WO2023112934A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2023112934A1
WO2023112934A1 PCT/JP2022/045943 JP2022045943W WO2023112934A1 WO 2023112934 A1 WO2023112934 A1 WO 2023112934A1 JP 2022045943 W JP2022045943 W JP 2022045943W WO 2023112934 A1 WO2023112934 A1 WO 2023112934A1
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WO
WIPO (PCT)
Prior art keywords
particles
layer
primer layer
resin
laminate
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Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/045943
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 東
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 Aluminum KK
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Toyo Aluminum KK
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Publication date
Application filed by Toyo Aluminum KK filed Critical Toyo Aluminum KK
Priority to JP2023567798A priority Critical patent/JPWO2023112934A1/ja
Publication of WO2023112934A1 publication Critical patent/WO2023112934A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the present invention relates to a novel laminate, particularly to a laminate having water repellency and/or oil repellency.
  • water-repellent technology or oil-repellent technology has been widely researched for the purpose of preventing adhesion of water, oil, food, and other materials.
  • products materials that have undergone water-repellent or oil-repellent treatment have been developed for the purpose of suppressing or preventing the contents from adhering to packaging materials. It is These water repellency and oil repellency are imparted by modification of chemical properties by coating or modification of physical properties by forming fine unevenness.
  • Patent Document 1 a package having water repellency in which a substrate, a heat-sealing layer made of a thermoplastic resin such as ethylene-vinyl acetate copolymer (EVA) or polyolefin resin, and hydrophobic particles are laminated in order Materials are disclosed.
  • a thermoplastic resin such as ethylene-vinyl acetate copolymer (EVA) or polyolefin resin
  • hydrophobic particles are laminated in order Materials.
  • an antifouling sheet having oil repellency which includes, in order, a base material, a base layer made of a thermoplastic resin, and a layer containing oxide composite particles coated with a polyfluoroalkyl methacrylate resin. is disclosed.
  • the main object of the present invention is to provide a laminate that can exhibit excellent water repellency or oil repellency even under severe use conditions or long-term use conditions.
  • the present invention relates to the following laminate.
  • a laminate characterized by: 2. 3.
  • the fine particle group is (a) Composite particles having a resin coating layer containing a polyfluoroalkyl methacrylate resin on the surface of oxide particles having an average primary particle diameter of 5 to 50 nm and (b) hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm Item 1.
  • a method for producing a laminate comprising a) a substrate layer, b) a primer layer, and c) a fine particle group having water repellency and/or oil repellency fixed inside and/or on the surface of the primer layer, the method comprising the steps of: (A) a step of applying a primer layer-forming coating solution containing a thermosetting resin to the substrate layer and drying the coating solution, and fine particles having water repellency and/or oil repellency on the coating film of the coating solution; A step of applying a dispersion liquid containing the group, or (B) a step of applying a primer layer forming coating liquid containing a fine particle group having water repellency and / or oil repellency and a thermosetting resin to the base layer
  • a method for manufacturing a laminate comprising:
  • a specific layer structure having a) a base layer, b) a primer layer, and c) a functional layer is provided so that the base layer and the functional layer are firmly formed by the thermosetting resin.
  • the fine particle groups in the functional layer are firmly bonded to the thermosetting resin in the primer layer, while on the functional layer surface side, the fine particle groups are By being formed in a three-dimensional network structure, it is possible to exhibit water repellency and/or oil repellency because it exists in a state in which voids are retained. Since part or all of the fine particle group is firmly bound (fixed) to the primer layer, the fine particle group is less likely to fall off, resulting in a laminate having excellent water repellency or oil repellency.
  • the base layer and the functional layer are made stronger by the thermosetting resin. combined. That is, it is possible to form a layer in which the fine particle group and the primer component are kneaded.
  • the microparticle group is formed in a three-dimensional network structure, it can exhibit water repellency and/or oil repellency because it exists in a state where voids are maintained. Since the fine particle group is firmly bound (fixed) by the primer layer, the functional layer is less likely to fall off, resulting in a layered product having excellent durability of water repellency or oil repellency.
  • a laminate having such characteristics can be suitably used, for example, as a packaging material.
  • a packaging material it can be suitably used not only for lids, but also for molded containers, wrapping paper, trays, tubes, and bag bodies such as bags and pouches.
  • the bag may be configured so that the functional layer is arranged on the side that contacts the contents to be packaged.
  • contents containing aqueous and/or oily liquids can be adopted as the contents. That is, a content having fluidity can be applied. More specifically, in addition to foods such as curry, stew, yogurt, jellies, puddings, and seasonings (e.g. yakiniku sauce, dressing, etc.), cosmetics such as liquid detergents, toothpastes, facial cleansing creams, and facial cleansing mousses, etc. It is useful as a packaging material for containing various contents such as pharmaceuticals.
  • FIG. 3 is a schematic diagram showing another layer configuration example of the laminate of the present invention.
  • FIG. 3 is a schematic diagram showing another layer configuration example of the laminate of the present invention.
  • 1 is a schematic diagram showing an outline of a friction wear test apparatus in Test Examples 1 and 2.
  • FIG. 1 is a schematic diagram showing an outline of an apparatus for measuring water repellency or oil repellency in Test Examples 1 and 2.
  • FIG. 1 is a schematic diagram showing an outline of an apparatus for measuring water repellency or oil repellency in Test Examples 1 and 2.
  • the laminate of the present invention is a laminate comprising a) a substrate layer, b) a primer layer, and c) a fine particle group having water repellency and/or oil repellency fixed inside and/or on the surface of the primer layer.
  • the primer layer contains an adhesive resin;
  • part or all of the adhesive resin is a thermosetting resin,
  • the thermosetting resin is contained in the primer layer in an amount of 5 to 100% by mass;
  • Part or all of the fine particle group forms a functional layer having a three-dimensional network structure, and part or all of the fine particle group is exposed on the outermost surface of the laminate. It is characterized by
  • 1 to 3 show layer configuration examples of embodiments of the laminate according to the present invention.
  • the fine particle group having water repellency and/or oil repellency is referred to as "functional particles" unless otherwise specified.
  • the laminate 10 shown in FIG. 1 has a primer layer 12 laminated on a substrate layer 11, and a water-repellent and/or oil-repellent fine particle group 13a (hereinafter referred to as “functionality” unless otherwise specified) on the primer layer. Also referred to as “particles”) are fixed (this form is referred to as "first form").
  • the functional particles 13a form a functional layer 13 having a three-dimensional network structure by sticking (aggregating) to each other. All of the plurality of functional particles may form the functional layer, but a part of the functional particles may form the functional layer as long as the effects of the present invention are not hindered.
  • the laminate 10 of the first embodiment has a structure in which the substrate layer 11, the primer layer 12 containing the adhesive resin, and the functional layer 13 are provided in this order. Since the functional layer 13 is arranged as the outermost layer of the laminate, substantially all of the functional layer is exposed to the outside without being substantially embedded in the primer layer.
  • the functional particles may be partially embedded in the primer layer as long as the effects of the present invention are not hindered.
  • the functional particle 13a' unlike the functional particle 13a', only the lower portion of one functional particle may be submerged in the primer layer.
  • the functional layer 13 is a porous layer with spaces (air layers) formed between the plurality of functional particles 13a.
  • the functional particles are adhered to each other by cohesive force without an adhesive component interposed therebetween.
  • the functional particles may be adhered to each other via an adhesive component within a range that does not impair the effects of the present invention.
  • the functional particles 13a in contact with the primer layer 12 are firmly fixed due to the strong adhesion of the primer layer 12.
  • the functional layer 13 is firmly fixed to the base material layer 11 via the primer layer 12 (especially thermosetting resin).
  • the laminate of the present invention may contain other layers as long as the effects of the present invention are not hindered, but the base layer 11, the primer layer 12 and the functional layer 13 are arranged so that they are in direct contact with each other. It is preferably laminated.
  • the primer layer 12 may contain filler particles (not shown). That is, the present invention includes both a primer layer containing filler particles and a primer layer not containing filler particles as a primer layer. When the primer layer contains filler particles, unevenness derived from the shape of the filler particles can be formed on the surface of the primer layer, whereby higher durability can be obtained. In this regard, filler particles (not shown) may be included in the primer layer 12 as in the embodiment of FIG. 2 below.
