinity of 64.4%. It is.
- the base layer (A) is composed of three layers of layer (A2) / layer (A1) / layer (A3), but the number of layers constituting the base layer (A) is almost equal to the result shown in Table 6. It does not affect.
- [Molding resin molded products with labels] [injection molding] Injection molding machine (made by Niigata Steel Co., Ltd., model: NV50ST, mold clamping force: 50 tons, vertical layout type) and resin molded product with a size of 130 mm in width, 150 mm in length, and 1 mm in thickness Using the mold for molding, the in-mold molding label obtained above was cut into a size of 100 mm wide and 130 mm long, and the base layer (A) side was placed on the surface of the female mold attached to the lower fixed platen side. The label was fixed so as to be in contact with the mold, the mold was then clamped, and the polystyrene melted from the injection device set at 200 ° C.
- melting start temperature after bonding the label injected molten resin into the mold from the gate section together with the solidified by cooling at a pressure of about 95 ° C.) to 745kgf / cm 2, mold opening It was to obtain a label stuck to the plate-shaped PS made injection molded product, which was used as a labeled resin shaped article.
- high-density polyethylene manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec HD HB330, melting point: 133 ° C.
- compressed air of 4.2 kg / cm 2 was supplied into the parison to adhere the label for in-mold molded with the inflate the parison is brought into close contact with the mold container shape, then After cooling the mold at 10 ° C. of the cooling water, taken out hollow container molded article label to the mold opening after about 10 seconds it has stuck, which was used as a labeled resin shaped article.
- the material of the resin molded product was changed to a polypropylene random copolymer (manufactured by Nippon Polypro Co., Ltd., trade name: Novatec PP EG-8, melting point: 143 ° C.), and melt-extruded at 200 ° C. in the same manner.
- the hollow container molded product with the label attached was taken out and used as a resin molded product with a label.
- the in-mold molding label of the present invention has printability, and even if the material of the resin molded product to be attached is changed variously, adhesion to the resin molded product is strong. Moreover, even if the molding conditions of the molded product are changed, it is possible to perform good bonding. For this reason, if this invention is utilized, it is not necessary to prepare the label for in-mold molding separately according to molding conditions, such as a raw material and temperature of a resin-molded product, and a single kind of label for in-mold molding is manufactured variously. It can be attached to various resin molded products molded under certain conditions.
- the present invention it is possible to easily separate the base layer (A) of the label from the resin molded product with a label. For this reason, if this invention is utilized, the collection
- a Base layer A1, A2, A3 Each layer constituting the base layer B Easy peelable layer Y Layer capable of delamination Z Intermediate layer
Abstract
Description
また本発明は、易剥離性フィルムからなるインモールド成形用ラベルにも関する。より具体的には、溶融した熱可塑性樹脂のパリソンを金型内に導き圧空を用いて付形する中空成形、或いは溶融した熱可塑性樹脂を金型内に導き該樹脂圧で付形する射出成形、或いは溶融した熱可塑性樹脂シートを金型上に導き減圧または加圧により付形する減圧成形または圧空成形において、予め該ラベルを金型内壁面に接するように配置し、次いで溶融した熱可塑性樹脂を金型内に導き樹脂成形品を成形する際に、該ラベルと該樹脂成形品が一体化したラベル付き樹脂成形品を製造することができるインモールド成形用ラベルに関するものである。
また、壁紙及びラベルの貼り替え時に剥がしたフィルムをマテリアルとしてそのままリサイクルすることができなくなるという問題がある。剥がしたフィルムをリサイクルするためには、フィルムと接着剤を分離する、もしくはフィルムと裏打ち材を分離しなければならないが、通常これらは強固に結合しているため実施は困難である。
また、本発明は、樹脂成形品の素材を問わずラベルと樹脂成形品との接着が強固であり、広範囲の成形品成形条件でラベルの貼り合わせが可能であり、且つ、インモールド成形したラベル付き樹脂成形品から、ラベルの基層を容易に分離することが可能であるインモールド成形用ラベルを提供することも課題とした。
さらに、該インモールド成形用ラベルを用いて樹脂の回収利用が容易なラベル付き樹脂成形品、および該インモールド成形用ラベルの易剥離層(B)側表面上に予め印刷を施しておくことによりラベル付き樹脂成形品からラベルの基層(A)を分離した際に樹脂成形品およびラベルの少なくとも一方で該印刷を視認することが可能であるラベル付き樹脂成形品を提供することも課題とした。
[1] 基層(A)と易剥離層(B)の積層樹脂フィルムを含む易剥離性フィルムであって、
該基層(A)が熱可塑性樹脂を含み、
