WO2017138635A1 - Feuille cosmétique et son procédé de fabrication - Google Patents

Feuille cosmétique et son procédé de fabrication Download PDF

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Publication number
WO2017138635A1
WO2017138635A1 PCT/JP2017/004928 JP2017004928W WO2017138635A1 WO 2017138635 A1 WO2017138635 A1 WO 2017138635A1 JP 2017004928 W JP2017004928 W JP 2017004928W WO 2017138635 A1 WO2017138635 A1 WO 2017138635A1
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Prior art keywords
layer
fabric layer
resin
decorative sheet
mass
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PCT/JP2017/004928
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English (en)
Japanese (ja)
Inventor
真志 服部
正光 長濱
佐藤　彰
高橋　昌利
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凸版印刷株式会社
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Publication of WO2017138635A1 publication Critical patent/WO2017138635A1/fr

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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
    • 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
    • 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

Definitions

  • the present invention relates to a decorative sheet used for a building interior material, a building exterior member such as a front door, a surface of a joinery, a surface material of home appliances, and a manufacturing method thereof.
  • Patent Document 1 discloses that a topcoat layer made of a resin containing a triazine-based organic ultraviolet absorber is provided on the surface of a polyolefin sheet.
  • the aggregated ultraviolet absorber bleeds on the surface of the resin composition.
  • the resin sheet is adhered to another resin sheet due to powder spraying or stickiness, it has a problem of poor adhesion.
  • the present invention has excellent adhesion between the original fabric layer and other resin layers by suppressing the aggregation of the ultraviolet absorber even when an ultraviolet absorber is contained in the original fabric layer, and further has excellent weather resistance. It aims at providing the decorative sheet which has property.
  • the decorative sheet of one embodiment of the present invention is a decorative sheet including a raw fabric layer made of a resin composition containing an olefin resin as a main component, and the raw fabric layer absorbs ultraviolet rays.
  • the ultraviolet absorber is added to the resin composition constituting the raw fabric layer in the state of the ultraviolet absorber vesicle included in the outer film.
  • the method for producing a decorative sheet according to one aspect of the present invention is a method for producing a decorative sheet comprising a raw fabric layer made of a resin composition containing an olefin resin as a main component, wherein the ultraviolet absorber is used as an outer membrane.
  • the included ultraviolet absorber vesicle is added to the resin composition.
  • the ultraviolet absorber may be added to the resin composition of the original fabric layer in a state where the ultraviolet absorber is included in the outer membrane of the vesicle, so that the original fabric layer may contain the ultraviolet absorber. It is possible to provide a decorative sheet having excellent weather resistance. Moreover, since generation
  • the decorative sheet of the present embodiment based on the present invention is a decorative sheet provided with a raw fabric layer made of a resin composition containing an olefin resin as a main component, and the raw fabric layer contains an ultraviolet absorber.
  • the ultraviolet absorber is added to the resin composition constituting the raw fabric layer in the state of the ultraviolet absorber vesicle included in the outer membrane (vesicle).
  • one of the features (invention specific matter) of the present invention is that "by adding an ultraviolet absorber to the resin composition constituting the raw fabric layer in the state of an ultraviolet absorber vesicle included in the outer membrane, In a decorative sheet as a product, an ultraviolet absorber is contained in the original fabric layer. And, by adding to the resin composition in the state of the ultraviolet absorber vesicle, there is an effect of dramatically improving the dispersibility of the ultraviolet absorber in the resin material, that is, in the raw fabric layer. It can be said that it is impractical to directly specify the structure and characteristics of the object in the state of the completed decorative sheet, depending on the situation. The reason is as follows.
  • the ultraviolet absorber added in the state of vesicle is in a dispersed state having high dispersibility, and the ultraviolet absorber is highly dispersed in the original fabric layer even in the state of the produced decorative sheet.
  • the compression treatment or curing treatment to the laminate is usually performed.
  • the outer membrane of the UV absorber vesicle is crushed or chemically reacted, and the UV absorber is not included in the outer membrane (skin).
  • the state in which the outer membrane is crushed or chemically reacted varies depending on the process of the decorative sheet.
  • the ultraviolet absorbent vesicle has a structure in which the ultraviolet absorbent is encapsulated in a vesicular capsule having a membrane structure closed in a spherical shell shape.