  • some particle groups of the plurality of functional particles 13a exist in the primer layer 12, and the remaining particle groups 12 (this form is also called “second form") is also included.
  • “present in the primer layer” means (i) a state in which one functional particle 13a is completely embedded in the primer layer and (ii) a state in which one functional particle 13a is partly in the primer layer. It means both the state of being buried in
  • the functional particles 13a adhere to each other to form a functional layer having a three-dimensional network structure.
  • the functional layer on the opposite side (upper side) of the primer layer or the functional particles constituting it are exposed to the outside. That is, although the functional layer 13 is arranged as the outermost layer of the laminate, part of the functional layer is buried in the primer layer, and the remaining functional layer or functional particles are exposed to the outside. Therefore, the exposed portion may expose substantially the entire three-dimensional network structure.
  • the present invention also includes a form in which the functional particles 13a are exposed in a state in which the functional particles 13a are scattered or interspersed on the surface (a form in which they exist discontinuously).
  • the area ratio of the functional particles to the entire surface of the laminate is, for example, in the range of about 10 to 90%, depending on the desired water repellency or oil repellency. Configurable, but not limited to.
  • part or all of the functional particles 13a form a functional layer having a three-dimensional network structure.
  • the gaps formed by the plurality of functional particles may be spaces, or may be filled with a component (especially an adhesive resin) that constitutes the primer layer.
  • a component especially an adhesive resin
  • some or all of the gaps formed by the plurality of functional particles are filled with the component (especially the adhesive resin) constituting the primer layer.
  • the laminate of the second embodiment may also contain other layers as long as the effect of the present invention is not hindered. preferably.
  • part or all of the fine particle groups 13a may be firmly fixed by the strong adhesive force of the adhesive resin. That is, the fine particle groups 13a may be fixed in direct contact with each other, or may be fixed with an adhesive resin.
  • the functional layer 13 is firmly fixed to the base material layer 11 by binding the fine particles to each other through the adhesive resin (especially thermosetting resin).
  • the layer structure of the laminate of the present invention can be confirmed, for example, with a scanning electron microscope, an optical microscope, or the like.
  • the base material layer is a layer that serves as the foundation (base) of the laminate of the present invention, and has a function of imparting rigidity, strength, and the like to the laminate.
  • Materials constituting the base material layer are not particularly limited, and examples thereof include resin films such as polyester films, polyethylene films, and polypropylene films, paper, synthetic paper, metal foil (aluminum foil, copper foil, etc.), and metal plates. , nonwoven fabric, woven fabric, wood, glass plate, etc., or a composite material or laminate thereof can be used.
  • a material for example, a resin film with a vapor deposition layer
  • an adhesive component is used in the primer layer, a laminate can be produced that adheres favorably to all base material layers and functional layers.
  • a resin film when used as the substrate layer, it may be either a stretched film or an unstretched film. Furthermore, as the stretched film, either a uniaxially stretched film or a biaxially stretched film can be used. As the resin film, various types of films subjected to surface treatment such as corona treatment can also be used as the resin film.
  • the thickness of the base material layer is not limited, but when used as a packaging material, etc., it can be appropriately set according to the type of the item to be packaged. In general, it can be appropriately set within a range of about 9 to 500 ⁇ m. Further, when a resin film is used as the base material layer, it may be subjected to unevenness treatment with a surface treatment agent or unevenness treatment by embossing, for example. In this case, the height of the unevenness can be, for example, about 5 to 60 ⁇ m, or can be about 20 to 50 ⁇ m, but is not limited to this.
  • the primer layer mainly has the function of adhering and fixing the functional particles (or functional layer) to the substrate layer. In some cases, it also has a function of strengthening the adhesion between functional particles.
  • the primer layer contains an adhesive resin, and part or all of the adhesive resin is composed of a thermosetting resin.
  • a thermosetting resin as the adhesive resin contained in the primer layer, the functional particles can be fixed more strongly, resulting in high durability (sustained water or oil repellency). can be done. That is, the thermosetting resin directly adheres to at least a part of the functional particles, so that the functional particles can be firmly solidified.
  • the content of the adhesive resin in the primer layer can be appropriately set, for example, within the range of 1 to 100% by mass (especially 90 to 100% by mass), but is not limited to this.
  • the above content does not include the content of filler particles. Therefore, even if the filler particles are made of a heat-adhesive resin, the content of the filler particles is not included in the content of the heat-adhesive resin.
  • Thermosetting Resin in the laminate of the present invention part or all of the adhesive resin is a thermosetting resin.
  • the proportion of the thermosetting resin in the adhesive resin is usually about 30 to 100% by mass, preferably 50 to 100% by mass. Therefore, for example, all (100% by mass) of the adhesive resin may be a thermosetting resin. As a result, as a result of exhibiting a higher adhesive strength than when a thermoplastic resin is used, excellent wear resistance and the like can be obtained.
  • thermosetting resin is not limited as long as it is thermoset and strongly adheres to the substrate layer and the functional particles (functional layer).
  • examples include phenol resin, urea resin, melamine resin, epoxy resin, In addition to saturated polyester resins, polyurethane resins, diallyl phthalate resins, silicone resins, alkyd resins, and the like, blended resins thereof, copolymers containing combinations of monomers constituting these, modified resins, and the like can be used. These can be used singly or in combination of two or more.
  • at least one of urea resins, melamine resins, epoxy resins, unsaturated polyester resins, polyurethane resins and alkyd resins can be preferably used in the present invention.
  • thermosetting resins at least one of polyurethane resin and melamine resin is more preferable because it can bond the functional particles and the substrate layer more strongly.
  • a polyurethane resin or a melamine resin is used as the thermosetting resin, it adheres well to any substrate layer, such as plastic film, metal foil, paper, etc., and the adhesion between the functional particles and the substrate layer is improved. It can be improved further. In other words, the functional particles or the functional layer are less likely to come off due to friction or the like, and the layered product can exhibit long-lasting water repellency or oil repellency.
  • thermosetting resin may be either a one-liquid curing type or a two-liquid curing type.
  • thermoplastic resin by using a two-liquid curing type thermoplastic resin, it is possible to cure at a relatively low temperature, and by securing the time until complete curing, for example, it contributes to the formation of a functional layer with functional particles. be able to.
  • the content of the thermosetting resin in the primer layer is not limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. . Therefore, for example, it can be set to 50% by mass or more, or 60% by mass or more.
  • the upper limit of the content is usually 100% by mass, but can be, for example, 80% by mass, or even 95% by mass.
  • the thermosetting resin is composed of a main agent and a curing agent, the above content is the sum of both. If the content of the thermosetting resin contained in the thermoadhesive resin is within the above range, durability can be obtained in at least one of water repellency and oil repellency.
  • the content of the thermosetting resin is the content in 100% by mass in total including the thermosetting resin, the thermoplastic resin, the filler particles, and the like.
  • the primer layer may contain no filler particles, but may contain filler particles.
  • the present invention encompasses either case.
  • unevenness is formed by the filler particles on the surface of the primer layer on the functional layer side, and the functional particles are laminated on the uneven surface, and a plurality of functional particles are also placed in the recesses of the uneven surface. exists.
  • the functional particles remaining in the convex portions remain, so that the water repellency and oil repellency can be more reliably maintained.
  • the filler particles in addition to particles consisting of inorganic components or particles consisting of organic components, particles containing both inorganic and organic components can be used. Among these, it is particularly preferable to use at least one of acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, charcoal powder, calcined calcium particles, uncalcined calcium particles, calcium stearate particles, and the like.
  • the shape of the filling particles is not limited, and may be, for example, spherical, spheroidal, irregular, teardrop, flat, hollow, porous, or the like.
  • the average particle size of the filler particles is not limited to Tokura, but is generally preferably about 0.5 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and more preferably 5 to 5 ⁇ m. 30 ⁇ m is most preferred. Therefore, filler particles having an average particle size of about 20 to 90 ⁇ m can also be used. If the average particle size is less than 0.5 ⁇ m, it is not suitable in terms of handleability, formation of the aforementioned gaps, and the like. On the other hand, when the average particle size exceeds 100 ⁇ m, it is not suitable in terms of dropout of the filling particles, dispersibility, and the like.
  • the filler particles have a larger particle size than the functional particles.
