WO2023063410A1 - 印刷層が脱離可能な印刷フィルム - Google Patents

印刷層が脱離可能な印刷フィルム Download PDF

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Publication number
WO2023063410A1
WO2023063410A1 PCT/JP2022/038332 JP2022038332W WO2023063410A1 WO 2023063410 A1 WO2023063410 A1 WO 2023063410A1 JP 2022038332 W JP2022038332 W JP 2022038332W WO 2023063410 A1 WO2023063410 A1 WO 2023063410A1
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WIPO (PCT)
Prior art keywords
layer
printed
film
curing agent
alkali
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Ceased
Application number
PCT/JP2022/038332
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English (en)
French (fr)
Japanese (ja)
Inventor
理行 前田
厚 深堀
隆裕 安海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Seikan Co Ltd
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Toyo Seikan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Seikan Co Ltd filed Critical Toyo Seikan Co Ltd
Priority to CN202280062901.6A priority Critical patent/CN117957117A/zh
Priority to EP22881105.5A priority patent/EP4417418A4/en
Priority to JP2023509794A priority patent/JP7268809B1/ja
Publication of WO2023063410A1 publication Critical patent/WO2023063410A1/ja
Priority to US18/627,974 priority patent/US12359085B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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
    • 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
    • B32B27/10—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 paper or cardboard
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B29B2017/0296—Dissolving the materials in aqueous alkaline solutions, e.g. NaOH or KOH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/385—Details of packaging materials of special type or form especially suited for or with means facilitating recycling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention relates to a printed film having a printed layer using a printing ink that can be removed by alkali treatment. It relates to a printed film from which a printed layer can be reliably removed.
  • Patent Document 1 proposes a bag container formed by laminating unstretched PET and stretched PET, and is printed with an ink that can be peeled off with a strong alkaline solution. The provision of a printed layer is described.
  • layers made of the same type of plastic are laminated without using an adhesive to facilitate recycling, and a printed layer is provided on the exposed surface opposite to the unstretched PET layer that serves as the sealant layer. allows the printed layer to be easily removed from the unstretched PET layer prior to recycling.
  • the printed layer is inferior in scratch resistance and the packaging bag is inferior in slipperiness. Therefore, when packaging bags filled with contents are boxed and transported, the packaging bags may collide with each other due to vibration, and the printed layer may be damaged or peeled off. In addition, there is a possibility that the packaging bags cannot be supplied efficiently when the packaging bags are stacked and stored and then subjected to a content filling process or the like. In order to solve such problems and to give the packaging bag a beautiful gloss, a protective layer is generally formed on the printed layer.
  • a protective layer capable of achieving the above purpose is formed using a finishing varnish (top coat) on a printed layer using an ink that can be removed by alkali treatment
  • the printed layer can be sufficiently removed even if the alkali treatment is performed.
  • a new problem arose in that it was not possible to remove SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a printed film in which the printed layer can be easily removed by alkali treatment, which has excellent lubricity and gloss, and which also has scratch resistance of the printed layer.
  • the finishing varnish layer comprises at least a curable resin and It comprises a curing agent, and the curing agent is blended in an amount of less than 40 parts by mass with respect to 100 parts by mass of the curable resin, and the removable printed layer can be detached from the base film by alkali treatment.
  • the coating amount of the removable printed layer is 1.2 g/m 2 or more
  • the curing agent In an epoxy isocyanate finishing varnish in which the curable resin is an epoxy resin and the curing agent is an isocyanate curing agent, the curing agent is blended in an amount such that the NCO/OH mol ratio is less than 8.4. that (3) In a urethane isocyanate-based finishing varnish in which the curable resin is a urethane-based resin and the curing agent is an isocyanate-based curing agent, the curing agent is blended in an amount such that the NCO/OH mol ratio is less than 21.3.
  • the coating amount of the removable printed layer is 2.6 g/m 2 or more, and the NCO/OH mol ratio in the epoxy isocyanate-based finishing varnish is less than 1.05; (5) The detachable printed layer has a coating weight of 2.6 g/m 2 or more, and the NCO/OH mol ratio in the urethane isocyanate-based finishing varnish is less than 1.07.