該易剥離層(B)が結晶化度が65%以上である結晶性ポリプロピレン樹脂及び該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂のブレンド物30~60重量%と、微細粉末40~70重量%を含み、該ブレンド物において結晶性ポリプロピレン樹脂100重量部に対し該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂が105~300重量部の割合でブレンドされており、且つ、
該易剥離層(B)が少なくとも1軸方向に延伸されていることを特徴とする易剥離性フィルム。
[2] 該微細粉末が、表面処理剤により表面を親水化処理されている無機微細粉末を含むことを特徴とする[1]に記載の易剥離性フィルム。
[3] 該表面処理剤が、水溶性アニオン系界面活性剤、水溶性カチオン系界面活性剤、及び水溶性非イオン系界面活性剤からなる群より選択される少なくとも一種の界面活性剤であることを特徴とする[2]に記載の易剥離性フィルム。
[4] 該微細粉末が、表面が親水化処理されている無機微細粉末を50~99.9重量%と、表面が親水化処理されていない無機微細粉末および有機微細粉末の少なくとも一方を0.1~50重量%含むことを特徴とする[2]または[3]に記載の易剥離性フィルム。
[5] 該易剥離層(B)の「Japan TAPPI No.51-2000」により測定される液体吸収容積が1~20ml/m2であることを特徴する[2]~[4]の何れか一項に記載の易剥離性フィルム。
[6] 該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂が、ポリエチレン樹脂、スチレン系樹脂、環状ポリオレフィン樹脂、エチレン-環状オレフィン共重合樹脂、ポリアミド系樹脂、ポリエステル系樹脂、及びポリカーボネートからなる群より選択される少なくとも1種の樹脂であることを特徴とする[1]~[5]の何れか一項に記載の易剥離性フィルム。
[7] 該易剥離層(B)が、更に微細粉末の分散剤を、微細粉末100重量部に対し0.5~30重量部含むことを特徴とする[1]~[6]の何れか一項に記載の易剥離性フィルム。
[8] 該分散剤が、マレイン酸変性ポリオレフィン及びシラノール変性ポリプロピレンの少なくとも一方であることを特徴とする[7]に記載の易剥離性フィルム。
[9] 該易剥離層(B)の厚みが、0.1~20μmであることを特徴とする[1]~[8]の何れか一項に記載の易剥離性フィルム。
[10] 該易剥離層(B)表面の開口率が、7~60%であることを特徴とする[1]~[9]の何れか一項に記載の易剥離性フィルム。
[11] 該易剥離層(B)表面の算術平均粗さが、0.3~1.8μmであることを特徴とする[1]~[10]の何れか一項に記載の易剥離性フィルム。
[12] 該基層(A)が、多層構造であることを特徴とする[1]~[11]の何れか一項に記載の易剥離性フィルム。
[13] 該易剥離層(B)表面上に印刷が施されていることを特徴とする[1]~[12]の何れか一項に記載の易剥離性フィルム。
[14] 更に隠蔽層(C)を有することを特徴とする[1]~[13]の何れか一項に記載の易剥離性フィルム。
[15] 該隠蔽層(C)が、易剥離層(B)側表面への黒色印刷または灰色印刷、基層(A)への隠蔽顔料添加、基層(A)間への黒色印刷挿入からなる群より選択される少なくとも一つの手法からなることを特徴とする[14]に記載の易剥離性フィルム。
[16] 該基層(A)側表面上に更にコート層(D)を有することを特徴とする[1]~[15]の何れか一項に記載の易剥離性フィルム。
[17] [1]~[16]のいずれか一項に記載の易剥離性フィルムからなるインモールド成形用ラベル。
[18] [17]に記載のインモールド成形用ラベルを樹脂成形品に貼着したラベル付き樹脂成形品。
[19] 該樹脂成形品が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリスチレン樹脂、及びポリエチレンテレフタレート樹脂からなる群より選択される少なくとも1種の熱可塑性樹脂からなることを特徴とする[18]に記載のラベル付き樹脂成形品。
[20] 該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がす際に、剥離が易剥離層(B)内の凝集破壊により進行することを特徴とする[18]または[19]に記載のラベル付き樹脂成形品。
[21] 該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がす際の、剥離に要する応力が、40~160gf/15mmであることを特徴とする[18]~[20]の何れか一項に記載のラベル付き樹脂成形品。
[22] 該インモールド成形用ラベルの易剥離層(B)表面上に印刷が施されており、該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がした際に、該印刷が樹脂成形品上に残ることを特徴とする[18]~[21]の何れか一項に記載のラベル付き樹脂成形品。
[23] 該インモールド成形用ラベルの易剥離層(B)表面上に印刷が施されており、該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がした際に、該印刷がラベル上に残ることを特徴とする[18]~[22]の何れか一項に記載のラベル付き樹脂成形品。
[24] [1]~[16]のいずれか一項に記載の易剥離性フィルムの易剥離層(B)側表面に水系接着剤層を施した壁紙。
[25] 壁から壁紙を剥がす際に、剥離が易剥離層(B)内の凝集破壊により進行することを特徴とする[24]に記載の壁紙。
[26] 壁から壁紙を剥がす際の剥離に要する応力が、50~180gf/18mmであることを特徴とする[24]または[25]に記載の壁紙。
[27] 壁から壁紙を剥がした後に、壁表面に易剥離層(B)の一部が薄膜として残留し、この残留物が液体を吸収することを特徴とする[24]~[26]のいずれか一項に記載の壁紙。
[28] [1]~[16]のいずれか一項に記載の易剥離性フィルムの易剥離層(B)側表面に水系接着剤層を施したグルーラベル。
[29] [28]のグルーラベルを貼着したラベル付き容器。
また、本発明のインモールド成形用ラベルは、樹脂成形品の素材を問わず樹脂成形品との接着が強固であり、広範囲の成形品成形条件で貼り合わせることが可能であり、且つ、インモールド成形したラベル付き樹脂成形品から、ラベルの基層を容易に分離することが可能であるという特徴を有する。
さらに、本発明のラベル付き樹脂成形品は、樹脂成形品の回収利用が容易であるとともに、インモールド成形用ラベルの易剥離層(B)側表面上に予め印刷を施しておくことによりラベル付き樹脂成形品からラベルの基層(A)を分離した際に樹脂成形品か基層(A)の少なくとも一方で該印刷を視認することが可能であるという特徴を有する。
本発明の易剥離性フィルムは、基層(A)と易剥離層(B)の積層樹脂フィルムを含むものである(図1参照)。本発明のインモールド成形用ラベルも、同じ構成の易剥離性フィルムからなるものである。
基層(A)は熱可塑性樹脂を含み、それ自体の強度が後述の易剥離層(B)の強度よりも高く、(A)層を持ってラベルを引き剥がしたときに、それ自体内は破断をしない強度を有するものである。より具体的には基層(A)自体の凝集力(剥離強度ないし引張破断強度)が200gf/15mm以上のものであることが好ましい。基層(A)は透明であっても、半透明であっても、不透明であっても良い。
基層(A)に用いる熱可塑性樹脂の種類は特に制限されない。例えば、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、プロピレン系樹脂、ポリメチル-1-ペンテン、エチレン-環状オレフィン共重合体等のポリオレフィン系樹脂、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体、マレイン酸変性ポリエチレン、マレイン酸変性ポリプロピレン等の官能基含有ポリオレフィン系樹脂、ナイロン-6、ナイロン-6,6等のポリアミド系樹脂、ポリエチレンテレフタレートやその共重合体、ポリブチレンテレフタレート、ポリブチレンサクシネート、ポリ乳酸、脂肪族ポリエステル等の熱可塑性ポリエステル系樹脂、ポリカーボネート、アタクティックポリスチレン、シンジオタクティックポリスチレン等を使用することができる。これらの熱可塑性樹脂の中では、加工性に優れるポリオレフィン系樹脂、官能基含有ポリオレフィン系樹脂を用いることが好ましい。ポリオレフィン系樹脂のより具体的な例としては、エチレン、プロピレン、ブチレン、ブタジエン、イソプレン、クロロプレン、メチル-1-ペンテン、環状オレフィンなどのオレフィン類の単独重合体、及び、これらオレフィン類2種類以上からなる共重合体が挙げられる。
基層(A)は、単層構造のものであってもよいし、2層以上の多層構造のものであってもよい。基層(A)の多層化により筆記性、印刷適性、耐擦過性、2次加工適性等の様々な機能の付加が可能となる。