  • the minimum particle size of the filler particles is larger than the maximum particle size of the composite particles.
  • the content can be appropriately changed according to, for example, the type of filler particles and the desired physical properties. 25 to 80% by mass is more preferable, and 30 to 70% by mass is most preferable. Therefore, for example, it can be set to about 30 to 50% by mass, and further to 30 to 40% by mass.
  • the said content is content in 100 mass % of total including thermosetting resin, a thermoplastic resin, a filler particle, etc.
  • the primer layer may contain components other than the thermosetting resin as long as the effects of the present invention are not impaired.
  • components other than the thermosetting resin include thermoplastic resins (thermoadhesive resins (heat sealing materials)), tackifiers, antiblocking agents, coloring agents, and thickeners.
  • thermoplastic resins thermoadhesive resins (heat sealing materials)
  • tackifiers tackifiers
  • antiblocking agents coloring agents
  • thickeners thickeners
  • an antiblocking agent can be preferably used.
  • the type of antiblocking agent is not particularly limited, and for example, at least one of polyethylene wax, polypropylene wax, inorganic particles (silica etc.), synthetic resin particles and the like can be preferably added.
  • thermoplastic resin examples include acrylic resins, polystyrene, ABS resins, vinyl chloride resins, polyethylene resins, polypropylene resins, polyamide resins, polycarbonates, polyacetals, fluorine resins, etc., as well as blended resins thereof and combinations of monomers constituting them. Copolymers, modified resins, and the like can be used.
  • the content of the thermoplastic resin in the primer layer is not limited, and can be set appropriately within a range of usually about 0 to 95% by mass (preferably 0 to 70% by mass). etc., it can be, for example, 20 to 90% by mass.
  • the primer layer is imparted with heat-sealing properties, and can be used for applications (packaging materials, etc.) in which the primer layer is heat-sealed.
  • the primer layer does not contain a thermoplastic resin or contains a thermoplastic resin in the range of 10% by mass or less, even under severe conditions. It is preferable because it can be used reliably.
  • the above content of thermoplastic resin does not include the content of filler particles. Therefore, for example, even if the filler particles are made of a thermoplastic resin, the content of the filler particles is not included in the content of the thermoplastic resin.
  • the thickness of the primer layer is not particularly limited, but from the viewpoint of adhesiveness, productivity, cost, etc., it is usually preferably about 0.01 ⁇ m to 5 mm, particularly about 0.01 ⁇ m to 2 mm. is more preferable.
  • the amount of the primer layer to be formed is not particularly limited, but the solid content of the adhesive resin is generally preferably 0.5 to 100 g/m 2 , and more preferably 1 to 100 g/m 2 . , and most preferably 2 to 7 g/m 2 . If the amount of the adhesive resin formed is less than 0.5 g/m 2 , adhesion of the functional particles will be insufficient, and durability may be reduced. On the other hand, if the amount exceeds 100 g/m 2 , the primer layer may be destroyed when a strong stress is applied to the laminate.
  • the ratio of the adhesive resin to the total amount of the adhesive resin (A) and the functional particles (B) [A/(A+B)] is not particularly limited, but generally within the range of about 5 to 97% by mass. It can be set as appropriate.
  • the ratio [A/(A+B)] is particularly preferably 5 to 91% by mass, more preferably 10 to 87% by mass, most preferably 14 to 50% by mass. If the above proportion is less than 5% by mass, the adhesion between the adhesive resin and the substrate may be insufficient and the durability may be reduced. On the other hand, if the above ratio exceeds 91% by mass, the desired three-dimensional network structure of the functional particles becomes difficult to be sufficiently formed, which may impair the water and oil repellency.
  • the method for forming the primer layer is not particularly limited. Further, as described later, when the functional particles are applied, a primer layer may be formed together with the application of the functional particles.
  • the coating liquid for forming the primer layer a solution in which at least the adhesive resin is dissolved in a solvent or a dispersion liquid in which the adhesive resin is dispersed in the solvent can be used.
  • the adhesive resin in addition to the above-described thermosetting resin itself, its raw material (main agent and curing agent) can also be used.
  • the above-described filler particles, thermoplastic resin, and the like can be blended into the coating liquid.
  • solvents include, but are not limited to, water, ethanol, methanol, cyclohexane, toluene, acetone, isopropyl alcohol (IPA), propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, n-pentane, n-hexane.
  • IPA isopropyl alcohol
  • hexyl alcohol methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, isopentyl acetate, normal-butyl acetate, normal-propyl acetate, normal-pentyl acetate (also known as normal-amyl acetate), cyclohexane, isobutyl Alcohol, isopropyl alcohol, isopentyl alcohol, ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ortho-dichlorobenzene, xylene, cresol, chlorobenzene , cyclohexanol, cyclohexanone, N,N-dimethylformamide, tetrahydrofur
  • the solid content concentration and the like of the primer layer-forming coating liquid can be appropriately set, for example, in consideration of coatability, etc., and can be, for example, in the range of about 5 to 60% by mass, but is not limited to this.
  • the method of preparing the primer layer-forming coating solution is not particularly limited, and it can be obtained by adding an adhesive resin or the like to the solvent and mixing. Moreover, the addition order of each component is not specifically limited, either.
  • the method of applying the primer layer-forming coating liquid is not particularly limited, and for example, the base layer is coated by known methods such as roll coating, various gravure coatings, bar coaters, doctor blade coatings, comma coaters, spray coating, and brush coating. can be applied to Also, when the primer layer-forming coating liquid contains filler particles, the adhesive resin (main agent and curing agent) and the filler particles may also be added to the solvent, mixed, and applied to the substrate layer by the above coating method. can be done.
  • the formed coating film is dried. Drying can evaporate the solvent and form a primer layer on the substrate layer.
  • the drying conditions can be appropriately set according to, for example, the type of solvent, the coating amount, and the like.
  • the temperature can be set, for example, in the range of 50 to 250° C., but is not limited to this.
  • the drying time can be in the range of 5 seconds to 60 minutes, but is not limited to this.
  • thermosetting resin contained in the coating film As described later, the functional layer is laminated on the primer layer. If the thermosetting resin contained in the primer layer is in a semi-cured state when laminating the functional layer, the functional particles are formed on the surface of the primer layer. It is more preferable because it becomes difficult for the functional particles to fall off due to sinking into a part.
  • Methods for semi-curing the thermosetting resin contained in the primer layer include, for example, a) a method of adjusting the drying temperature or time, b) a method of adjusting the curing temperature or time of the primer layer formed after drying, and the like. can be adopted. Thereby, the cured state of the thermosetting resin can be controlled.
  • thermosetting resin as a drying condition, a drying temperature of about 90 to 120° C. can be used, but it is not limited to this. Also, the drying time can be about 30 to 90 seconds (especially 30 to 60 seconds), but is not limited to this. Further, if the thermosetting resin is in a semi-cured state even after lamination of the functional layers, the thermosetting resin may be completely cured in the drying process when forming the functional layers.
  • the functional layer is a layer formed by bonding functional particles to each other in a three-dimensional network structure.
  • hydrophobic particles or oleophobic particles can be used depending on the desired function.
  • hydrophobic particles for example, at least one kind of inorganic oxide particles (powder) such as silicon oxide, titanium oxide, aluminum oxide and zinc oxide can be used. Among these, silicon oxide particles are more preferable.
  • hydrophobic particles for example, hydrophilic fine particles hydrophilized by etching, ultraviolet irradiation, blasting, plasma treatment, etc. are hydrophobized with a silane coupling agent or the like, and the hydroxyl groups are partially left. etc. can also be used.
  • a functional layer having a three-dimensional network structure the surface on the primer layer side strongly adheres to the thermosetting resin, and the other surface exhibits super water repellency and/or super oil repellency. can.
  • the inorganic oxide particles preferably have an average primary particle size of 5 to 50 nm, more preferably 7 to 30 nm.
  • the average primary particle diameter of inorganic oxide particles can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle size is obtained by photographing with a transmission electron microscope or scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value. be able to.
  • the nano-level inorganic oxide particles as described above are not limited, and known or commercially available ones can also be used.