  • This ultraviolet absorbent vesicle has extremely high dispersibility without causing the particles to aggregate due to the action of repelling each other's outer membranes. This action makes it possible to uniformly disperse the ultraviolet absorber in the resin composition constituting the raw fabric layer.
  • Examples of the method for obtaining the ultraviolet absorber vesicle include the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method, and the like. Briefly explaining such a vesicle treatment method, in the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further dissolved therein.
  • the extrusion method is a method of preparing a vesicle by preparing a thin phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method.
  • the hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing without using a mixer.
  • phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to make a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added.
  • the freeze-thaw method is a method using cooling / heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling / heating.
  • a supercritical reverse phase evaporation method may be mentioned as a method for obtaining an ultraviolet absorbent vesicle having an outer film composed of a single layer film.
  • the supercritical reverse phase evaporation method is disclosed in JP-T-2002 / 032564, JP-A-2003-119120, JP-A-2005-298407, and JP-A-2008-063274 (provided by the present inventors). (Hereinafter referred to as “supercritical reverse phase evaporation method publications”), and can be carried out using the method and apparatus described in the supercritical reverse phase evaporation method publications.
  • supercritical reverse phase evaporation is a method in which a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide under supercritical conditions or temperature conditions or pressure conditions above the critical point.
  • an aqueous phase containing an ultraviolet absorber as a water-soluble or hydrophilic encapsulating substance is added to form a capsule-like vesicle including the ultraviolet absorber as an encapsulating substance in a single layer.
  • an ultraviolet absorbent vesicle in which the outer membrane is composed of a substance containing a biological lipid such as phospholipid is referred to as an ultraviolet absorbent liposome.
  • the supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or more, and a temperature condition above the critical point.
  • Carbon dioxide under lower or pressure conditions means carbon dioxide having only critical temperature or critical pressure exceeding the critical condition.
  • Phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated yolk lecithin, soybean lecithin, glycerophospholipid such as hydrogenated soybean lecithin, sphingomyelin, Examples include sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol. Other substances that form the outer membrane of vesicles include nonionic surfactants and dispersants such as a mixture of this with cholesterols or triacylglycerols.
  • nonionic surfactants include polyglycerol ether, dialkyl glycerol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene.
  • polyoxyethylene copolymer polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. More than seeds can be used.
  • cholesterol As cholesterols, cholesterol, ⁇ -cholestanol, ⁇ -cholestanol, cholestane, desmosterol (5,24-cholestadien-3 ⁇ -ol), sodium cholate or cholecalciferol can be used.
  • the ultraviolet absorbent vesicle is preferably an ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid, so that The compatibility between the resin material as the component and the vesicle can be improved.
  • the ultraviolet absorber an inorganic ultraviolet absorber or an organic ultraviolet absorber can be used.
  • inorganic ultraviolet absorbers have little deterioration over time and can obtain stable ultraviolet absorption performance over a long period of time.
  • the organic ultraviolet absorber is excellent in transparency and can improve the weather resistance without impairing the design of the original fabric layer.
  • inorganic ultraviolet absorbers examples include zinc oxide, titanium oxide, and ceria oxide.
  • zinc oxide is suitable because it is excellent in transparency and can improve the weather resistance without impairing the design of the original fabric layer.
  • Such an inorganic ultraviolet absorber is contained in the resin composition constituting the raw fabric layer in a range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin material as the main component.
  • it is. More preferably, it is the range of 0.5 mass part or more and 2 mass parts or less with respect to 100 mass parts of resin materials.
  • ultraviolet absorption performance will not fully be acquired, but when there is more content than 10 mass parts, possibility that a bleedout will arise will become high.
  • the organic ultraviolet absorber at least one selected from benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate can be used.
  • benzotriazole and triazine ultraviolet absorbers can be used.
  • the agent is suitable because it is excellent in transparency and can improve the weather resistance without impairing the design of the original fabric layer, and is suitable from at least one of the benzotriazole-based or triazine-based organic ultraviolet absorbers. It is preferable to select and use.
  • Such an organic ultraviolet absorber is contained in the resin composition constituting the raw fabric layer in a range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin material as the main component. Preferably it is.