基層(A)を多層構造にする場合は、後述の易剥離層(B)に接する層である(A1)層の無機微細粉末及び有機フィラーの少なくとも一方の含有量は易剥離層(B)よりも5重量%以上、好ましくは10重量%以上少ないことが望ましい。(A1)層の無機微細粉末及び有機フィラーの少なくとも一方の含有量が易剥離層(B)に対して、5重量%以上低いことによって易剥離層(B)と(A1)層の空孔率に差ができ、易剥離性フィルムを被着体から剥離する際に易剥離層(B)のみに破壊伝播することができる。具体的には、(A1)層は熱可塑性樹脂を35~100重量%、好ましくは40~100重量%、無機微細粉末及び有機フィラーの少なくとも一方を0~65重量%、好ましくは0~60重量%を含む。
この多層構造の延伸軸数は、例えば2層構造の場合は、表面層/(A1)層として、無延伸/1軸、無延伸/2軸、1軸/1軸、1軸/2軸、2軸/1軸、2軸/2軸、を例示できる。
本発明における易剥離層(B)は、基層(A)の上に形成される。本発明の易剥離性フィルムの剥離は、易剥離層(B)の破壊(凝集破壊)により行われる。本発明では、同層(B)の破壊をより円滑にするため、樹脂材料として相互に非相溶の少なくとも2種の樹脂を配合し、相分離した状態のまま延伸することで、上記空孔の界面のみならず、これら樹脂間の界面でも剥離が起こり、同層(B)は均一面状に剥離することが可能になった。
本発明における易剥離層(B)は、液体の吸収が可能である。特に、表面処理剤により表面を親水化処理された無機微細粉末を配合した場合は、液体の吸収性が高い。これは、同層(B)を延伸した際にこれを核として多数の表面開口や内部空孔が形成されることに因る。このため、本発明の易剥離性フィルムには、特に水系の接着剤を適用可能であり、同接着剤を介して被着体との接着を可能にすることができるため、壁紙等の吸水易剥離性フィルムとして利用することができる。また、同層(B)は基層(A)よりも脆性で強度が弱い層であり、同層(B)の破壊により接着剤を含まない様態でフィルムを容易に剥離することができる。また同層(B)は従来公知の吸水層と比べて均一面状に剥離することができることから、被着体表面に同層(B)に由来する粗大な凹凸を残すことはなく、同被着体は再度別のフィルムを貼り付けても外観を損ねることはない。
本発明の易剥離層(B)は結晶性ポリプロピレン樹脂及び該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂のブレンド物を30~60重量%、好ましくは35~50重量%、微細粉末40~70重量%、好ましくは50~65重量%を含み、該易剥離層(B)が少なくとも1軸方向に延伸されていることを特徴とする。易剥離層(B)中の微細粉末の含有量が40重量%未満では、充分な剥離性が得られない。逆に70重量%を越えては成形安定性が損なわれる。
該ブレンド物において、結晶性ポリプロピレン樹脂100重量部に対して該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂は105~300重量部、好ましくは120~280重量部、より好ましくは140~270重量部の配合割合でブレンドされている。
結晶性ポリプロピレン樹脂とは上記のプロピレン系樹脂であって、その結晶化度が65%以上であり、66%以上であることが好ましく、67~80%であることが特に好ましいものである。結晶化度が65%以上であれば、結晶性ポリプロピレン樹脂の非晶部と熱可塑性樹脂の相溶が進みにくくて所期の界面剥離の効果が得られやすくなり、剥離に要する応力(剥離強度)を適度に小さくすることができる。また、結晶化度が80%以下であれば、商業的に入手することが容易である。
そのため上記の結晶化度を達成するためには、易剥離層(B)に用いる結晶性ポリプロピレン樹脂の密度が0.906g/cm3以上であることが好ましく、0.907g/cm3以上であることがより好ましく、0.908g/cm3以上であることが特に好ましい。
該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂は、ポリエチレン樹脂、スチレン系樹脂、環状ポリオレフィン樹脂、エチレン-環状オレフィン共重合樹脂、ナイロン-6、ナイロン-6,6、ナイロン-6,10、ナイロン-6,12等のポリアミド系樹脂、ポリエチレンテレフタレートやその共重合体、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンサクシネート、ポリ乳酸、脂肪族ポリエステル等の熱可塑性ポリエステル系樹脂、ポリカーボネート等が挙げられる。これらは2種以上混合して用いることもできる。これらの中でも、耐薬品性や生産コスト等の観点より、ポリエチレン樹脂を用いることが好ましい。非相溶性の熱可塑性樹脂の存在により、延伸フィルム作製時に結晶性ポリプロピレン樹脂とポリプロピレン樹脂に非相溶性の熱可塑性樹脂間で界面剥離が生じ剥離性を向上させている。ポリプロピレン樹脂に非相溶性の熱可塑性樹脂が105重量部未満、または300重量部を超える場合は十分な剥離性が得られない。
本発明において「非相溶」とは、結晶性ポリプロピレン樹脂と、非相溶性の熱可塑性樹脂のブレンド物を電子顕微鏡で観察した場合、海島構造のモルフォロジーを有しており、その構造の寸法が0.3~10μmであることを指す。
該微細粉末としては、親水化処理された無機微細粉末や、親水化処理されていない無機微細粉末や有機微細粉末を用いることができる。該微細粉末としては、親水化処理された無機微細粉末だけを用いてもよいし、親水化処理されていない無機微細粉末や有機微細粉末だけを用いてもよいし、親水化処理された無機微細粉末と親水化処理されていない無機微細粉末および/または有機微細粉末とを組み合わせて用いてもよい。
該無機微細粉末としては、重質炭酸カルシウム、軽質炭酸カルシウム、焼成クレイ、タルク、酸化チタン、硫酸バリウム、酸化亜鉛、酸化マグネシウム、珪藻土、酸化珪素などの無機微細粉末、無機微細粉末の核の周囲にアルミニウム酸化物ないしは水酸化物を有する複合無機微細粉末、中空ガラスビーズ等を例示することができる。中でも重質炭酸カルシウム、焼成クレイ、珪藻土は、安価で延伸時に多くの空孔を形成させることができるために好ましい。
該有機微細粉末としては、易剥離層(B)に用いるポリプロピレン樹脂とは異なる種類の樹脂を選択することが好ましい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ナイロン-6、ナイロン-6,6、環状ポリオレフィン、ポリスチレン、ポリメタクリレート等の重合体であって、ポリプロピレン樹脂の融点よりも高い融点(例えば170~300℃)ないしはガラス転移温度(例えば170~280℃)を有し、かつ非相溶のものを使用することができる。
表面を親水化処理した無機微細粉末を用いて易剥離層(B)を形成すれば、該易剥離層(B)表面の印刷適性が向上して美麗なフィルムやラベルを提供することができる。特に、インモールド成形用ラベルとして使用した場合は、綺麗なラベル付き成形品が得られると同時に、これらにより形成された易剥離層(B)は無機微細粉末と結晶性ポリプロピレンの界面剥離がより起こりやすいことから、より容易に成形品と分離することができる。
かかる界面活性剤の具体例として、例えば水溶性アニオン系界面活性剤としては、炭素数4~40の範囲の炭化水素基を有するスルホン酸塩、炭素数4~40の範囲の炭化水素基を有するリン酸エステル塩、炭素数4~40の範囲の高級アルコールのリン酸モノまたはジエステルの塩、炭素数4~40の範囲の炭化水素基を有するアルキルベタインやアルキルスルホベタインなどが挙げられる。例えば水溶性カチオン系界面活性剤としては、ジアリルアミン塩、炭素数1~4の範囲のアルキルジアリルアミン塩及びジアルキルジアリルアミン塩、すなわちメチルジアリルアミン塩やエチルジアリルアミン塩、ジメチルジアリルアミン塩、メタクリロイルオキシエチルトリメチルアンモニウム、アクリロイルオキシエチルトリメリルアンモニウム、メタクリロイルオキシエチルジメチルエチルアンモニウムやアクリロイルオキシエチルジメチルエチルアンモニウムのクライド、ブロマイド、メトサルフェート、またはエトサルフェート、N,N-ジメチルアミノエチルメタクリレートやN,N-ジメチルアミノエチルアクリレートをエピクロロヒドリン、グリシドール、グリシシジルトリメチルアンモニウムクロライドなどのエポキシ化合物でアルキル化して得られる4級アンモニウム塩が挙げられる。これらの中でも、好ましくはジアリルアミン塩、メチルジアリルアミン塩及びジメチルジアリルアミン塩である。例えば水溶性非イオン系界面活性剤としては、アクリルアミド、メタクリルアミド、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニルピロドリン、2-ヒドロキシエチルメタクリレート、2-ヒドロキシエチルアクリレート、2-ヒドロキシ(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、(メタ)アクリル酸メチルエステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸ブチルエステルが挙げられる。これらの中でも好ましくはアクリルアミド、メタクリルアミドである。
表面処理剤としては、平均分子量が1,000~15,000であるものを好ましく用いることができる。
これらの表面処理剤により表面処理された無機微細粉末の具体例として、例えばファイマテック社製の商品名「AFF」等を挙げることができる。