  • silica product names "AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974", “AEROSIL RX200”, “AEROSIL RY200” (manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R202 ”, “AEROSIL R805”, “AEROSIL R812”, “AEROSIL R812S”, (manufactured by Evonik Degussa), “Syrophobic 100”, “Syrophobic 200”, “Sylophobic 603” (Fuji Silysia Chemical Co., Ltd.) and the like.
  • titania examples include the product name "AEROXIDE TiO 2 T805" (manufactured by Evonik Degussa).
  • alumina examples include fine particles obtained by treating the product name "AEROXIDE Alu C” (manufactured by Evonik Degussa) with a silane coupling agent to make the particle surface hydrophobic.
  • hydrophobic silica fine particles can be suitably used.
  • hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferred in terms of obtaining superior non-adhesiveness.
  • Examples of commercially available products corresponding to this include the aforementioned “AEROSIL R812” and “AEROSIL R812S” (both manufactured by Evonik Degussa).
  • the adhesion amount (weight after drying) of the hydrophobic particles is not limited, but it can usually be set within the range of about 0.01 to 100 g/m 2 , particularly preferably 0.01 to 10 g/m 2 . , more preferably 0.2 to 1.5 g/m 2 , and most preferably 0.2 to 1 g/m 2 .
  • composite particles containing a) inorganic oxide particles and b) a coating layer containing a polyfluoroalkyl methacrylate resin formed on the surface thereof can be used.
  • a layer containing composite particles it is possible to reduce the adhesion of oil itself or oil-rich components.
  • the particle size of the oil-repellent composite particles those in the same range as the above-described water-repellent inorganic oxide particles can be preferably used.
  • Composite particles having oil repellency include silicon oxide under the product names "AEROSIL 200"("AEROSIL” is a registered trademark; hereinafter the same), "AEROSIL 130", “AEROSIL 300", “AEROSIL 50”, “AEROSIL 200FAD”, It is possible to use oil-repellent particles in which the core is a particle exemplified by “AEROSIL 380” (manufactured by Nippon Aerosil Co., Ltd.) and the surface of the core is coated with a polyfluoroalkyl methacrylate resin.
  • AEROSIL 380 manufactured by Nippon Aerosil Co., Ltd.
  • titanium oxide for example, oleophobic particles in which the core is a particle exemplified by the product name "AEROXIDE TiO 2 T805" (manufactured by Evonik Degussa) and the core surface is coated with a polyfluoroalkyl methacrylate resin can be used.
  • the aluminum oxide for example, particles exemplified by the product name "AEROXIDE Alu C 805" (manufactured by Evonik Degussa) are used as a core, and the core surface is coated with a polyfluoroalkyl methacrylate resin.
  • the polyfluoroalkyl methacrylate resin used as the coating layer has excellent affinity with the core oxide particles (especially silicon oxide particles) as described above, so a strong coating layer with relatively high adhesion is formed on the particle surface. In addition to being able to form on the surface, high water repellency and oil repellency can also be expressed. Known or commercially available resins can be used as such resins.
  • a copolymer obtained by copolymerizing 2,2'-ethylenedioxydiethyldimethacrylate can be suitably employed as the resin.
  • This commercial product is in the form of an aqueous dispersion, but may be in other forms.
  • the method of coating the core surface with the polyfluoroalkyl methacrylate resin is not particularly limited, and a known coating method using the polyfluoroalkyl methacrylate resin as a coating material for the core particles (powder).
  • a coating layer may be formed according to a granulation method or the like.
  • composite oxide fine particles are preferably prepared by a production method including a step (coating step) of coating inorganic oxide particles with a liquid agent in which a liquid polyfluoroalkyl methacrylate resin is dissolved or dispersed in a solvent. be able to.
  • a polyfluoroalkyl methacrylate resin that is liquid at normal temperature (25°C) and normal pressure can be suitably used.
  • a polyfluoroalkyl methacrylate resin the commercially available products exemplified above can also be used.
  • the solvent used for the liquid agent is not particularly limited, and in addition to water, organic solvents such as alcohol and toluene can be used, but it is preferable to use water in the present invention. That is, it is preferable to use a) an aqueous solution in which a polyfluoroalkyl methacrylate resin is dissolved in water, and/or b) a dispersion in which a polyfluoroalkyl methacrylate resin is dispersed in water, as the liquid agent.
  • the content of the polyfluoroalkyl methacrylate resin in the liquid agent is not particularly limited, but is generally set to 10 to 80% by mass, preferably within the range of 20 to 60% by mass.
  • the method of coating the surface of the core particles with the liquid agent may be according to a known method, for example, any of the spray method and the immersion method can be applied.
  • coating by a spray method is particularly preferable in terms of excellent uniformity and the like.
  • the coated particles can be obtained by removing the solvent by heat treatment.
  • the heat treatment temperature is usually about 150 to 250.degree. C., preferably 180 to 200.degree.
  • the heat treatment atmosphere is not limited, but an inert gas atmosphere such as nitrogen gas or argon gas is desirable.
  • a series of steps including a coating step and a heat treatment step can be carried out one or more times as necessary. This makes it possible to suitably control the amount of coating and the like.
  • the amount of oil-repellent particles attached is not limited, but can usually be set within the range of about 0.01 to 100 g/m 2 . It is particularly preferably 0.5 to 100 g/m 2 , more preferably 1 to 100 g/m 2 , and most preferably 15 to 100 g/m 2 .
  • the method for imparting the functional particles to the primer layer or the like is not limited, and for example, (a) a method including a step of coating the surface of the primer layer with a dispersion liquid in which the functional particles are dispersed in a solvent, (b) a functional and a method including a step of coating the surface of the base material layer with a mixed liquid containing organic particles and a primer component. These can also be employed in combination. More specifically, it can be appropriately selected according to the structure/configuration of the laminate of the present invention. Representative examples are shown below.
  • the first embodiment has a structure in which the functional particles are substantially fixed on the primer layer, as shown in FIG. 1, for example.
  • the method for imparting the functional particles is not particularly limited, but it can be preferably carried out by a method including a step of coating the surface of the primer layer with a dispersion liquid in which the functional particles are dispersed in a solvent.
  • the solvent used in the dispersion is not particularly limited, and examples include water, alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane. , normal hexane, and hexyl alcohol.
  • the content of the functional particles in the dispersion liquid can be appropriately determined, for example, in the range of about 20 to 50 g/L (liter) depending on the type of the functional particles, the degree of water repellency and oil repellency, and the like. .
  • the method of coating the material surface with the dispersion liquid is not limited, and a known method can be adopted.
  • any known method such as roll coating, gravure coating, bar coating, doctor blade coating, comma coater, and brush coating can be employed.
  • the coating amount is desirably adjusted so that the weight of the composite particles after drying of the coating film is the above-described coating amount.
  • Drying may be natural drying or heat drying.
  • the temperature for drying by heating is not particularly limited, but it is usually 100° C. or less (preferably 90 to 100° C.).
  • the drying time can be about 30 to 90 seconds (especially 30 to 60 seconds), but is not limited to this.
  • Laminate according to Second Embodiment has a structure in which functional particles are fixed in and on the primer layer, as shown in FIG. 2, for example.
  • the functional particles can be suitably imparted by a method including a step of coating the surface of the base material layer or the surface of the primer layer with a mixture containing the adhesive resin and the functional particles.
  • this mixed liquid is coated on the surface of the base material layer, the application of the functional particles and the formation of the primer layer can be performed at the same time.
  • the mixed liquid may be applied to the layer previously formed from the coating liquid for forming the primer layer as described above.
  • the solvent used in the mixed solution is not particularly limited, and examples include water, ethanol, methanol, cyclohexane, toluene, acetone, isopropyl alcohol (IPA), propylene glycol, hexylene glycol, butyl diglycol, and pentamethylene glycol.
  • IPA isopropyl alcohol
  • the contents of the adhesive resin and the functional particles in the mixed liquid may be adjusted so as to achieve the above-mentioned ratio [A/(A+B)]. can be determined as appropriate.
  • the solid content of the mixed liquid can be, for example, in the range of about 1 to 60% by mass, but is not limited to this. Therefore, it can be, for example, 5 to 25% by mass (especially 5 to 20% by mass). Thereby, for example, the functional particles can be more reliably exposed.
  • the method of coating the material surface with the mixed liquid is not limited, and a known method can be adopted.