  • the curable resin is an epoxy resin, the curing agent is an isocyanate curing agent, the coating amount of the removable printed layer is 2.6 g/m 2 or more, and the other printed layer is The coating amount is 2.2 g/m 2 or more, and the curing agent is blended in an amount such that the NCO/OH mol ratio is less than 4.2; (9) The curable resin is a urethane-based resin, the curing agent is an isocyanate-based curing agent, the coating amount of the removable printed layer is 2.6 g/m 2 or more, and the other printed layer is The coating amount is 2.2 g/m 2 or more, and the curing agent is blended in an amount such that the NCO/OH mol ratio is less than 3.2; (10) A sealant layer is formed on the opposite side of the base film to the removable printed layer; (11) The base film is a stretched film made
  • the printed film of the present invention has a finishing varnish layer formed on a printing layer made of an alkali-releasing ink (hereinafter sometimes referred to as an "alkali-releasing printing layer"), it can be treated with an alkali. It is possible to easily remove the printed layer by , and it has excellent recyclability. Further, by using the same type of olefin resin or polyester resin for the base film and the sealant layer, separation of different resins becomes unnecessary, and recyclability can be further improved. In addition, since a finishing varnish layer is formed on the surface of the printed film, it is possible to improve the handleability when used as a packaging bag, etc., and effectively prevent the printed layer from being scratched or peeled off.
  • the coefficient of dynamic friction of the surface of the finishing varnish layer is less than 0.8, the slipperiness and scratch resistance of the finishing varnish layer are significantly improved, and peeling of the printed layer due to vibration during transportation can be effectively prevented. Further, by forming a finish varnish layer, it is possible to provide a printed film having excellent surface glossiness.
  • the printed film of the present invention by forming another layer such as a gravure printed layer between the alkali-releasable printed layer and the finishing varnish layer, migration of the curing agent component to the alkali-releasable printed layer can be prevented. Since it can be suppressed, the printing layer can be efficiently removed by alkali treatment, and the amount of curing agent in the finishing varnish layer can be increased, and the performance required for the finishing varnish layer (protection effect of the printing layer, etc.) can also be improved. Furthermore, there is also the effect that the thickness of the alkali-releasable printed layer can be reduced.
  • FIG. 1 is a cross-sectional view showing a laminated structure of an example of the printed film of the present invention
  • FIG. FIG. 4 is a cross-sectional view showing a laminated structure of another example of the printed film of the present invention
  • FIG. 4 is a cross-sectional view showing a laminated structure of another example of the printed film of the present invention
  • the printed film of the present invention comprises a substrate film 1, an alkali-releasable printed layer 2 made of an alkali-releasable ink, and a finishing varnish layer 3 formed at least.
  • the finishing varnish layer which is a film and consists of a curable resin and a curing agent, can protect the printed layer and achieve the performance required for the finishing varnish layer, such as scratch resistance and slipperiness, while also being alkali-releasing. It is an important feature that it is formed with a composition that does not impair the removability of the printed layer by alkali treatment.
  • the components of the finishing varnish are transferred to the alkali-releasable printed layer.
  • the alkali-releasable ink crosslinks through diffusion and permeation, or the infiltrated finish varnish component hardens near the interface between the alkali-releasable printed layer and the base material, and as a result, it can be easily removed even if alkali treatment is performed. presumably gone. Therefore, in the present invention, the composition of the finishing varnish has been found which does not affect the alkali-releasable printed layer and which can maintain the performance required of the finishing varnish layer.
  • the finishing varnish layer constituting the printed film of the present invention is composed of a curable resin and a curing agent, and it is important that the curing agent is blended in an amount of less than 40 parts by mass with respect to 100 parts by mass of the curable resin. Yes, especially depending on the combination of curable resin and curing agent, the thickness of the alkali-releasable printed layer, or the presence or absence of other layers between the finishing varnish layer and the alkali-releasable printed layer, and the amounts described later are blended.
  • the components of the finishing varnish, particularly the curing agent are suppressed from migrating to the alkali-releasing printing layer, thereby preventing the alkali-releasing printing layer from moving. can be reliably desorbed.
  • curable resins conventionally used for finishing varnishes can be used, but it is particularly preferable to use epoxy resins or urethane resins.
  • curing agent isocyanate curing agents and amino curing agents known as curing agents for epoxy resins or urethane resins can be used. It is preferable to use an isocyanate-based curing agent capable of forming a finish varnish layer having the properties described above.