ここで「表面が親水化処理されていない無機微細粉末」とは、上記表面処理剤により意図して親水化処理を施していない無機微細粉末を指し、通常の粉砕、分級、沈降等のプロセスを経て得られた無機微細粉末を指す。例えば親水化処理された炭酸カルシウム微細粉末と、通常の重質炭酸カルシウム微細粉末とを混合すれば易剥離層(B)からの溶出物量を調整することができ、例えば親水化処理された炭酸カルシウム微細粉末と、有機微細粉末とを組み合わせれば吸水性を調整することができる。このように異なる種類の微細粉末を配合する場合であっても、接着剤層(B)に含まれる微細粉末の総量が70重量%を超える場合は易剥離性フィルムの延伸成形性が悪化し成形安定性が損なわれるため好ましくない。
また本発明の易剥離層(B)は、無機微細粉末を均一に微分散するために、分散剤を含むことが好ましい。
無機微細粉末の分散剤として、例えば酸変性ポリオレフィン、シラノール変性ポリオレフィンなどを例示することができる。本発明においては、特にマレイン酸変性ポリオレフィン及びシラノール変性ポリプロピレンを用いることが好ましい。
該酸変性ポリオレフィンとしては、無水マレイン酸をランダム共重合もしくはグラフト共重合した無水酸基含有ポリオレフィン、あるいはメタクリル酸、アクリル酸などの不飽和カルボン酸をランダム共重合もしくはグラフト共重合したカルボン酸基含有ポリオレフィン、グリシジルメタクリレートをランダム共重合もしくはグラフト共重合したエポキシ基含有ポリオレフィンなどが挙げられる。具体例としては、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリエチレン、アクリル酸変性ポリプロピレン、エチレン・メタクリル酸ランダム共重合体、エチレン・グリシジルメタクリレートランダム共重合体、エチレン・グリシジルメタクリレートグラフト共重合体、グリシジルメタクリレート変性ポリプロピレンなどが挙げられ、なかでも特に好ましくは無水マレイン酸変性ポリプロピレン及び無水マレイン酸変性ポリエチレンである。
無水マレイン酸変性ポリプロピレン及び無水マレイン酸変性ポリエチレンの具体例としては、三菱化学(株)製のモディックAP、商品名「P513V」や商品名「M513」や商品名「P928」、三洋化成工業(株)製、商品名「Umex1001」や商品名「Umex1010」や商品名「Umex2000」、三井・デュポンケミカル(株)製のHPR、商品名「VR101」が挙げられる。
酸変性ポリオレフィンの酸変性率は、0.01~20%が好ましく、0.05~15%がより好ましい。酸変性率が0.01%以上であれば、無機微細粉末の樹脂ブレンド物中への分散効果が十分に得られやすい。酸変性率が20%以下であれば、酸変性ポリオレフィンの軟化点が低くなりすぎることがないため熱可塑性樹脂とのコンパウンドが比較的容易である。
易剥離層(B)の肉厚は0.1~30μmとすることが好ましい。より好ましい範囲は、本発明の易剥離性フィルムの用途によって異なる。
例えば、本発明の易剥離性フィルムを壁紙等の吸水易剥離性フィルムとして用いる場合は、易剥離層(B)の肉厚は1~30μmとすることがより好ましく、1.5~15μmとすることがさらに好ましい。1μm以上であれば、十分な剥離性と液体吸収容積が得られやすくなる傾向がある。また30μmを越えても剥離する際の剥離強度には問題はないが、30μm以下であれば剥離位置が安定して剥離面が均一になりやすいため、壁紙等の吸水易剥離性フィルムを再貼り付けする際に凹凸が表面に浮き出しにくい傾向がある。
易剥離層(B)の表面開口率は7%以上であることが好ましく、7~60%であることがより好ましく、12~50%であることがより好ましく、15~40%であることが特に好ましい。表面開口率が7%以上であれば十分な液体吸収性や接着性が得られやすい傾向がある。表面開口率が60%以下であれば後述する延伸成形時に易剥離層(B)が破断しにくく積層樹脂フィルムの成形を安定に行いやすくなる傾向がある。
本発明における「表面開口率」は、易剥離層(B)側の面を電子顕微鏡で観察したときの観察領域中に空孔が占める面積割合を示す。具体的には、積層樹脂フィルム試料より任意の一部を切り取り、観察試料台に貼り付け、その観察面に金ないしは金-パラジウム等を蒸着して電子顕微鏡(例えば日立製作所(株)製の走査型顕微鏡S-2400)を使用して観察しやすい任意の倍率(例えば500倍~3000倍に拡大)にて表面の空孔を観察することにより求めることができる。さらに観察した領域を写真等に撮影し、空孔をトレーシングフィルムにトレースして塗りつぶした図を画像解析装置(ニレコ(株)製:型式ルーゼックスIID)で画像処理し、空孔の面積率を易剥離層(B)表面の開口率とした。
易剥離層(B)の空孔率は、20~60%であることが好ましく、30~55%であることがより好ましく、35~50%であることが特に好ましい。空孔率が20%以上であれば十分な接着性が得られやすい傾向がある。空孔率が60%以下であれば後述する延伸成形時に易剥離層(B)が破断しにくく安定した積層樹脂フィルムの成形が可能となる。
本発明における「空孔率」は、易剥離層(B)断面の電子顕微鏡写真を撮影し、その写真に撮影された断面領域内に占める空孔の面積割合(%)を求めることにより得られる。具体的には、積層樹脂フィルムをエポキシ樹脂で包埋して固化させた後、ミクロトームを用いて例えばフィルムの厚さ方向に対して平行(すなわち面方向に垂直)な切断面を作製し、この切断面を蒸着してメタライジングした後、上記電子顕微鏡で観察しやすい任意の倍率(例えば500倍~3000倍)に拡大して観察し、空孔部分をトレーシングフィルムにトレースし塗りつぶした図を上記画像解析装置で画像処理を行い、測定範囲を占める空孔の面積割合(%)を求めて空孔率(%)とした。
易剥離層(B)表面の算術平均粗さRaは0.3~1.8μmであることが好ましく、0.5~1.6μmであることがより好ましく、0.7~1.4μmであることが特に好ましい。算術平均粗さが0.3μm以上であれば成形品樹脂の成形時の樹脂圧力で易剥離層表面の凹凸に入り込む嵌合効果を得て、接着力向上に寄与できる。算術平均粗さが1.8μm以下であれば、印刷を施した際に凹凸に起因するドット抜け等による画質低下を招くこともない。
本発明における「算術平均粗さ」は、JIS-B0601の規定に基づき、表面粗さ計((株)小坂研究所製、商品名:サーフコーダーSE30)を用いて測定した。
基層(A)及び易剥離層(B)は積層後に少なくとも1軸方向に延伸することが好ましい。本発明の易剥離層(B)は強度が低く、肉厚が薄いため、易剥離層(B)単層での延伸成形は極めて困難である。基層(A)と易剥離層(B)を積層後延伸することにより、易剥離層(B)の延伸が容易となる。従って基層(A)は易剥離層(B)を延伸するための担持体としても有用である。
かかる積層方法についても公知の種々の方法が使用できるが、具体例としては、複数の押出機とフィードブロック、マルチマニホールド、多層ダイスを使用した多層ダイス方式と、複数の押出機とダイスを使用する押出しラミネーション方式等がある。又、多層ダイス方式と押出しラミネーション方式を組み合わせて使用することも可能である。
延伸倍率は特に限定されるものではなく、本発明の易剥離性フィルムの使用目的と、用いる樹脂の特性を考慮して決定する。延伸軸数が一軸である場合、延伸倍率は通常は2~11倍であり、好ましくは3~10倍の範囲内で延伸する。なかでも延伸倍率は4~7倍がより好ましい。テンターオーブンを利用したクリップ延伸の場合は4~11倍で延伸することが好ましい。延伸軸数が二軸である場合の面積倍率としては、通常は2~80倍であり、好ましくは3~60倍、より好ましくは4~50倍である。面積倍率が2倍以上であれば、フィルムの表面に所望の開口率が得らやすくなり、十分な接着性が得られやすくなる傾向がある。また80倍以下であれば、延伸切れや粗大な穴あきを防ぎやすくなる傾向がある。
こうして製造される易剥離層(B)の液体吸収容積は1~20ml/m2であるのが好ましい。これは表面処理した無機微細粉末の配合量及び延伸倍率に影響される易剥離層(B)の内部の空孔率、ならびに易剥離層(B)の肉厚により調整することができる。液体吸収容積が1ml/m2未満の場合は接着剤を介して易剥離性フィルムを被着体に貼り付けた際に接着剤が乾燥せず、本発明の所期の性能を発揮しない。本明細書において「液体吸収容積」とは、JAPAN TAPPI No.51:2000に準拠するブリストー液体吸収性試験により測定されるものであって、熊谷理機工業(株)製ブリストー試験機II型を使用して無加圧の状態でイオン交換水に赤色の水性インキを20:1に配合した混合物を20μl滴下して、50msにおける液体の転移量を求めたものである。
本発明の易剥離性フィルムは、下地が透けて見えないように不透明にすることもできる。易剥離性フィルムを不透明化するために、易剥離性フィルムは隠蔽層(C)を有することが好ましい。隠蔽層(C)の具体例としては、易剥離層(B)表面への黒色印刷または灰色印刷などの有色印刷が挙げられる。これらは容易に易剥離性フィルムに適用できるものであるが、後述の接着剤の適用を阻害しない程度に行うことが好ましい。