  • any known method such as roll coating, gravure coating, bar coating, doctor blade coating, comma coater, and brush coating can be employed.
  • the components (adhesive resin, etc.) forming the primer layer move toward the substrate layer (downward) due to gravity, and some of the functional particles move to the surface.
  • a mixed liquid having sufficient drying or curing time to expose the functional particles after coating can also be preferably used.
  • the ratio of the adhesive resin to the functional particles within the range of the ratio [A/(A+B)]
  • the functional particles (especially the functional layer) are more reliably formed into the laminate. It can be exposed to the surface.
  • Drying may be natural drying or heat drying. In the case of drying by heating, heating may be performed at about 150° C. or less (preferably 90 to 145° C.).
  • the drying time can be, for example, about 30 to 90 seconds, but is not limited to this.
  • the manufacturing method of the second mode it is possible to mold a structure in which a part of the functional particles are embedded in the primer layer and the rest of the functional particles are exposed. That is, part of the functional particles may enter the primer layer, and the other part of the functional particles may be a) exposed from the primer layer or b) stacked on the primer layer. .
  • the functional particles By embedding a part of the functional layer in a part of the primer layer, the functional particles can be more strongly adhered to the primer layer and the durability can be improved, and a part of the functional particle layer is exposed from the primer layer. By doing so, more excellent water repellency and oil repellency can be obtained. As a result, it is possible to maintain excellent water repellency and oil repellency even under severe use conditions or long-term use conditions.
  • a dispersion liquid in which the functional particles are dispersed in a solvent is applied to the surface of the primer layer.
  • a method including a step of pressing the functional particles after coating, and 2) a method including a step of applying a dispersion of functional particles in a solvent to the surface of the primer layer before heat curing is completed. can be done.
  • a method is adopted in which a pressure plate is brought into contact with the functional particles (particle group) deposited on the primer layer, and the pressure plate or the like is pressed downward in the thickness direction. can be done.
  • the dispersion liquid is applied to the primer layer before the thermal curing is completed.
  • part of the functional particles are embedded in the primer layer by their own weight or by being incorporated into the curing reaction of the primer layer.
  • a method of pressing the functional particles can be used together as needed.
  • "before the completion of heat curing” means, for example, a wet state immediately after application of the primer layer forming coating liquid, a naturally dried state, a dry but semi-cured state that has not reached complete curing, and the like. includes any of
  • Example 1 Preparation of base sheet As an adhesive resin, a two-liquid curing type urethane resin (a main ingredient polyester polyurethane polyol (LX500) manufactured by DIC Graphics Co., Ltd.) and a toluene diisocyanate (KW75) manufactured by DIC Graphics as a curing agent are used. 21 parts by weight of an acrylic modified polyolefin resin (APO, manufactured by Tanaka Chemical Co., Ltd.), which is a thermoplastic resin 300214-1 dissolved in ethanol as a solvent with a solid content of 20% by weight) is added, and the ratio of the urethane resin and the acrylic-modified polyolefin resin becomes 10% by mass to 90% by mass in terms of solid content.
  • APO acrylic modified polyolefin resin
  • a primer solution (coating solution for forming a primer layer, hereinafter the same) was prepared. At this time, the total solid content was adjusted to 10% by mass using ethyl acetate. To 100 parts by weight of this primer solution, 5 parts by weight of polyethylene beads (product name "Miperon (registered trademark) XM-221U” manufactured by Mitsui Chemicals, Inc., average particle size: 25 ⁇ m, melting point: 136° C.) were added as filler particles. The mixture was stirred at room temperature for 30 minutes to prepare a coating solution. This coating liquid was dried using a bar coater #6, and the dry weight of the adhesive resin was 7.5 g/m 2 and the dry weight of the adhesive resin was 5.0 g/m 2 .
  • polyethylene beads product name "Miperon (registered trademark) XM-221U” manufactured by Mitsui Chemicals, Inc., average particle size: 25 ⁇ m, melting point: 136° C.
  • a base sheet in which a primer layer is laminated on an aluminum foil by coating the surface of a foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then heating and drying it in an oven at 100 ° C. for 40 seconds to evaporate the solvent. was made.
  • (2) Preparation of composite particles (2-1) Preparation of fluorine-containing composite particles Hydrophilic silica particles (product name “AEROSIL 200”, manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 200 m 2 /g, average primary particle diameter 12 nm) A 100 g portion was placed in a reactor, and 500 g of a commercially available surface treatment agent was sprayed while stirring in a nitrogen gas atmosphere, followed by stirring at 200° C. for 30 minutes and cooling.
  • AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 200 m 2 /g, average primary particle diameter 12 nm
  • the above surface treatment agents include polyfluorooctyl methacrylate, 2-N,N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2'-ethylenedioxydiethyl diethylmethacrylate.
  • An aqueous dispersion of a methacrylate copolymer (solid concentration: 20% by mass) was used.
  • (2-2) Preparation of Dispersion Liquid Containing Composite Particles A dispersion liquid was prepared by adding and mixing 44 parts by weight of the obtained composite particles with 56 parts by weight of ethanol.
  • Example 2 A laminate sample was obtained in the same manner as in Example 1, except that the primer liquid was prepared so that the ratio of the urethane resin and the acrylic-modified polyolefin resin was 30% by mass to 70% by mass.
  • Example 3 A laminate sample was obtained in the same manner as in Example 1, except that the primer liquid was prepared so that the solid content ratio of the urethane resin and the acrylic-modified polyolefin resin (APO) was 50% by mass to 50% by mass.
  • the primer liquid was prepared so that the solid content ratio of the urethane resin and the acrylic-modified polyolefin resin (APO) was 50% by mass to 50% by mass.
  • Example 4 Maleic anhydride-modified polyolefin resin (MAPO) (Tanaka Chemical Co., Ltd. 290628-2) is a thermoplastic resin instead of urethane resin and acrylic-modified polyolefin resin in the primer solution. 20% by mass) is dissolved to a solid content ratio of 50% by mass to 50% by mass, and the base material used for the base sheet is a linear low-density polyethylene having a thickness of 50 ⁇ m from an aluminum foil. (LLDPE, RIX (registered trademark) film L4102 manufactured by Toyobo Co., Ltd., the surface of which was subjected to corona treatment) was changed to obtain a laminate sample in the same manner as in Example 1.
  • MAPO Maleic anhydride-modified polyolefin resin
  • RIX registered trademark
  • Example 5 A laminate sample was obtained in the same manner as in Example 1, except that the urethane resin in the primer liquid was 100% by mass.
  • Example 6 Lamination was carried out in the same manner as in Example 5 except that the amount of the primer liquid applied to the base sheet was 0.75 g/m 2 after drying and the dry weight of the adhesive resin was 0.5 g/m 2 . A body sample was obtained.
  • Example 7 Lamination was carried out in the same manner as in Example 5 except that the amount of the primer liquid applied to the base sheet was 1.5 g/m 2 after drying and the dry weight of the adhesive resin was 1.0 g/m 2 . A body sample was obtained.
  • Example 8 A laminate was produced in the same manner as in Example 5 except that the amount of the primer liquid applied to the base sheet was 15 g/m 2 after drying and the dry weight of the adhesive resin was 10.0 g/m 2 . Got a sample.
  • Example 9 A laminate was produced in the same manner as in Example 5 except that the amount of the primer liquid applied to the base sheet was 150 g/m 2 after drying and the dry weight of the adhesive resin was 100.0 g/m 2 . Got a sample.
  • Example 10 A laminate sample was obtained in the same manner as in Example 5, except that the target lamination amount of the composite particles in the functional layer was changed from 3.0 g/m 2 to 0.3 g/m 2 as the weight after drying.
  • Example 11 A laminate sample was obtained in the same manner as in Example 5, except that the target lamination amount of the composite particles in the functional layer was changed from 3.0 g/m 2 to 0.5 g/m 2 as the weight after drying.
  • Example 12 A laminate sample was obtained in the same manner as in Example 5, except that the target lamination amount of the composite particles in the functional layer was changed from 3.0 g/m 2 to 1.0 g/m 2 as the weight after drying.
  • Example 13 A laminate sample was obtained in the same manner as in Example 5, except that the target lamination amount of the composite particles in the functional layer was changed from 3.0 g/m 2 to 15.0 g/m 2 in terms of weight after drying.