  • an isocyanate-based curing agent capable of forming a finish varnish layer having the properties described above.
  • epoxy resin conventionally known epoxy resins can be used, but not limited thereto, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, polyethylene glycol glycidyl. Ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether and the like can be exemplified.
  • Conventionally known urethane resins can be used as the urethane resin, and examples thereof include, but are not limited to, polyether urethane resins, polyester urethane resins, polycarbonate urethane resins, and the like.
  • Usable isocyanate curing agents include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), aliphatic isocyanates such as trimethylhexamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1 Aliphatic cyclic isocyanates such as ,4-cyclohexane diisocyanate and 1,2-cyclohexane diisocyanate; aromatic isocyanates such as xylylene diisocyanate (XDI), 2,4-tolylene diisocyanate (TDI) and 2,6-tolylene diisocyanate , isophorone diisocyanate (IPDI), norbornene diisocyanatomethyl and other alicyclic isocyanates, their burettes, nurates and other polymers and mixtures thereof. These can also be used in combination of two or more.
  • an epoxy-isocyanate-based finishing varnish which is a combination of an epoxy-based resin and an isocyanate-based curing agent, as the finishing varnish, the molar ratio of the hydroxyl group (OH) of the epoxy-based resin to the isocyanate group (NCO) of the isocyanate-based curing agent
  • an isocyanate curing agent so that the (NCO/OH mol ratio) is less than 8.4.
  • the isocyanate-based curing agent when the NCO/OH mol ratio is equal to or higher than the above value, the isocyanate-based curing agent is excessive relative to the epoxy-based resin or urethane-based resin, and the excess curing agent not used for curing the finishing varnish layer is alkaline. It may migrate to the releasable printed layer and not only hinder detachment from the alkali releasable printed layer, but also impair the economy and the performance of the finishing varnish layer.
  • the lower limit of the NCO/OH mol ratio may be the minimum required for the finish varnish layer to be sufficiently crosslinked, and may be as close to zero as possible depending on the curing conditions.
  • the range of the NCO/OH mol ratio for achieving both the performance required for the finishing varnish layer and the releasability of the alkali-releasable printed layer is determined by the coating amount (thickness) of the alkali-releasable printed layer described later. It also varies depending on the presence or absence of other printed layers and the coating amount (thickness). That is, when the thickness of the alkali-releasable printed layer is large, or when another layer is interposed between the alkali-releasable printed layer and the finishing varnish layer, peeling of the alkali-releasable printed layer occurs.
  • the distance from the finish varnish layer to the vicinity of the interface between the material and the alkali-releasable printed layer is long, and the curing agent in the finish varnish is difficult to reach near the interface, so when the alkali-releasable printed layer is thin
  • the amount of hardening agent in the finishing varnish can be set higher than when there are no other layers.
  • the coating weight of the alkali-releasable print layer is 1.2 g/m 2 or more
  • the NCO/OH mol ratio is preferably less than 8.4. It is desirable to be less than 1.05, particularly 0.21 to 0.525.
  • the coating amount of the alkali-releasable printed layer is 2.6 g/m2. 2 or more, the coating amount of the other printed layer is 2.2 g/m 2 or more, and the NCO/OH mol ratio is preferably less than 4.2, particularly 0.21 or more and 3.15 or less.
  • the coating weight of the alkali-releasing printed layer is 1.2 g/m 2 or more.
  • the NCO/OH mol ratio is preferably less than 3.2 . It is desirable to be less than 1.07, particularly 0.27 or more and 0.53 or less.
  • the coating amount of the alkali-releasable printed layer is 2.6 g/m2. 2 or more, the coating amount of the other printed layer is 2.2 g/m 2 or more, and the NCO/OH mol ratio is preferably less than 3.2, particularly 0.27 or more and 1.6 or less.
  • the finishing varnish may contain lubricants such as paraffin wax and polyethylene wax, and conventionally known additives such as anti-blocking agents as long as they do not impair the transparency of the finishing varnish layer.
  • lubricants such as paraffin wax and polyethylene wax
  • conventionally known additives such as anti-blocking agents as long as they do not impair the transparency of the finishing varnish layer.