該隠蔽層(C)の別の具体例としては、基層(A)の不透明度を向上させるものが挙げられる。例えば基層(A)の原料配合へ隠蔽性の強い顔料、例えば酸化チタン粉末、アルミニウム粉末、カーボンブラック等を添加して不透明度の底上げを図る手法や、基層(A)を多層構造としてその層間に黒色印刷を挿入する手法が挙げられる。層間に黒色印刷を挿入する手法は、これを構成する層の一方または両方の表面に予め黒色印刷を施し、接着剤を用いたドライラミネート等の手法で黒色印刷を挟み込むようにこれらを積層すればよい。
本発明の易剥離性フィルムは、基層(A)の多層化により筆記性、印刷適性、耐擦過性、2次加工適性等の様々な機能の付加が可能となる。特に本発明品は壁紙や樹脂容器等のラベルとして表示に使用することができるため、特に印刷適性は必要とされる。易剥離性フィルムへの印刷適性の付与はコート層の積層など従来公知の手法を用いることができる。印刷としてはグラビア印刷、オフセット印刷、フレキソ印刷、スクリーン印刷、インクジェット印刷、電子写真印刷などの手法を用いて、ラベル上に絵柄、バーコード、製造元、販売会社名、キャラクター、商品名、使用方法などの意匠や情報を付与することができる。
また本発明の易剥離性フィルムは、易剥離層(B)側表面もまた良好な印刷適性を具備している。これは前述のとおり易剥離層(B)の表面が平滑であり、好ましくは表面を親水化処理した無機微細粉末を使用していることに起因するものである。同表面は凹凸が少ないことから、ドットゲイン(ドット太り)が小さく、高精細な印刷が可能である。また好ましくは表面を親水化処理した無機微細粉末を使用することによりインク等へぬれ(親和性)が向上し、開口による毛細管現象と併せて優れたインクの転移性を示す。
本発明の易剥離性フィルムを壁紙等の吸水易剥離性フィルムとして適用する場合について、以下に説明する。本発明の易剥離性フィルムは、裏面である易剥離層(B)側に直接接着剤を塗工して、木質壁材、石膏ボード、各種複合材料(樹脂化粧板、木質合板等)や鉄板、アルミニウム板、ガラス、陶器、樹脂からなる被着体に適し、直接貼り合わせて使用することができる。このため、本発明の易剥離性フィルムを壁紙及びラベル等に使用する場合、裏打ち材(天然紙等)を裏面に裏打ち加工する必要はない。このため、壁紙及びラベル等として施工した本発明の易剥離性フィルムを被着体からはがしてリサイクルする際には、裏打ち材(天然紙等)がリサイクル原料に混入せず、均一面状の剥離により接着剤は全て被着体側に残り、同フィルム側には残留しないため、材料のリサイクルが可能となる。
剥離強度が50gf/18mm未満の場合は、被着体に貼り付けた際に外部からの衝撃により剥がれやすく、剥離強度が180gf/18mmを超える場合は、接着剤の種類にもよるが接着剤の強度を上回ってしまう、もしくは被着体に貼り付けた際に被着体の表面強度を上回ってしまい、易剥離層(B)内で凝集破壊が発生しない。本明細書において「剥離強度」とは、易剥離層(B)面に粘着テープ(ニチバン(株)製セロハンテープ、商品名「セロテープ」、銘柄名「CT-18」)を貼着し、長さ100mmに切り取り、引張試験機((株)島津制作所製、商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と粘着テープとの剥離を易剥離層(B)にて発生させ、剥離が安定している時の応力をロードセルにより測定し、横方向と縦方向の平均値から求めた。
被着体である壁面もしくはボトル等には本発明の易剥離性フィルムの接着・剥離のサイクルにより都度、接着剤と易剥離層(B)が残留し蓄積してゆくが、同層(B)は薄く均一面状に剥離するために不均一な凹凸は発生せず、外観悪化は殆ど発生しない。
本発明の易剥離性フィルムをインモールド成形用ラベルとして利用する場合について説明する。
本発明の易剥離性フィルムは、溶融樹脂パリソンを圧空により金型内壁に圧着するダイレクトブロー成形用やプリフォームを用いた延伸ブロー成形用のインモールドラベルとしても好適であるが、射出装置で金型内に溶融樹脂を注入し冷却固化するインジェクション成形用のインモールドラベルとしても好適に使用できる。
更に差圧成形用のラベルとして、差圧成形金型の下雌金型の内面にラベルの印刷面が接するように設置した後、吸引により金型内壁に固定し、次いで成形品成形材料用の樹脂シートの溶融物を下雌金型の上方に導き、差圧によりラベルを成形品外壁に一体に融着させることもできる。差圧成形は、真空成形、圧空成形のいずれも採用できるが、一般には両者を併用し、かつプラグアシストを利用した差圧成形が好ましい。
本発明のインモールド成形用ラベルが貼着一体化した樹脂成形品は、ラベルが金型内で固定された後に、ラベルと樹脂成形品が一体に成形されるので、ラベルの変形もなく、成形品とラベルは適度な接着強度を有しており、ふくれ(ブリスター)もなく、ラベルにより加飾された外観が良好な成形品が得られる。
剥離強度が40gf/15mm以上であれば、樹脂成形品に貼り付けた際に外部からの衝撃により剥がれにくくなる傾向がある。剥離強度が160gf/15mm以下であれば、接着剤の強度を上回ったり、樹脂成形品に貼り付けた際に樹脂成形品の表面強度を上回ったりすることがないため、易剥離層(B)内で凝集破壊が発生しやすくなる傾向がある。
本発明における「剥離強度」とは、ラベル(基材層(A))を剥離する際に要する応力であり、ラベル付き樹脂成形品において成形品のラベル貼着部分を幅15mm、長さ100mmに切り取り、引張試験機((株)島津制作所製、商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と成形品部分とを剥離させ、安定している時の応力をロードセルにより測定し、横方向と縦方向の平均値をもって求めた。
この剥離強度は、易剥離層(B)に用いる結晶性ポリプロピレンの結晶化度を65%以上にすることや、これに非相溶性の熱可塑性樹脂や無機微細粉末を所定量ブレンドすること、さらに同易剥離層(B)を少なくとも一軸方向に延伸することにより達成できる。またこの剥離強度は、好ましくは、上記無機微細粉末としてその表面を親水化処理したものを使用すること、上記延伸を結晶性ポリプロピレンの結晶化部位の融点よりも低い温度で実施すること、上記熱可塑性樹脂として比較的低粘度なものを選定すること、上記易剥離層(B)の空孔率を特定の範囲とすること等によって調整することができる。
積層樹脂フィルム単体における剥離強度は、易剥離層(B)面に粘着テープ(ニチバン(株)製セロハンテープ、商品名「セロテープ」、銘柄名「CT-18」)を貼着し、長さ100mmに切り取り、引張試験機((株)島津制作所製、商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と粘着テープとの剥離を易剥離層(B)にて発生させ、剥離が安定している時の応力をロードセルにより測定し、横方向と縦方向の平均値から求めた。この方法により求めた剥離強度は、40~200gf/18mmであることが好ましく、50~190gf/18mmであることがより好ましく、60~180gf/18mmであることが特に好ましい。この剥離強度は、ラベル(基材層(A))を剥離する際に要する応力の調整法として記載した上記方法を用いることによって調整することができる。
以下の手順に従って積層樹脂フィルム(実施例1~19、比較例1~7)を製造した。表1に使用した材料の詳細を記載した。表中の「MFR」はメルトフローレートを意味する。表2および表3に各積層樹脂フィルムの製造にあたって使用した材料の種類と量(重量%)、延伸条件、全厚と[B]層の厚み、[C]層の有無を記載した。表2および表3に記載される材料の番号は、表1に記載される材料の番号に対応している。
特に実施例9は、実施例2で得た積層樹脂フィルムの[B]層側の表面に、グラビアインキ(商品名:XS-756、DICグラフィックス(株)製)及びグラビア印刷機を用いて灰色印刷を施して、隠蔽層(C)を設けた積層樹脂フィルムを得た。
比較例6において、表3に記載の配合物[A1]と配合物[B]を250℃に設定された2台の押出機でそれぞれ溶融混練してフィードブロック、マルチマニホールドを使用した多層ダイスを介してダイス内で積層し、これをシート状に共押出成形し、冷却装置にて70℃まで冷却して2層構造の無延伸シートを得た。この無延伸シートを145℃に加熱した後、縦方向にロール間で5倍に延伸し、縦一軸延伸フィルムを得た。次いで表3に記載の配合物[A2]を250℃に設定された押出機で溶融混練してダイスを介してシート状に押出し、前記縦一軸延伸フィルムの[A1]側に積層した。積層物を158℃に加熱してテンター延伸機を用いて横方向に9倍延伸し、1軸延伸/2軸延伸/2軸延伸された3層構造の積層樹脂フィルムを得た(図2参照)。
実施例2の積層樹脂フィルムを得る際、押出機の樹脂吐出量を変更しながら、縦一軸延伸フィルムの両面に配合物[A2]および配合物[B]を積層して得た積層物を、比較例7の積層樹脂フィルムとした。
上記実施例2により得た積層樹脂フィルムの[A2]層側の表面に、グラビアコーターを用いて次の組成を有する塗工液を固形分量で約2.0g/m2となるように塗工し、乾燥させて水性インクジェット印刷に好適なコート層(D)を形成した。
《塗工液組成》
合成シリカ粉末 100重量部
(商品名「ミズカシルP-78D」、平均粒径8μm、水澤化学工業(株)製)
ポリビニルアルコール 30重量部
(商品名「クラレポバール PVA-117」、クラレ(株)製)
ポリアミドポリアミンのエピクロルヒドリン付加物 10重量部