  • Example 14 A laminate sample was obtained in the same manner as in Example 5, except that the target lamination amount of the composite particles in the functional layer was changed from 3.0 g/m 2 to 100.0 g/m 2 as the weight after drying. In addition, since the target lamination amount of 100.0 g / m 2 of the composite particles could not be laminated at once with a bar coater, it was applied with a bar coater, dried, the dry weight was measured, and then applied again with a bar coater and dried. The process of measuring the dry weight was repeated.
  • Example 15 The thermosetting resin was changed from urethane resin to isocyanate (manufactured by DIC Graphics, KW75 toluene diisocyanate dissolved in ethyl acetate as a solvent with a solid content of 20% by mass), and a sample was prepared to function as a base layer and a primer layer. After obtaining a sample comprising layers in order, the obtained sample was cured under 40 ° C. ⁇ 75 RH% for 2 days, and a sample of the laminate was obtained in the same manner as in Example 5, except that the isocyanate was converted to a urea resin. Obtained.
  • isocyanate manufactured by DIC Graphics, KW75 toluene diisocyanate dissolved in ethyl acetate as a solvent with a solid content of 20% by mass
  • Example 16 A laminate sample was obtained in the same manner as in Example 5 except that the base material used for the base material sheet was changed from aluminum foil to biaxially oriented polypropylene (OPP, P2102 manufactured by Toyobo Co., Ltd., corona-treated surface) having a thickness of 20 ⁇ m. .
  • OPP biaxially oriented polypropylene
  • Example 17 A laminate sample was obtained in the same manner as in Example 5 except that the urethane resin was 100% by mass, no thermoplastic resin was added, and filler particles were not added to this primer solution.
  • the adhesive resin is a mixture of 50 parts by weight of epoxy resin (adhesive No. 31 manufactured by Daiso Co., Ltd., 100% epoxy as the main agent) and 50 parts by weight of melamine resin (TF842 heat-resistant reinforcing agent manufactured by DIC Graphics), which is a thermosetting resin.
  • the solid content is 20% by mass and dissolved in ethyl acetate as a solvent. No thermoplastic resin is added.
  • a sample of the laminate was obtained in the same manner as in Example 1, except that it was not added.
  • the adhesive resin is an epoxy resin (adhesive No. 31 manufactured by Daiso Co., Ltd., a 1:1 mixture of 100% epoxy as the main agent and 100% polythiol as the curing agent), which is a thermosetting resin, and the solid content is 20% by mass. was dissolved in ethyl acetate as a solvent, no thermoplastic resin was added, the proportion of the thermosetting resin in the primer layer was 100% by mass, and no filler particles were added to this primer solution. A sample of the laminate was obtained in the same manner as in Example 1.
  • Example 20 To 100 parts by weight of the primer solution, 10 parts by weight of polyethylene beads (product name “Mipelon (registered trademark) XM-221U” manufactured by Mitsui Chemicals, Inc., average particle diameter: 25 ⁇ m, melting point: 136° C.) are added as filler particles. A laminate sample was obtained in the same manner as in Example 19, except that the mixture was stirred at room temperature for 30 minutes.
  • polyethylene beads product name “Mipelon (registered trademark) XM-221U” manufactured by Mitsui Chemicals, Inc., average particle diameter: 25 ⁇ m, melting point: 136° C.
  • the adhesive resin is a thermosetting unsaturated polyester resin (5013PT light color transparent type FRP resin non-paraffin manufactured by PROST) 100 parts by weight and a solid content of 20% by weight dissolved in ethyl acetate as a solvent.
  • a sample of the laminate was prepared in the same manner as in Example 1 except that no plastic resin was added, the proportion of the thermosetting resin in the primer layer was 100% by mass, and no filler particles were added to this primer liquid. Obtained.
  • Example 22 The adhesive resin is 100 parts by weight of an alkyd resin (WOOD LOVE Oil Finish), no thermoplastic resin is added, the proportion of the thermosetting resin in the primer layer is 100% by mass, and the primer liquid is filled with particles A sample of the laminate was obtained in the same manner as in Example 1, except that the was not added.
  • an alkyd resin WOOD LOVE Oil Finish
  • Example 23 The adhesive resin is a silicone resin (repair agent A No. 1 silicone repair agent manufactured by Daiso Co., Ltd.) of 100 parts by weight and a solid content of 20% by mass dissolved in distilled water as a solvent, and no thermoplastic resin is added.
  • a laminate sample was obtained in the same manner as in Example 1, except that the proportion of the thermosetting resin in the primer layer was set to 100% by mass, and the filler particles were not added to the primer liquid.
  • Example 24 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1. 44.6 parts by weight of the solid content of 32% by mass and dissolved in ethyl acetate as a solvent). 857 parts by weight of a coating liquid containing composite particles adjusted to 10% by weight was added, and a mixed solution was prepared so that the ratio of the urethane resin to the composite particles was 14% by weight to 86% by weight in terms of solid content.
  • DIGI Graphics' main agent polyester polyurethane polyol (LX500) which is a thermosetting resin
  • KW75 company's toluene diisocyanate
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #12 to a weight of 3.5 g/m 2 after drying, and the thickness of the substrate layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 . It is coated on the surface of a 30 ⁇ m aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30), and then heated and dried in an oven at 140 ° C. for 40 seconds to evaporate the solvent.
  • a laminate sample comprising a primer layer and a functional layer was obtained.
  • Example 25 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1.
  • DI Graphics' main agent polyester polyurethane polyol (LX500) which is a thermosetting resin
  • KW75 company's toluene diisocyanate
  • This coating solution was dried using a bar coater #28 to a weight of 11.5 g/m 2 after drying, and the dry weight of the adhesive resin was 10 g/m 2 . It was applied to the surface of an aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C. for 60 seconds to evaporate the solvent. After that, by performing the same operation again using the coating liquid, a sample of a laminate having a primer layer containing composite particles and a functional layer on an aluminum foil was obtained. The total dry weight of the primer layer and the composite particles was 23 g/m 2 , in which the dry weight of the adhesive resin was 20 g/m 2 .
  • Example 26 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1. Ethyl acetate was added to the composite particles obtained in "(2) Preparation of composite particles" of Example 1 for 284 parts by weight of the mixture dissolved in ethyl acetate as a solvent with a solid content of 32% by mass.
  • DIGI Graphics' main agent polyester polyurethane polyol (LX500) which is a thermosetting resin
  • KW75 company's toluene diisocyanate
  • a coating liquid containing 10% by mass of composite particles was added to prepare a mixture so that the ratio of the urethane resin to the composite particles was 91% by mass to 9% by mass in terms of solid content.
  • the total solid content was adjusted to 15% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #14 to a weight of 5.5 g/m 2 after drying, and the dry weight of the adhesive resin was 5 g/m 2 .
  • a primer layer containing composite particles and a functional layer are formed by coating the surface of an aluminum foil (1N30, manufactured by Toyo Aluminum Co., Ltd.), followed by heating and drying in an oven at 140 ° C. for 40 seconds to evaporate the solvent. A sample of the laminate was obtained.
  • Example 27 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1.
  • the composite particles obtained in "(2) Preparation of composite particles" in Example 1 were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass, and ethyl acetate was added to 78.1 parts by weight.
  • a coating liquid containing 10% by mass of composite particles was added to prepare a mixture so that the solid content ratio of the urethane resin and the composite particles was 25% by mass to 75% by mass.
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating liquid was dried using a bar coater #22 to a weight of 10 g/m 2 , and the dry weight of the adhesive resin was 2.5 g/m 2 , and the thickness of the substrate layer was 30 ⁇ m. (Toyo Aluminum Co., Ltd., 1N30), and then heated and dried in an oven at 140° C. for 60 seconds to evaporate the solvent.
  • a sample of a laminate having a primer layer containing composite particles and a functional layer on an aluminum foil was obtained.
  • the total weight of the primer layer and the composite particles after drying was 20 g/m 2 , in which the dry weight of the adhesive resin was 5 g/m 2 .
  • Example 28 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1.
  • the composite particles obtained in "(2) Preparation of composite particles" in Example 1 were dissolved in ethyl acetate as a solvent with a solid content of 32% by mass), and ethyl acetate was added to the composite particles.