  • the wax is contained in an amount of 0.1 to 1.0 parts by mass per 100 parts by mass of the curable resin. This makes it possible to control the coefficient of dynamic friction of the surface of the finish varnish layer to less than 0.8, particularly in the range of 0.1 to 0.3, thereby improving the slipperiness and scratch resistance of the finish varnish layer.
  • the value of the coefficient of dynamic friction of the surface of the finishing varnish layer is determined by using a finishing varnish containing epoxy resin as the main material and changing the type and content of the wax contained, and flat pouches having surfaces with different coefficients of dynamic friction. This is the value obtained from the result of the vibration test performed on the manufactured product. Except for the pouch size (1 kg capacity), cardboard size, stacking shape (3 bags of 6 pouches were laid down and stacked vertically in 2 rows), etc., under the same test conditions as in the examples described later, according to JIS standards. gone. As a result, when the dynamic friction coefficient was 0.8 or more, ink peeling of 1 mm or more was observed.
  • the slipperiness and scratch resistance of the finishing varnish layer depend on the value of the dynamic friction coefficient of the surface of the finishing varnish layer regardless of the composition of the finishing varnish layer, and it is considered that the above preferred range also applies to the finishing varnish layer of the present invention.
  • the amount of finish varnish applied is preferably in the range of 0.5 to 2.5 g/m 2 , particularly 1.4 to 1.7 g/m 2 . If the coating amount is less than the above range, the effect of protecting the printed layer by the finishing varnish layer cannot be sufficiently obtained, while if the coating amount is greater than the above range, it is only economically inferior. However, there is a possibility that the alkali-releasing property may be impaired as compared with the case in which the content is within the above range.
  • the alkali-releasable ink constituting the printed film of the present invention may be any conventionally known alkali-releasable ink, as long as the printing layer can be detached from the base film by alkali treatment in a state where the finishing varnish layer is formed on the surface. Ink can be used.
  • binder resins for alkali-releasing ink include, but are not limited to, acrylic resins, urethane resins, polyamide resins, polyester resins, amino resins, phenol resins, epoxy resins, ethylene-vinyl acetate copolymer resins, vinyl chloride- It preferably contains at least one selected from the group consisting of vinyl acetate copolymer resins, vinyl acetate resins, cellulose resins, and the like.
  • the permeation of the finishing varnish component, particularly the curing agent component, into the alkali-releasing ink layer is suppressed. It is effective when using an alkali-releasing ink containing one or a combination of a base resin (nitrocellulose) and the like.
  • a known organic solvent can be used together with the above binder resin.
  • examples include, but are not limited to, ketone-based solvents, hydrocarbon-based solvents, ester-based solvents, ether-based solvents, glycol ether-based solvents, and alcohols.
  • System solvents and the like can be mentioned, and one of them can be used alone or two or more of them can be used in combination.
  • the thickness of the alkali-releasable printed layer is preferably 1.2 g/m 2 or more, particularly in the range of 2.6 g/m 2 to 6.0 g/m 2 in terms of coating weight.
  • the finish varnish components from the finish varnish layer do not reach the vicinity of the interface with the base film, and cross-linking in the vicinity of the interface can be suppressed.
  • the alkali-releasing ink on the finishing varnish layer side is crosslinked by the curing agent, it is not crosslinked on the base film side, so the hydrophilicity of the resin in the alkali-releasing ink is reduced by the alkali treatment.
  • the swelling increases and the printed layer can be easily detached from the surface of the substrate film.
  • the printed layer in the printed film of the present invention is not limited to a single layer, and may be multiple layers as long as it has an alkali-releasable printed layer using an alkali-releasable ink. In the case of multiple layers, it is necessary that the layer using the alkali-releasing ink is positioned on the substrate film side. As described above, as the alkali-releasing printed layer is removed from the interface with the base film, the printed layer formed on the layer made of the alkali-releasing ink is also removed at the same time. be done.
  • the alkali-releasable printed layer in the multilayer structure may be a solid printed layer formed by roll coating or the like, or a transparent printed layer (medium layer) containing no coloring material.
  • a pattern layer may be formed by gravure printing using an alkali-releasing ink, or gravure printing using a normal ink other than an alkali-releasing ink.
  • Printing using alkali-releasing ink can also be performed by conventionally known printing methods such as inkjet printing, gravure printing, offset printing, and flexographic printing.