(商品名「WS4082」、星光PMC(株)製)
ポリアクリル酸ソーダ 5重量部
(試薬、和光純薬工業(株)製)
水 1600重量部
上記実施例2により得た積層樹脂フィルムの[A2]層側の表面に金属箔を転写蒸着し、同金属箔面上にグラビアコーターを用いてポリアミドポリアミン樹脂を含む塗工液(商品名「トパーズ17液」、東洋インキ製造(株)製)を固形分量で約0.5g/m2となるように塗工し、乾燥させて湿式電子写真方式の印刷機(例えば商品名「Indigo WS4000」、ヒューレット・パッカード社製)による印刷に好適なコート層(D)を形成した。
実施例、比較例において製造した各積層樹脂フィルムについて、印刷特性、不透明度、液体吸収容積、剥離強度、石膏ボードに対する剥離性、ビンに対する接着性・剥離性、隠蔽性、再貼付け施工性、リサイクル適性を評価した。各試験の詳細は以下に示す通りである。
[A2]側表面にグラビア印刷された各積層樹脂フィルムのインキ表面に粘着テープ(ニチバン(株)製、商品名「セロテープ」、銘柄名「CT-18」)を貼り付け、指で十分に押しつけた後、粘着テープの未貼着部分と積層樹脂フィルムとがなす角度を90度に保ちながら未貼着部分を引っ張ることにより約1000mm/secの速度で手で粘着テープを引き剥がし、インキの取られ方を下記の基準により評価し、以下の4段階で評価した。
◎: 全くインキが剥がれない
○: フィルムの材料部分の破壊に伴い一部のインキが剥がれるが、実用上問題ない
△: 剥離するときに抵抗はあるが、インキの殆どが剥がれ、実用上問題がある
X: インキ全量が剥がれ、剥離するときの抵抗もなく、実用上使用できない
JIS-P-8149に準拠し、各積層樹脂フィルム背面([B]側)に黒色及び白色標準板を当てて測定した光の反射率の比(単一シート視感反射率/固有視感反射率)を百分率で示した値として求めた。
JAPAN TAPPI No.51:2000に準拠するブリストー液体吸収性試験により測定した。具体的には、熊谷理機工業(株)製ブリストー試験機II型を使用して無加圧の状態でイオン交換水に赤色の水性インキを20:1に配合した混合物を20μl滴下して、50msにおける液体の転移量を求めた。
各積層樹脂フィルムを、恒温室(温度20℃、相対湿度65%)に12時間保管した後、易剥離層(B)面に粘着テープ(ニチバン(株)製、商品名「セロテープ」、銘柄名「CT-18」)を貼着し、これを長さ100mmに切り取り、(株)島津制作所製の引張試験機(商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と粘着テープとを剥離させ、安定している時の応力をロードセルにより測定した。この測定は、各積層樹脂フィルムの横方向と縦方向についてそれぞれ行い、これらの平均値をもって剥離強度とした。粘着テープは18mm幅のものを使用した。
各積層樹脂フィルムを10cm×10cmの正方形に切り取り、易剥離層(B)側に澱粉を主成分とした水系接着剤(ヤヨイ化学工業(株)製、商品名「ルーアマイルド」とヤヨイ化学工業(株)製、商品名「プラゾール100S」と水をそれぞれ5:1:4で混合したもの)を自動壁紙糊付機(極東産機(株)製)で固形分量が8g/m2となるように塗工し、石膏ボード(吉野石膏(株)製、商品名「タイガーボード」)の上に貼着させた。これを常温にて一週間保管した後、下記の(1)剥離開始性と(2)剥離伝播性を評価した。
各積層樹脂フィルムの4辺の内1辺を爪で剥がすことにより端から1cmだけ石膏ボードから剥がした後、剥がした辺を手で持ち、石膏ボードより引き剥がし、易剥離層(B)の凝集破壊による剥離が開始するまでの状態をその距離から観察し、以下の4段階で評価した。なお、石膏ボードから手で引き剥がす際は、石膏ボード表面と基層(A)の剥離部分のなす角度を約135°に維持しながら、積層樹脂フィルムの剥離部分を引っ張ることにより引き剥がした。
◎: 易剥離層(B)の剥離がすぐに(1mm未満で)開始する
○: 易剥離層(B)の剥離が開始するまでに1~2mm要する
△: 易剥離層(B)の剥離が開始するまでに3~9mm要する
×: 易剥離層(B)の剥離が開始するまでに10mm以上要する
各積層樹脂フィルムの4辺の内1辺に粘着テープ(ニチバン(株)製、商品名「セロテープ」、銘柄名「CT-18」)を辺の全長にわたって辺に沿って貼り、手で持ち易い状態にし、石膏ボード表面と基層(A)の剥離部分のなす角度を約135°に維持しながら、基層(A)の剥離部分を引っ張ることにより基層(A)を石膏ボードより引き剥がした。このときの易剥離層(B)の剥離伝播状態と剥離力を、以下の4段階で評価した。
◎: 剥離力が軽く、全面綺麗に剥離が伝播する
○: 剥離力はやや重いが、全面綺麗に剥離が伝播する
△: 剥離力が非常に重いが、全面綺麗に剥離が伝播する
×: 剥離が全面に伝播できずに途中で切れてしまう
各積層樹脂フィルムを5cm×5cmの正方形に切り取り、易剥離層(B)側に市販の水系性接着剤((株)T&K TOKA製、商品名「フジアットAL-8L」)を自動糊付機(TY精機製)で固形分量が8g/m2となるように塗工し、ガラスビンに貼着させた。常温にて一週間保管した後、(1)ビンへの接着性、(2)剥離開始性、(3)剥離伝播性を評価した。
各積層樹脂フィルムの4辺の内1辺を爪で剥がすことにより端から1cmだけビンから剥がした後、剥がした辺を手で持ち、ビンより引き剥がし、易剥離層(B)の剥離が開始するまでの状態を観察し、以下の3段階で評価した。なお、ビンから手で引き剥がす際は、ビン表面と積層樹脂フィルムの剥離部分のなす角度を約135°に維持しながら、積層樹脂フィルムの剥離部分を引っ張ることにより引き剥がした。
○: 剥離する際に基材が易剥離もしくは材破する
△: ラベルの端のみが易剥離もしくは材破する
×: 接着剤が乾燥せずにビンに接着しない
(2)剥離開始性と(3)剥離伝播性については、前述の石膏ボードに対する試験((1)剥離開始性と(2)剥離伝播性)と同様の方法、判断基準で評価した。
官製ハガキに文字サイズ10ポイントのアルファベット26文字を印字して、各積層樹脂フィルムの易剥離層(B)側に澱粉を主成分とした水系接着剤(ヤヨイ化学工業(株)製、商品名「ルーアマイルド」とヤヨイ化学工業(株)製、商品名「プラゾール100S」と水を5:1:4で混合したもの)を固形分量が8g/m2となるように塗工し、ハガキの上に貼り付けた。各積層樹脂フィルムを透して見える文字の隠蔽性を目視にて判断し、以下の4段階で評価した。
◎: 文字があることが全く判らず良好
○: 文字は全く読み取れずやや良好
△: 文字の一部が読み取れやや不良
×: 文字の全てが読み取れ不良
各積層樹脂フィルムの易剥離層(B)側(裏打ち紙のある場合は裏打ち紙面)に澱粉を主成分とした水系接着剤(ヤヨイ化学工業(株)製、商品名「ルーアマイルド」とヤヨイ化学工業(株)製、商品名「プラゾール100S」と水を5:1:4で混合したもの)を自動壁紙糊付機(極東産機(株)社製)で固形分量が8g/m2となるように塗工し、石膏ボード(吉野石膏(株)製、商品名「タイガーボード」)の上に貼着させた。常温にて1週間保管した後に、前記石膏ボードに対する剥離開始性試験と同様の方法で各積層樹脂フィルムを石膏ボードから剥がした。次いで剥がされた各積層樹脂フィルムの剥離面に同じの水系接着剤を自動壁紙糊付機(極東産機(株)社製)で固形分量が8g/m2となるように塗工し、何も貼られていない石膏ボードの上に再貼着させ、その外観を評価した。またこれを常温にて1週間保管した後に各積層樹脂フィルムの4辺の内1辺を再び爪で剥がすことにより端から1cmだけ石膏ボードから剥がした後、剥がした辺を手で持ち、石膏ボードより引き剥がし、易剥離層(B)の剥離面の状態を観察し、以下の3段階で評価した。なお、石膏ボードから手で引き剥がす際は、石膏ボード表面と積層樹脂フィルムの剥離部分のなす角度を約135°に維持しながら、積層樹脂フィルムの剥離部分を引っ張ることにより引き剥がした。
○: 再貼着後の積層樹脂フィルムに凹凸の外観不良は見られず、剥離時はフィルムの易剥離層(B)部分から再度均一に剥離する
△: 再貼着後の積層樹脂フィルムに凹凸の外観不良が見られ、且つ再接着面からの易剥離層(B)の剥離は不均一であり、実用上問題がある
X: 再貼着後の積層樹脂フィルムに凹凸の外観不良が見られ、且つ再接着面からの剥離はフィルム側と被着体側と両方から起こるため非常に不均一であり、実用上使用できない
上記[壁紙の接着性]評価にて施工された各壁紙を、前記石膏ボードに対する剥離開始性試験と同様の方法で1ヶ月後に壁面から剥がし、剥がした壁紙を粉砕機にかけてチップ状にした後、これを225℃に設定され、100メッシュのスクリーンパックを装備した2軸押出機にて再溶融混練及び押出しを行った。このときのスクリーンパックの詰まりや発煙、変色などの状態から再溶融押出し(樹脂再生)が可能か否かを判定した。スクリーンパックの詰まりや発煙、変色が無く、再溶融押出し(樹脂再生)が可能である状態を「良好」と判定した。