  • the decorative sheet 1 of the present embodiment has an ink layer 5, an adhesive layer 4, a transparent resin layer 3, and a topcoat layer 2 formed in this order on the raw fabric layer 6. Is illustrated. And in FIG. 1, the state of the decorative board with which the decorative sheet 1 was affixed on the base material B is illustrated. And the ultraviolet absorber was contained in the original fabric layer 6 by adding the above ultraviolet absorber vesicles to the original fabric layer 6.
  • Such a decorative sheet 1 is prepared by, for example, preparing an original fabric layer 6 by adding an ultraviolet absorbent vesicle containing an ultraviolet absorber in a vesicle to a resin composition constituting the original fabric layer 6.
  • the top surface of the decorative sheet 1 is provided with a topcoat layer 2 that plays a role of protecting the surface and adjusting gloss.
  • the main resin material is polyurethane, acrylic silicon, fluorine, epoxy. Resin materials such as those based on vinyl, vinyl, polyester, melamine, aminoalkyd, and urea can be appropriately selected and used.
  • the form of the resin material is not particularly limited, such as aqueous, emulsion, solvent type.
  • the curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like.
  • the top coat layer 2 is configured to be embedded in the concave portion of the embossed pattern 3a of the transparent resin layer 3, and the layer thickness is reduced by forming the embossed pattern 3a. It can be set as the decorative sheet 1 which filled the recessed part and was excellent in the designability. 1 illustrates the case where the top coat layer 2 is formed so as to cover the entire surface of the transparent resin layer 3, the top coat layer 2 is embedded only in the recesses of the embossed pattern 3a. It may be formed. When such a topcoat layer 2 is formed, it may be formed by wiping or the like by applying a topcoat resin material composition to the recesses of the embossed pattern 3a and scraping off unnecessary coating liquid with a squeegee or the like. it can.
  • urethane-based materials using isocyanate are suitable from the viewpoints of workability, cost, cohesion of the resin itself, and the like.
  • isocyanate tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI),
  • HXDI methylcyclohexanone diisocyanate
  • TMDI trimethylhexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate having a linear molecular structure is preferred.
  • a resin curable with active energy rays such as ultraviolet rays and electron beams.
  • active energy rays such as ultraviolet rays and electron beams.
  • These resins can be used in combination with each other.
  • a hybrid type of a thermosetting resin and a photocurable resin surface hardness is improved, curing shrinkage is suppressed, and a transparent resin layer is used. It is possible to improve the adhesion.
  • a transparent resin layer 3 is provided on the lower surface of the top coat layer 2.
  • the resin material used as the main component of the transparent resin layer 3 is preferably made of an olefin resin, and in addition to polypropylene, polyethylene, polybutene and the like, ⁇ -olefin (for example, propylene, 1-butene, 1-pentene, 1 -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene
  • the resin composition constituting the transparent resin layer 3 includes a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, an ultraviolet absorber, and a gloss adjustment as necessary.
  • Various functional additives such as an agent may be contained. These various functional additives are preferably selected from known ones and used.
  • an embossed pattern 3a is formed on the surface of the transparent resin layer 3 in order to improve the design.
  • the embossed pattern 3a is formed by a method of forming the embossed pattern 3a by applying heat and pressure using an embossed plate having a concavo-convex pattern before forming the topcoat layer 2, or when forming a film using an extruder.
  • the embossed pattern 3a can be formed simultaneously with the cooling of the sheet using a cooling roll having an uneven pattern. Further, it is possible to further improve the design by embedding ink or the like in the recesses of the embossed pattern 3a.
  • the adhesive resin layer 3 b When nonpolar polypropylene is used for the transparent resin layer 3, it is preferable to provide the adhesive resin layer 3 b when the adhesion between the transparent resin layer 3 and the resin layer disposed on the lower surface is low.
  • the adhesive resin layer 3b is preferably an acid-modified resin such as polypropylene, polyethylene, or acrylic resin, and the layer thickness is desirably 2 to 20 ⁇ m from the viewpoint of adhesion and heat resistance.
  • the adhesive resin layer 3b is preferably formed by coextrusion laminating with the transparent resin layer 3 from the viewpoint of improving the adhesive strength.