  • the coating amount (thickness) of the other printed layer formed between the alkali-releasable printed layer formed on the base film and the finishing varnish layer is not particularly limited, but as described above, the curing agent from the finishing varnish is preferably 2.2 g/m 2 or more, because the effect of suppressing the permeation of the alkali-releasable printed layer is obtained.
  • a film-forming thermoplastic resin known per se such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl- Olefin resins such as 1-pentene or random or block copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and cyclic olefin copolymers; Polymer, ethylene-vinyl copolymer resin such as ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer; polystyrene, acrylonitrile-styrene copolymer, ABS, ⁇ -methylstyrene-styrene copolymer, etc.
  • ethylene-vinyl copolymer resin such as ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer
  • polystyrene acrylonitrile-st
  • styrene resins vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride/vinylidene chloride copolymer, polymethyl acrylate, and polymethyl methacrylate; nylon 6, nylon 6-6, nylon 6-10, Amide resins such as nylon 11 and nylon 12; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polycarbonate; polyphenylene oxide; biodegradable resins such as polylactic acid; can do.
  • olefin resins and polyester resins can be preferably used from the viewpoint of mechanical strength, printability, and the like.
  • the base film is preferably a stretched film, particularly preferably a biaxially stretched film.
  • the thickness of the base film is not particularly limited, and can be appropriately set in the range of 5.0 to 50.0 ⁇ m, particularly 10.0 to 30.0 ⁇ m, depending on the application.
  • conventionally known resin additives such as lubricants, antiblocking agents, antistatic agents, antioxidants, etc. can be blended into the substrate film according to known formulations.
  • the printed film of the present invention can have other layers such as other printed layers and sealant layers as long as it has at least the base film, the alkali-releasing printed layer and the finishing varnish layer described above.
  • a removable printed layer 2a made of alkali-releasable ink and a printed layer 2b by gravure printing are formed on a base film 1, and a finishing layer is formed on the gravure printed layer 2b.
  • a varnish layer 3 is formed, and a sealant layer 4 is formed on the opposite side of the base film layer 1 to the removable printed layer 2a.
  • a gas barrier resin layer for example, a gas barrier resin layer, an easily tearable resin layer, an oxygen-absorbing resin layer, a UV barrier resin layer, a visible light barrier resin layer, a rigid resin layer, an impact resistant resin layer, a resistant
  • Various functional resin layers such as a chemical layer, a puncture-resistant layer, a heat-resistant layer, etc., or layers made of environmentally friendly resin such as reproduct resin, recycled resin, biomass polyester, etc. may be provided.
  • the functional resin layer uses the same type of resin as the base resin as the base resin and uses a reduced amount of other components.
  • the sealant layer formed on the opposite side of the base film to the alkali-releasable printed layer is made of an olefin resin when the base film is made of an olefin resin, and is made of polyester.
  • a resin it is preferably made of a polyester resin, and an unstretched film by extrusion coating or an amorphous film can be preferably used from the viewpoint of heat sealability.
  • the sealant layer is formed by extrusion coating the base film with an olefin resin such as polyethylene or polypropylene.
  • an amorphous polyester such as PETG can be suitably used as the sealant layer.
  • the thickness of the sealant layer is not particularly limited, it is preferably in the range of 10.0 to 300.0 ⁇ m.
  • a functional resin layer 5 may be formed on the other surface of the material film 1, and a sealant layer 4 may be formed on the functional resin layer 5.
  • the substrate film and alkali desorption may be formed. It may be formed between the printed layers.
  • the printed film of the present invention is produced by forming an alkali-releasable printed layer on a substrate film using an alkali-releasable ink, and then applying a finishing varnish to the alkali-releasable printed layer. be able to.
  • the alkali-releasable printed layer formed on the substrate film is generally formed by heating (drying) at a temperature of 50.0 to 100.0° C. for 0.2 to 10.0 seconds. Next, a finish varnish is applied onto the printed layer thus formed using known means such as roller coating, doctor coating, wire coating, and spray coating.
  • the content of the curing agent in the finishing varnish used in the present invention is reduced, it is desirable to appropriately adjust the heating temperature and heating time according to the amount of the curing agent.
  • heat (dry) at a temperature of 50.0 to 150.0° C. for 0.2 to 10.0 seconds.