表5または表6に記載の配合物[A1]を250℃に設定した押出機で溶融混練し、ダイスを介してシート状に押出成形し、冷却装置にて70℃まで冷却して単層の無延伸シートを得た。この無延伸シートを145℃に再加熱した後、多数のロール間の周速差を利用して縦方向に5倍に延伸し、縦一軸延伸フィルムを得た。次いで表5または表6に記載の配合物[A2]および配合物[B]をそれぞれ個別に250℃に設定した押出機で溶融混練し、ダイスを介してシート状に押出し、前記縦一軸延伸フィルムの一方の面に配合物[A2]を、もう一方の面に配合物[B]をそれぞれ積層し、[A2]/[A1]/[B]の3層構造を有する積層物を得た。次いで前記積層物を、オーブンを用いて158℃に再加熱した後、テンター延伸機を用いて横方向に9倍延伸し、1軸延伸/2軸延伸/1軸延伸された3層構造の積層樹脂フィルムを得てこれをインモールド成形用ラベルとした(図2参照)。積層樹脂フィルムの全厚み、および易剥離層(B)の厚みを表5または表6に示す。
表6に記載の配合物[A2]、配合物[A1]および配合物[B]を250℃に設定された3台の押出機でそれぞれ溶融混練してフィードブロック、マルチマニホールドを使用した多層ダイスを介してダイス内で積層し、これをシート状に共押出成形し、冷却装置にて70℃まで冷却して3層構造の無延伸シートを得た。この無延伸シートを145℃に加熱した後、縦方向にロール間で5倍に延伸し、次いで158℃に加熱してテンター延伸機を用いて横方向に9倍延伸し、2軸延伸/2軸延伸/2軸延伸された3層構造の積層樹脂フィルムを得てこれを実施例117のインモールド成形用ラベルとした(図2参照)。積層樹脂フィルムの全厚み、および易剥離層(B)の厚みを表6に示す。
実施例103の積層樹脂フィルムを得る際、押出機の樹脂吐出量を変更しながら、縦一軸延伸フィルムの両面に配合物[A2]および配合物[B]を積層して得た積層物を得てこれを比較例106のインモールド成形用ラベルとした。
特開2003-295767号公報の実施例101の多層フィルムを得てこれをインモールド成形用ラベルとした(図3参照)。このものは層間剥離を可能とする層(Y)と層(B)を中間層(C)を介して個別に設けたものであり、多層フィルムの全厚みが100μm、層間剥離を可能とする層(Y)の厚みが5μm、層(B)の厚みが5μmである。該層(B)はエチレン・1-ヘキセン共重合体のみからなるヒートシール層であり、同層の表面開口率は0%であった。
特開2006-309175号公報の実施例101の多層フィルムを得てこれをインモールド成形用ラベルとした(図4参照)。この層(B)に用いるプロピレン単独重合体(日本ポリプロ(株)製、商品名:FY4)は、融点が164℃、密度が0.9055g/cm3、結晶化度が64.4%のものである。このものは基層(A)が、層(A2)/層(A1)/層(A3)の3層からなるものであるが、基層(A)を構成する層数は表6に示す結果にほとんど影響しない。
上記各実施例、比較例で得た積層樹脂フィルムの両面に、オフセット印刷機(三菱重工業(株)製、型式:ダイヤII型)およびUVオフセットインキ((株)T&K TOKA製、商品名:ベストキュアー161)を用いて基層(A)(配合物[A2])側にキャラクターの絵柄、および50%網点を含む意匠を、易剥離層(B)(配合物[B])側に50%網点を含むパターンを印刷し乾燥させ、これを用いて後述の樹脂成形品を成形した。
[射出成形]
射出成形機((株)新潟鐵工所製、型式:NV50ST、型締力:50トン、縦型配置式)および樹脂成形品のサイズが横130mm、縦150mm、肉厚1mmの平板となる射出成形用割型を使用し、上記で得たインモールド成形用ラベルを横100mm、縦130mmのサイズに断裁したものを下部固定盤側に取り付けたれた雌型の金型表面に基層(A)側が金型と接するようにラベルを固定し、次いで割型を型締めし、200℃に設定した射出装置より溶融したポリスチレン(PSジャパン(株)製、商品名:HIPS 433、MFR:21g/10分(200℃、5kg荷重)、溶融開始温度:約95℃)を745kgf/cm2の圧力でゲート部より金型内に注入し溶融樹脂を冷却固化させるとともにラベルを接着させた後、型開きをしてラベルが貼着した平板状のPS製射出成形品を得て、これをラベル付き樹脂成形品とした。
中空成形機((株)プラコー製、型式:V-50型)および自動ラベル供給装置(ぺんてる(株)製)および内容量1,000mlのボトル容器が得られる中空成形用割型を使用し、上記で得たインモールド成形用ラベルを横109mm、縦171mmのサイズに打ち抜いたものをブロー成形用割型の一方に真空を利用して基層(A)側が金型と接するようにラベルを固定した後、高密度ポリエチレン(日本ポリエチレン(株)製、商品名:ノバテックHD HB330、融点:133℃)を170℃または200℃で溶融押出しパリソンとし、割型間に導入後に割型を型締めし、次いで4.2kg/cm2の圧空をパリソン内に供給し、パリソンを膨張させて型に密着させて容器状とすると共にインモールド成形用ラベルと接着させ、次いで該型を10℃の冷却水で冷却した後、約10秒後に型開きをしてラベルが貼着した中空容器成形品を取り出し、これをラベル付き樹脂成形品とした。
また、樹脂成形品の素材をポリプロピレンランダム共重合体(日本ポリプロ(株)製、商品名:ノバテックPP EG-8、融点:143℃)に替え、同様に200℃で溶融押出し、同様の手順でラベルが貼着した中空容器成形品を取り出し、これをラベル付き樹脂成形品とした。
上記の各実施例、比較例で製造したインモールド成形用ラベルは、易剥離層(B)側表面の開口率、空孔率、算術平均粗さ、剥離強度、および両面の印刷適性について下記の手法で評価を行った。また、これらのインモールド成形用ラベルを貼着したラベル付き樹脂成形品は、その接着性と剥離強度について下記の手法で評価を行った。各試験の詳細は以下に示す通りであり、結果を表7にまとめて示す。
積層樹脂フィルム試料より任意の一部を切り取り、観察試料台に貼り付け、易剥離層(B)側表面を金蒸着し、電子顕微鏡(日立製作所(株)製、走査型顕微鏡S-2400)を使用して1000倍に拡大し、観察した領域を写真撮影し、空孔をトレーシングフィルムにトレースして塗りつぶし、これを画像解析装置(ニレコ(株)製:型式ルーゼックスIID)で画像処理し、観察領域中に空孔が占める面積割合を求めて、易剥離層(B)表面の開口率とした。
積層樹脂フィルム試料をエポキシ樹脂で包埋して固化させた後、ミクロトームを用いてフィルムの厚さ方向に対して平行(すなわち面方向に垂直)な切断面を作製した。この切断面を蒸着してメタライジングした後、電子顕微鏡(日立製作所(株)製、走査型顕微鏡S-2400)を使用して3000倍に拡大して観察し、易剥離層(B)の空孔部分をトレーシングフィルムにトレースし塗りつぶした図を画像解析装置(ニレコ(株)製:型式ルーゼックスIID)で画像処理し、測定範囲を占める空孔の面積割合(%)を求めて易剥離層(B)の空孔率(%)とした。
JIS-B0601の規定に基づき、表面粗さ計((株)小坂研究所製、商品名:サーフコーダーSE30)を用いて測定した。
ラベル付き樹脂成形品における剥離強度の目安を得る目的から、各積層樹脂フィルム試料を、恒温室(温度20℃、相対湿度65%)に12時間保管した後、易剥離層(B)面に粘着テープ(ニチバン(株)製、商品名「セロテープ」、銘柄名「CT-18」)を貼着し、これを長さ100mmに切り取り、(株)島津制作所製の引張試験機(商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と粘着テープとを剥離させ、安定している時の応力をロードセルにより測定した。この測定は、各積層樹脂フィルムの横方向と縦方向についてそれぞれ行い、これらの平均値をもって剥離強度とした。粘着テープは18mm幅のものを使用した。
上記の印刷工程を経て、基層(A)側及び易剥離層(B)側にオフセット印刷された各積層樹脂フィルムの50%網点印刷部を目視で観察し、A4サイズ当りの白抜け発生個数をもってインキ転移評価とし、以下の3段階で評価した。
○: 白抜けが5個以内 :実用上問題ない。
△: 白抜けが6~20個:実用上問題となる。
X: 白抜けが21個以上:実用上使用できない。
ラベル付き樹脂成形品において、ラベルと樹脂成形品との間に皺やふくれの発生が認められるか否かを目視で確認し、以下の2段階で評価した。
○: 皺やふくれの発生が確認されない。
×: 皺やふくれの発生が確認される。
ラベル付き樹脂成形品のラベル貼着部分から幅15mm、長さ100mmの試料を切り出し、各試料を恒温室(温度20℃、相対湿度65%)にて12時間保管した後、引張試験機((株)島津制作所製、商品名「AUTOGRAPH」)を使用し、引張速度300mm/分にて、180゜の角度で基層(A)と樹脂成形品とを剥離させ、安定している時の応力をロードセルにより測定した。この測定は、各積層樹脂フィルムの横方向と縦方向(易剥離層(B)の延伸方向とそれに直交する方向)についてそれぞれ行い、これらの平均値をもって剥離強度とした。
A1,A2,A3 基層を構成する各層
B 易剥離層
Y 層間剥離を可能とする層
Z 中間層
Claims (29)
- 基層(A)と易剥離層(B)の積層樹脂フィルムを含む易剥離性フィルムであって、
該基層(A)が熱可塑性樹脂を含み、
該易剥離層(B)が結晶化度が65%以上である結晶性ポリプロピレン樹脂及び該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂のブレンド物30~60重量%と、微細粉末40~70重量%を含み、該ブレンド物において結晶性ポリプロピレン樹脂100重量部に対し該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂が105~300重量部の割合でブレンドされており、且つ、