  • a coating liquid containing 10% by mass of composite particles was added to prepare a mixture so that the ratio of the urethane resin to the composite particles was 5% by mass to 95% by mass in terms of solid content.
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #22 to a weight of 10 g/m 2 after drying, and the dry weight of the adhesive resin was 0.5 g/m 2 . It was applied to the surface of an aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C.
  • Example 29 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1.
  • a modified polyolefin resin which is a thermoplastic resin, is dispersed in methylcyclohexane at a solid content of 20% by mass.
  • a mixed solution was prepared so that the ratio of the resin to the composite particles was 14% by mass to 86% by mass in solid content ratio.
  • the total solid content was adjusted to 15% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #14 to a weight of 3.5 g/m 2 , and the thickness of the base material layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 .
  • a primer layer containing composite particles and a functional layer were coated on the surface of a 30 ⁇ m aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C. for 40 seconds to evaporate the solvent. A sample of the laminate was obtained.
  • Example 30 As the adhesive resin, a two-liquid curing type urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent, at a weight ratio of 10:1. 156 parts by weight of the compound blended in (32% by mass of solids) dissolved in ethyl acetate, which is a solvent, and a modified polyolefin resin, which is a thermoplastic resin, is dispersed in methylcyclohexane at a solids content of 20% by mass.
  • DIGI Graphics' main agent polyester polyurethane polyol (LX500) which is a thermosetting resin
  • KW75 company's toluene diisocyanate
  • a mixed solution was prepared so that the ratio of the resin to the composite particles was 14% by mass to 86% by mass in solid content ratio.
  • the total solid content was adjusted to 15% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #14 to a weight of 3.5 g/m 2 , and the thickness of the base material layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 .
  • a primer layer containing composite particles and a functional layer were coated on the surface of a 30 ⁇ m aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C. for 40 seconds to evaporate the solvent. A sample of the laminate was obtained.
  • Example 31 50 parts by weight of epoxy resin (adhesive No. 31 manufactured by Daiso Co., Ltd., main epoxy resin 100%) and 50 parts by weight of melamine resin (manufactured by DIC Graphics, TF842 heat-resistant reinforcing agent) are used as adhesive resins.
  • Ethyl acetate was added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1, with respect to 71.4 parts by weight of a mixture dissolved in ethyl acetate as a solvent to make a solid content of 20% by mass.
  • a coating liquid containing composite particles adjusted to 10% by mass was added to prepare a mixture so that the ratio of the urethane resin to the composite particles was 14% by mass to 86% by mass in terms of solid content.
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #12 to a weight of 3.5 g/m 2 after drying, and the thickness of the substrate layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 .
  • Example 32 A thermosetting resin was added to 71.4 parts by weight of isocyanate (manufactured by DIC Graphics, KW75 toluene diisocyanate dissolved in ethyl acetate as a solvent with a solid content of 20% by mass) in Example 1, "(2) Composite 857 parts by weight of a coating liquid containing composite particles was added to the composite particles obtained in "Preparation of particles” to make it 10% by mass by adding ethyl acetate, and the ratio of isocyanate and composite particles was 14% by mass to 86% by mass in terms of solid content. %.
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #12 to a weight of 3.5 g/m 2 after drying, and the thickness of the substrate layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 . It was applied to the surface of a 30 ⁇ m aluminum foil (1N30, manufactured by Toyo Aluminum Co., Ltd.) and then heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent.
  • the obtained sample was aged at 40° C. ⁇ 75 RH % for 2 days to convert the isocyanate into a polyurea resin (urea resin) by reacting the isocyanate with moisture in the air.
  • a laminate sample including a primer layer containing composite particles and a functional layer was obtained.
  • Example 33 100 parts by weight of an unsaturated polyester resin (5013PT light-colored transparent type FRP resin non-paraffin manufactured by PROST Co., Ltd.) as an adhesive resin is dissolved in ethyl acetate as a solvent with a solid content of 20% by weight. 857 parts by weight of a coating liquid containing composite particles obtained by adding ethyl acetate to the composite particles obtained in "(2) Preparation of composite particles" of Example 1 to make the composite particles 10% by weight was added to 4 parts by weight, and urethane was added. A mixed solution was prepared so that the ratio of the resin to the composite particles was 14% by mass to 86% by mass in terms of solid content.
  • an unsaturated polyester resin 5013PT light-colored transparent type FRP resin non-paraffin manufactured by PROST Co., Ltd.
  • the total solid content was adjusted to 10% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #12 to a weight of 3.5 g/m 2 after drying, and the thickness of the substrate layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 .
  • a primer layer containing composite particles and a functional layer were coated on the surface of a 30 ⁇ m aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C. for 40 seconds to evaporate the solvent. A sample of the laminate was obtained.
  • Example 34 As the adhesive resin, a two-liquid curable urethane resin (DIC Graphics' main agent polyester polyurethane polyol (LX500), which is a thermosetting resin, and the company's toluene diisocyanate (KW75) as a curing agent are blended at a weight ratio of 10:1. Ethyl acetate was added to the composite particles obtained in "(2) Preparation of composite particles" in Example 1 for 156 parts by weight of the mixture obtained by dissolving the solid content of 32% by mass in ethyl acetate as a solvent.
  • DIGI Graphics' main agent polyester polyurethane polyol (LX500) which is a thermosetting resin
  • KW75 company's toluene diisocyanate
  • a mixed solution was prepared by adding 500 parts by weight of a coating liquid containing composite particles to 10% by weight so that the ratio of the urethane resin to the composite particles was 50% by weight to 50% by weight in terms of solid content.
  • a coating liquid containing composite particles to 10% by weight so that the ratio of the urethane resin to the composite particles was 50% by weight to 50% by weight in terms of solid content.
  • 25 parts by weight of polyethylene beads product name “Mipelon (registered trademark) XM-221U” manufactured by Mitsui Chemicals, Inc., average particle diameter: 25 ⁇ m, melting point: 136° C.
  • the mixture was stirred at room temperature for 30 minutes to prepare a coating solution.
  • the total solid content was adjusted to 15% by mass using ethyl acetate, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #18 to a weight of 7.5 g/m 2 , and the thickness of the base material layer was adjusted so that the dry weight of the adhesive resin was 3.0 g/m 2 .
  • a primer layer containing composite particles and a functional layer were coated on the surface of a 30 ⁇ m aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) and then dried by heating in an oven at 140° C. for 40 seconds to evaporate the solvent. A sample of the laminate was obtained.
  • Example 35 Instead of the composite particles of Example 1 (2), 5 g of hydrophobic particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 /g, primary particle average diameter: 7 nm) were dispersed in 100 mL of ethanol. to prepare a coating liquid, coat the surface of the base sheet of Example 5 on which the primer layer is laminated using a bar coater #16, and heat and dry it in an oven at 100 ° C. for 40 seconds to remove ethanol. Evaporation gave a laminate sample comprising a base layer, a primer layer and a functional layer in that order. The target lamination amount of the hydrophobic particles was 3.0 g/m 2 in terms of weight after drying.
  • AEROSIL R812S manufactured by Evonik Degussa
  • Example 36 Instead of the fluorine-containing composite particles of Example 1 (2), 5 g of hydrophobic particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 /g, primary particle average diameter: 7 nm) was added to 100 mL of ethanol. to prepare a coating liquid, coat the surface of the base sheet of Example 1 on which the primer layer is laminated using a bar coater #16, and heat and dry in an oven at 100 ° C. for 40 seconds. By evaporating ethanol, a laminate sample having a base layer, a primer layer and a functional layer in this order was obtained. The target lamination amount of the hydrophobic particles was 3.0 g/m 2 in terms of weight after drying.
  • AEROSIL R812S manufactured by Evonik Degussa
  • Example 37 Instead of the fluorine-containing composite particles of Example 1 (2), 5 g of hydrophobic particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 /g, primary particle average diameter: 7 nm) was added to 100 mL of ethanol. to prepare a coating liquid, coat the surface of the base sheet of Example 3 on which the primer layer is laminated using a bar coater #16, and heat and dry for 40 seconds in an oven at 100 ° C. By evaporating ethanol, a laminate sample having a base layer, a primer layer and a functional layer in this order was obtained. The target lamination amount of the hydrophobic particles was 3.0 g/m 2 in terms of weight after drying.