  • the resin constituting the sealant layer may be extrusion-coated on the base film, and the sealant layer may be laminated directly on the base film, or may be adhered.
  • Lamination can also be performed by dry lamination using an agent or non-solvent lamination.
  • alkali treatment By subjecting the printed film of the present invention to alkali treatment, the alkali-releasable printed layer is separated from the substrate film, so that only the substrate film can be separated. Moreover, even when a sealant layer is formed on the base film, if the laminated film is composed of the same kind of sealant layer as the base film, there is no need to separate them, and the recyclability is excellent. Alkali treatment can be carried out according to the formulation of the alkali-releasing ink to be used. Layers can be removed.
  • Example 5 A film (thickness: 25 ⁇ m) made of low-density polyethylene was used as the base film, and a transparent alkali-releasing ink was applied to the base film at a coating weight of 1.2 g/m 2 . Cured for 10 seconds. Next, on this transparent printed layer, an epoxy isocyanate-based coating composition (finishing varnish) having an NCO/OH mol ratio shown in Table 1 was applied at a coating weight of 1.48 g/m 2 and heated at 70°C for 10 seconds. It was cured to form a finished varnish layer to produce a printed film.
  • the alkali-releasing ink commercially available alkali-releasing ink containing polyamide resin and nitrocellulose was used.
  • Example 21 A urethane isocyanate-based coating composition (finishing varnish) having an NCO/OH mol ratio shown in Table 5 was prepared in the same manner as in Experimental Example 16, except that the coating amount of the alkali-releasing ink was 2.6 g/m 2 . was used to form a finish varnish layer to produce a printed film.
  • Example 26-30 A urethane isocyanate-based coating composition (finishing varnish) having an NCO/OH mol ratio shown in Table 6 was prepared in the same manner as in Experimental Example 16, except that the coating amount of the alkali-releasing ink was 5.1 g/m 2 . was used to form a finish varnish layer to produce a printed film.
  • Example 91 to 100 A urethane isocyanate-based coating composition (finishing varnish) having an NCO/OH mol ratio shown in Table 13 was used in the same manner as in Experimental Example 81, except that the coating amount of the gravure-printed layer was 5.9 g/m 2 . A finishing varnish layer was formed to produce a printed film.
  • Example 101 A urethane isocyanate-based coating composition (finishing varnish) having an NCO/OH mol ratio shown in Table 14 was used in the same manner as in Experimental Example 81, except that the coating amount of the gravure-printed layer was 11.9 g/m 2 . A finishing varnish layer was formed to produce a printed film.
  • Example 132 A film (thickness: 25 ⁇ m) made of low-density polyethylene was used as the base film, and a transparent alkali-releasing ink was applied to the base film at a coating weight of 2.6 g/m 2 . Cured for 10 seconds.
  • Type of vibration random vibration (vertical vibration) 23 30 27 Frequency range: 2 to 200Hz (JISZ0232 (2020) compliant) Test time: 90 minutes (JISZ0200 level 2 conditions)
  • Verical vibration random vibration
  • Test time 90 minutes (JISZ0200 level 2 conditions)
  • the printed film of the present invention prevents the printed layer from being scratched or peeled off during use, and at the time of disposal, the printed layer can be reliably removed by alkaline treatment, making it suitable for packaging bags that require recycling. can be used for
  • Base film 2. Alkali desorption printing layer, 3. Finishing varnish layer, 4. Sealant layer.

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PCT/JP2022/038332 2021-10-15 2022-10-14 印刷層が脱離可能な印刷フィルム Ceased WO2023063410A1 (ja)

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CN202280062901.6A CN117957117A (zh) 2021-10-15 2022-10-14 印刷层可脱离的印刷膜
EP22881105.5A EP4417418A4 (en) 2021-10-15 2022-10-14 PRINTING FILM FROM WHICH A PRINTED LAYER CAN BE DETACHED
JP2023509794A JP7268809B1 (ja) 2021-10-15 2022-10-14 印刷層が脱離可能な印刷フィルム
US18/627,974 US12359085B2 (en) 2021-10-15 2024-04-05 Printing film from which printing layer can be detached

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WO2023074311A1 (ja) * 2021-10-29 2023-05-04 富士フイルム株式会社 画像記録方法及び非浸透性基材用インクセット
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