該易剥離層(B)が少なくとも1軸方向に延伸されていることを特徴とする易剥離性フィルム。 - 該微細粉末が、表面処理剤により表面を親水化処理されている無機微細粉末を含むことを特徴とする請求項1に記載の易剥離性フィルム。
- 該表面処理剤が、水溶性アニオン系界面活性剤、水溶性カチオン系界面活性剤、及び水溶性非イオン系界面活性剤からなる群より選択される少なくとも一種の界面活性剤であることを特徴とする請求項2に記載の易剥離性フィルム。
- 該微細粉末が、表面が親水化処理されている無機微細粉末を50~99.9重量%と、表面が親水化処理されていない無機微細粉末および有機微細粉末の少なくとも一方を0.1~50重量%含むことを特徴とする請求項2または3に記載の易剥離性フィルム。
- 該易剥離層(B)の「Japan TAPPI No.51-2000」により測定される液体吸収容積が1~20ml/m2であることを特徴する請求項2~4の何れか一項に記載の易剥離性フィルム。
- 該結晶性ポリプロピレン樹脂に非相溶性の熱可塑性樹脂が、ポリエチレン樹脂、スチレン系樹脂、環状ポリオレフィン樹脂、エチレン-環状オレフィン共重合樹脂、ポリアミド系樹脂、ポリエステル系樹脂、及びポリカーボネートからなる群より選択される少なくとも1種の樹脂であることを特徴とする請求項1~5の何れか一項に記載の易剥離性フィルム。
- 該易剥離層(B)が、更に微細粉末の分散剤を、微細粉末100重量部に対し0.5~30重量部含むことを特徴とする請求項1~6の何れか一項に記載の易剥離性フィルム。
- 該分散剤が、マレイン酸変性ポリオレフィン及びシラノール変性ポリプロピレンの少なくとも一方であることを特徴とする請求項7に記載の易剥離性フィルム。
- 該易剥離層(B)の厚みが、0.1~20μmであることを特徴とする請求項1~8の何れか一項に記載の易剥離性フィルム。
- 該易剥離層(B)表面の開口率が、7~60%であることを特徴とする請求項1~9の何れか一項に記載の易剥離性フィルム。
- 該易剥離層(B)表面の算術平均粗さが、0.3~1.8μmであることを特徴とする請求項1~10の何れか一項に記載の易剥離性フィルム。
- 該基層(A)が、多層構造であることを特徴とする請求項1~11の何れか一項に記載の易剥離性フィルム。
- 該易剥離層(B)表面上に印刷が施されていることを特徴とする請求項1~12の何れか一項に記載の易剥離性フィルム。
- 更に隠蔽層(C)を有することを特徴とする請求項1~13の何れか一項に記載の易剥離性フィルム。
- 該隠蔽層(C)が、易剥離層(B)側表面への黒色印刷または灰色印刷、基層(A)への隠蔽顔料添加、基層(A)間への黒色印刷挿入からなる群より選択される少なくとも一つの手法からなることを特徴とする請求項14に記載の易剥離性フィルム。
- 該基層(A)側表面上に更にコート層(D)を有することを特徴とする請求項1~15の何れか一項に記載の易剥離性フィルム。
- 請求項1~16のいずれか一項に記載の易剥離性フィルムからなるインモールド成形用ラベル。
- 請求項17に記載のインモールド成形用ラベルを樹脂成形品に貼着したラベル付き樹脂成形品。
- 該樹脂成形品が、ポリプロピレン樹脂、ポリエチレン樹脂、ポリスチレン樹脂、及びポリエチレンテレフタレート樹脂からなる群より選択される少なくとも1種の熱可塑性樹脂からなることを特徴とする請求項18に記載のラベル付き樹脂成形品。
- 該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がす際に、剥離が易剥離層(B)内の凝集破壊により進行することを特徴とする請求項18または19に記載のラベル付き樹脂成形品。
- 該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がす際の、剥離に要する応力が、40~160gf/15mmであることを特徴とする請求項18~20の何れか一項に記載のラベル付き樹脂成形品。
- 該インモールド成形用ラベルの易剥離層(B)表面上に印刷が施されており、該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がした際に、該印刷が樹脂成形品上に残ることを特徴とする請求項18~21の何れか一項に記載のラベル付き樹脂成形品。
- 該インモールド成形用ラベルの易剥離層(B)表面上に印刷が施されており、該ラベル付き樹脂成形品からインモールド成形用ラベルを剥がした際に、該印刷がラベル上に残ることを特徴とする請求項18~22の何れか一項に記載のラベル付き樹脂成形品。
- 請求項1~16のいずれか一項に記載の易剥離性フィルムの易剥離層(B)側表面に水系接着剤層を施した壁紙。
- 壁から壁紙を剥がす際に、剥離が易剥離層(B)内の凝集破壊により進行することを特徴とする請求項24に記載の壁紙。
- 壁から壁紙を剥がす際の剥離に要する応力が、50~180gf/18mmであることを特徴とする請求項24または25に記載の壁紙。
- 壁から壁紙を剥がした後に、壁表面に易剥離層(B)の一部が薄膜として残留し、この残留物が液体を吸収することを特徴とする請求項24~26のいずれか一項に記載の壁紙。
- 請求項1~16のいずれか一項に記載の易剥離性フィルムの易剥離層(B)側表面に水系接着剤層を施したグルーラベル。
- 請求項28のグルーラベルを貼着したラベル付き容器。
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JP2011-080735 | 2011-03-31 | ||
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US13/806,435 A-371-Of-International US9102126B2 (en) | 2010-06-30 | 2011-06-30 | Readily removable film, label for in-mold molding, molded resin article having label attached thereto, wallpaper, glue label, and container having label attached thereto |
US14/790,226 Continuation US20150375477A1 (en) | 2010-06-30 | 2015-07-02 | Readily removable film, label for in-mold molding, molded resin article having label attached thereto, wallpaper, glue label, and container having label attached thereto |
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WO2012002510A1 true WO2012002510A1 (ja) | 2012-01-05 |
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PCT/JP2011/065098 WO2012002510A1 (ja) | 2010-06-30 | 2011-06-30 | 易剥離性フィルム、インモールド成形用ラベル、ラベル付き樹脂成形品、壁紙、グルーラベルおよびラベル付き容器 |
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GB2489775A (en) * | 2011-04-05 | 2012-10-10 | Systems Labelling Ltd | Removable in-mould label |
JP2014080025A (ja) * | 2012-09-28 | 2014-05-08 | Yupo Corp | 樹脂延伸フィルム、その製造方法およびその樹脂延伸フィルムを用いた積層体 |
CN104684725A (zh) * | 2012-09-28 | 2015-06-03 | 优泊公司 | 树脂拉伸薄膜、其制造方法和使用该树脂拉伸薄膜的层叠体 |
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Also Published As
Publication number | Publication date |
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US20150375477A1 (en) | 2015-12-31 |
CN102971144A (zh) | 2013-03-13 |
CN102971144B (zh) | 2015-04-08 |
US20130164471A1 (en) | 2013-06-27 |
US9102126B2 (en) | 2015-08-11 |
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