  • a nano-sized nucleating agent is added to the transparent resin layer 3.
  • the nano-sized nucleating agent is preferably added in the form of a nucleating agent vesicle encapsulated in a vesicle having a single-layer outer membrane.
  • the dispersibility of the nucleating agent can be improved, and aggregation of the nucleating agent can be suppressed and uniformly dispersed.
  • the crystallinity of the resin is improved, thereby suppressing light scattering due to the addition of the nucleating agent and extremely high transparency.
  • the transparent resin sheet which has can be obtained.
  • the addition of the nano-sized nucleating agent can further improve the scratch resistance and post-processability of the surface of the transparent resin sheet.
  • the nucleating agent vesicle can be prepared by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method and the like. Among them, the supercritical reverse phase evaporation method is particularly preferable.
  • Supercritical reversed-phase evaporation method is a method of producing nano-sized vesicles (capsules) encapsulating target substances using carbon dioxide under supercritical conditions, temperature conditions above the critical point or pressure conditions above the critical point. It is.
  • Carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or higher, under temperature conditions above the critical point or Carbon dioxide under pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition.
  • an emulsion of supercritical carbon dioxide and an aqueous phase is produced by injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipid, and a nucleating agent as an inclusion substance, and stirring. Thereafter, when the pressure is reduced, carbon dioxide expands and evaporates to cause phase inversion, and nanovesicles in which the surface of the nucleating agent nanoparticles are covered with a monolayer film are generated. According to this supercritical reverse phase evaporation method, since a vesicle of a single layer film can be generated, a very small size vesicle can be obtained.
  • the average particle diameter of the nucleating agent vesicle encapsulating the nano-sized nucleating agent is preferably 1 ⁇ 2 or less of the visible light wavelength (400 to 750 nm), more specifically 200 to 375 nm or less.
  • the nucleating agent vesicle is present in the resin composition in a state where the outer membrane of the vesicle is broken and the nano-sized nucleating agent is exposed.
  • the nucleating agent is not particularly limited as long as it is a substance that becomes a starting point of crystallization when the resin is crystallized.
  • the nucleating agent include phosphoric acid ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc.
  • phosphoric acid ester metal salts phosphoric acid ester metal salts
  • benzoic acid metal salts pimelic acid metal salts
  • rosin metal salts benzylidene sorbitol
  • quinacridone quinacridone
  • cyanine blue and talc cyanine blue and talc.
  • the material itself can be made transparent by nano-treatment
  • colored quinacridone, cyanine blue, talc and the like can also be used.
  • a molten benzylidene sorbitol may be appropriately mixed and used with a non-melting nucleating agent. As described above, by adding the nucleating agent vesicle, the transparency, that is, the design of the decorative sheet can be further improved while improving the post-processability.
  • an adhesive layer 4 for further improving the adhesion between the ink layer 5 on the lower surface side and the transparent resin layer 3 is provided.
  • the material of the adhesive layer 4 is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, and the like.
  • the coating method can be appropriately selected according to the viscosity of the adhesive and the like, but generally, a gravure coat is used and applied to the raw fabric layer 6 side on which the ink layer 5 has been applied. Thereafter, it is laminated with the transparent resin layer 3 or the adhesive resin layer 3b.
  • the adhesive layer 4 can be omitted when the adhesive strength between the transparent resin layer 3 and the ink layer 5 is sufficiently obtained.
  • the ink layer 5 is provided on the lower surface side of the adhesive layer 4.
  • the ink layer 5 includes a pattern pattern layer 5a having a pattern or a pattern, and a solid ink layer 5b which is located on the lower surface of the pattern pattern layer 5a and has a concealing property.
  • the pattern layer 5a is formed of ink containing at least a light stabilizer, so that a colorful pattern or pattern can be maintained over a long period of time.
  • the ink can be selected from nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester or the like, or can be appropriately selected and used.
  • the binder is not particularly limited such as aqueous, solvent-based, or emulsion-based, and the curing method may be a one-component type or a two-component type using a curing agent.
  • a general method is a method in which urethane-based ink is used and is cured by isocyanate.
  • coloring agents such as pigments and dyes, extender pigments, solvents, various additives, and the like that are included in ordinary inks are included.