  • AEROSIL R812S manufactured by Evonik Degussa
  • Comparative example 1 The adhesive resin is 100 parts by weight of an acrylic-modified polyolefin resin that is a thermoplastic resin, no thermosetting resin is added, the proportion of the thermosetting resin in the primer layer is 0% by mass, and the primer liquid is filled.
  • a laminate sample was obtained in the same manner as in Example 1, except that no particles were added.
  • Comparative example 2 Example 1 was used, except that the adhesive resin was 100 parts by weight of an acrylic-modified polyolefin resin, which is a thermoplastic resin, and no thermosetting resin was added, and the proportion of the thermosetting resin in the primer layer was 0% by mass. A laminate sample was obtained in the same manner.
  • the adhesive resin is a thermoplastic resin maleic anhydride-modified polyolefin resin (290628-2 manufactured by Tanaka Chemical Co., Ltd. dissolved in AP-NT solvent manufactured by Tanaka Chemical Co., Ltd. as a solvent with a solid content of 20% by weight).
  • No curable resin is added, the ratio of the thermosetting resin in the primer layer is set to 0% by mass, and the base material used for the base sheet is a linear low-density polyethylene (LLDPE, Toyobo Co., Ltd.) having a thickness of 50 ⁇ m from aluminum foil.
  • LLDPE linear low-density polyethylene
  • thermosetting resin is obtained by dissolving the adhesive resin in ethyl acetate as a solvent with 100 parts by weight of butadiene rubber (adhesive No. 44 for bond plastic manufactured by Daiso Co., Ltd.) as a thermoplastic resin and a solid content of 20% by weight.
  • the proportion of the thermosetting resin in the primer layer is set to 0% by mass, and the base material used for the base sheet is made of aluminum foil with a thickness of 20 ⁇ m biaxially oriented polypropylene (P2102 manufactured by Toyobo Co., Ltd., corona-treated surface )), a laminate sample was obtained in the same manner as in Example 1.
  • Comparative example 5 71.4 parts by weight of a solution in which a modified polyolefin resin, which is a thermoplastic resin, is dispersed in methylcyclohexane at a solid content of 20% by mass (modified polyolefin, AP-31Z-EA manufactured by Tanaka Chemical Co., Ltd.), Ethyl acetate was added to the composite particles obtained in "(2) Preparation of composite particles" to add 857 parts by weight of the coating liquid containing the composite particles to 10% by mass, and the ratio of the modified polyolefin and the composite particles in terms of solid content ratio was Mixtures were prepared to be 14% by weight to 86% by weight.
  • a modified polyolefin resin which is a thermoplastic resin
  • the total solid content was adjusted to 10% by mass using methylcyclohexane, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid.
  • This coating solution was dried using a bar coater #12 to a weight of 3.5 g/m 2 after drying, and the thickness of the substrate layer was adjusted so that the dry weight of the adhesive resin was 0.5 g/m 2 .
  • a primer containing composite particles is coated on the surface of a 30 ⁇ m aluminum foil (1N30, manufactured by Toyo Aluminum Co., Ltd.) and then heated and dried in an oven at 140° C. for 40 seconds to evaporate the solvent.
  • a sample of a laminate comprising a layer and a functional layer was obtained.
  • Comparative example 6 As the adhesive resin, a solution (modified polyolefin, AP-31Z-EA manufactured by Tanaka Chemical Co., Ltd.) in which a modified polyolefin resin, which is a thermoplastic resin, is dispersed in methylcyclohexane at a solid content of 20% by mass was used as a coating liquid. This coating liquid is applied to the surface of a 30 ⁇ m thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) serving as a base layer so that the weight after drying is 0.5 g/m 2 using a bar coater #3. Then, the substrate was dried by heating in an oven at 100° C. for 40 seconds to evaporate the solvent.
  • a solution modified polyolefin, AP-31Z-EA manufactured by Tanaka Chemical Co., Ltd.
  • a modified polyolefin resin which is a thermoplastic resin
  • hydrophobic particles product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 /g, primary particle average diameter: 7 nm
  • the surface of the material sheet on which the primer layer is laminated is coated with a bar coater #18 and dried by heating in an oven at 100 ° C. for 40 seconds to evaporate the ethanol, thereby forming the base layer and the primer layer. , and a functional layer were obtained.
  • the target lamination amount of the hydrophobic particles was 3.0 g/m 2 in terms of weight after drying.
  • Test Example 1 water repellency test
  • a friction wear tester "TRIBOGEAR TYPE: 4.0" manufactured by Shinto Kagaku Co., Ltd.
  • a friction test was carried out by the following method according to the friction coefficient test method specified in the Japanese Industrial Standard "JIS K7125: 1999”.
  • a laminate sample was cut into a size of 80 mm (width direction) x 200 mm (machine direction).
  • the cut laminate sample was fixed so that the flow direction of the sample was parallel to the friction wear direction of the friction wear tester.
  • a 63.5 mm ⁇ 63.5 mm ASTM flat indenter (hereinafter referred to as "indenter") is attached so that the rough surface of a paper towel (Kimwipe, manufactured by Nippon Paper Crecia) is in contact with the functional layer surface of the laminate sample. rice field. At this time, as shown in FIG. 4, the paper towel and the indenter were brought into close contact with each other, and careful attention was paid so that wrinkles or the like would not occur.
  • the indenter with the paper towel set was attached to the friction wear tester. At this time, the grain direction of the paper towel was adjusted to be parallel to the frictional wear direction.
  • the location where the liquid was dropped was within 3 cm from the center of the frictionally worn location of the measurement sample obtained in (1) above in the direction of frictional wear.
  • the outline of the test method is shown in FIG. " ⁇ " indicates that all three of the dropped water droplets rolled on the functional layer, " ⁇ ” indicates that both of the dropped water droplets rolled on the functional layer and some did not roll, and the dripped water droplets were on the functional layer When all three droplets did not roll over and stayed on the surface, they were marked with "x”.
  • Tables 1-3 The results are shown in Tables 1-3.
  • Test Example 2 oil repellency test
  • (1) Preparation of measurement sample A measurement sample was prepared in the same manner as in “(1) Preparation of measurement sample” in Test Example 1 above.
  • (2) Confirmation of oil repellency of measurement sample On a table tilted at 15 degrees with respect to the horizontal surface, the surface of the measurement sample obtained in (1) above with the functional layer faces upward, and the direction of friction wear is It was left still so that it would be perpendicular to the direction in which the water droplets roll.
  • 30 ⁇ 3 g/drop of commercially available edible oil (Nissin Oilio Group, Nisshin Canola Oil Healthy Light 900 g) was dropped from a height of 1 cm near the center of the surface provided with the functional layer with a dropper.
  • the laminate of each example has improved durability (sustainability) in terms of water repellency and/or oil repellency as compared to a laminate having a primer layer containing only a conventional thermoplastic resin. It can be seen that Further, when filler particles are added to the primer layer, the durability of water repellency and/or oil repellency is further improved. It is also found that the higher the content of the thermosetting resin in the primer layer, the greater the effect of improving the durability.

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WO2024053489A1 (ja) * 2022-09-06 2024-03-14 日本製紙株式会社 （メタ）アクリレート変性ポリオレフィン樹脂

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Publication number Priority date Publication date Assignee Title
WO2018150455A1 (ja) * 2017-02-14 2018-08-23 三菱電機株式会社 撥水性被膜及びそれが形成された製品
JP2019038554A (ja) * 2017-08-23 2019-03-14 昭和電工パッケージング株式会社 内容物付着防止蓋材
WO2020179412A1 (ja) * 2019-03-07 2020-09-10 東洋紡株式会社 積層フィルム

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018150455A1 (ja) * 2017-02-14 2018-08-23 三菱電機株式会社 撥水性被膜及びそれが形成された製品
JP2019038554A (ja) * 2017-08-23 2019-03-14 昭和電工パッケージング株式会社 内容物付着防止蓋材
WO2020179412A1 (ja) * 2019-03-07 2020-09-10 東洋紡株式会社 積層フィルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024053489A1 (ja) * 2022-09-06 2024-03-14 日本製紙株式会社 （メタ）アクリレート変性ポリオレフィン樹脂

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