  • highly versatile pigments include pearls such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.
  • the same material as the ink used for the pattern layer 5a can be used.
  • the ink is a transparent material, an opaque pigment, titanium oxide, iron oxide, or the like is used. be able to.
  • flaky aluminum is used.
  • a comma coater knife coater, lip coater, metal vapor deposition or sputtering method.
  • the surface to be laminated is subjected to corona treatment, ozone treatment, plasma treatment, electron beam in consideration of its adhesiveness before applying the resin material or ink. Adhesion between layers can be improved by performing a lamination process after activating the surface by performing surface treatment such as treatment, ultraviolet treatment, or dichromic acid treatment.
  • an original fabric layer 6 made of a resin composition containing an olefin resin as a main component is provided on the lower surface side of the ink layer 5.
  • the olefin resin used in the resin composition constituting the raw fabric layer 6 include the following (a) to (c).
  • (b) an ethylene / propylene / butene copolymer Japanese Patent Laid-Open Nos. 9-1111055 and 5) No. 077371, JP-A-7-316358)
  • C A mixture of isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment
  • (a) as the high-density polyethylene as the hard segment, a resin composition having a specific gravity of 0.94 to 0.96 and a high crystallinity obtained by the low-pressure method and having a small number of branched structures in the molecule can be mentioned. It is done. Moreover, it is preferable to use isotactic polypropylene as the polypropylene as the hard segment.
  • (A) diene rubber, hydrogenated diene rubber, olefin elastomer, and the like can be used as the elastomer as the soft segment.
  • diene rubber examples include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber.
  • a hydrogenated diene rubber is one obtained by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and suppresses crystallization of a polyolefin resin to improve flexibility.
  • the olefin elastomer is an elastic copolymer to which at least one polyene that can be copolymerized with two or three or more olefins is added.
  • olefin ethylene, propylene, ⁇ -olefin, or the like is used.
  • polyene include 1,4 hexadiene, cyclic diene, norbornene and the like.
  • olefin elastomer it is preferable to use an elastic copolymer containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber.
  • ethylene-propylene copolymer rubber ethylene-propylene-nonconjugated diene rubber
  • ethylene-butadiene copolymer rubber ethylene-butadiene copolymer rubber.
  • the amount of these elastomers added is preferably in the range of 10 to 60% by mass, more preferably 30% by mass.
  • the added amount of the elastomer is less than 10% by mass, the change in the constant excess elongation becomes steep, and the elongation at break, impact resistance, and easy adhesion are reduced.
  • the amount of the elastomer added is more than 60% by mass, transparency, weather resistance and creep resistance are lowered.
  • the inorganic filler a powder having an average particle size of about 0.1 to 10 ⁇ m, such as calcium carbonate, barium sulfate, clay, talc, and the like can be used.
  • the added amount of such an inorganic filler is preferably in the range of 1 to 60% by mass, more preferably in the range of 5 to 30% by mass. This is because when the addition amount of the inorganic filler is less than 1% by mass, the creep deformation resistance and easy adhesion are insufficient, and when the addition amount is more than 60% by mass, the elongation at break and impact resistance are high. Decreases.
  • (B) includes a thermoplastic elastomer made of a copolymer resin of ethylene, propylene and butene as a polyolefin resin.
  • a copolymer resin of ethylene, propylene and butene as a polyolefin resin.
  • the copolymer is preferably a random copolymer that partially contains an amorphous part.
  • Specific examples of the ethylene / propylene / butene copolymer resin include the following (a) to (c).
  • the ethylene / propylene / butene copolymer resins listed in the following (a) to (c) may be used in combination with other polyolefin resins as required, in addition to being used alone.
  • (A) As a first specific example, there is a random copolymer resin made of a terpolymer of ethylene, propylene and butene described in JP-A-9-1111055.
  • the mass ratio of the propylene component is preferably 90% by mass or more, and the melt flow rate (MFR) is preferably 1 to 50 g / 10 min (230 ° C., 2.16 kg).
  • MFR melt flow rate
  • 0.01 to 50 parts by mass of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound and 12 to 12 carbon atoms with respect to 100 parts by mass of the random copolymer resin. It is preferable that 0.003 to 0.3 parts by mass of 22 fatty acid amides are melt-kneaded.
  • (B) As a second specific example, there is a terpolymer resin of ethylene, propylene and butene described in JP-A-5-077371. In this ternary copolymer resin, crystalline polypropylene is added at a ratio of 80 to 0% by mass with respect to 20 to 100% by mass of the amorphous polymer having a mass ratio of the propylene component of 50% by mass or more. It will be.
  • (C) As a third specific example, there is a terpolymer resin of ethylene, propylene and 1-butene described in JP-A-7-316358.
  • propylene and / or 1 butene content is 50% by mass or more to a low crystalline polymer 20 to 100% by mass, and crystalline polyolefin 80 to 100% such as isotactic polypropylene is used.
  • the melt index as a hard segment is 0.1 to 4 g / 10 minutes boiling heptane insoluble isotactic polypropylene 90 to 10% by mass
  • the number average molecular weight Mn as a soft segment is 25000 or more
  • the molecular weight distribution An olefinic thermoplastic elastomer which is a soft polypropylene composed of a mixture of 10 to 90% by mass of atactic polypropylene soluble in boiling heptane having an MWD (Mw / Mn) of 7 or less.
  • the mass ratio of the atactic polypropylene in the mixture of the isotactic polypropylene as the hard segment and the atactic polypropylene as the soft segment is 10 to 50% by mass. In particular, 20 to 40% by mass is more preferable. This is because when the mass ratio of the atactic polypropylene is less than 10% by mass, deformation due to necking occurs when embossing is performed or when forming a three-dimensional or concavo-convex article, and the resulting raw sheet This is because wrinkles and distortion occur in the skin. On the other hand, if the mass ratio is more than 50% by mass, sufficient rigidity cannot be obtained and the material sheet is often torn during molding.
  • the ink layer 5 is deformed when the formed original sheet is passed through a printing machine and the ink layer 5 is distorted or the "registration" used for multicolor printing is not suitable due to the deformation of the original sheet. Or other defects will occur.
  • the raw fabric layer 6 of the decorative sheet 1 of the present embodiment contains the olefin resin as a main component and contains an ultraviolet absorber, but it is important that the ultraviolet absorber is added in the form of an ultraviolet absorber vesicle. It is.
  • the ultraviolet absorber vesicle contains an inorganic ultraviolet absorber, it is contained in the resin composition in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the main resin material.
  • the resin composition contains 0.1 to 10 parts by mass with respect to 100 parts by mass of the main resin material. It is preferable.
  • the ultraviolet absorber vesicle is contained in the resin composition in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the main resin material. It is substantially synonymous with the content in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the main resin material.
  • the resin composition which comprises the raw fabric layer 6 you may contain functional additives, such as a coloring agent, a heat stabilizer, a flame retardant, and a radical scavenger, as needed.
  • a functional additive a well-known material can be appropriately selected and used.
  • olefin resin as a main component, between the original fabric layer 6 and the base material which pastes the decorative sheet 1, It is preferable to provide a primer layer.
  • corona treatment in order to improve the adhesion between the raw fabric layer 6 made of a resin composition containing an olefin resin as a main component and the base material, corona treatment, plasma treatment, Ozone treatment, electron beam treatment, ultraviolet treatment or dichromic acid treatment is preferably performed.
  • the primer layer is made of an inorganic filler such as silica, alumina, magnesia, titanium oxide, or barium sulfate in order to avoid blocking and increase adhesion to the adhesive. It is preferable to contain.
  • the original fabric layer 6 is 20 ⁇ m to 150 ⁇ m
  • the ink layer 5 is 5 ⁇ m to 20 ⁇ m
  • the adhesive layer 4 is 1 ⁇ m to 20 ⁇ m
  • the transparent resin layer 3 in consideration of printing workability and cost.
  • Is preferably 20 ⁇ m to 200 ⁇ m
  • the top coat layer 2 is preferably 3 ⁇ m to 20 ⁇ m.
  • the total thickness of the decorative sheet 1 is preferably in the range of 45 ⁇ m to 410 ⁇ m.
  • the decorative sheet 1 of the present embodiment including the raw fabric layer 6 containing the ultraviolet absorbent vesicle includes the raw fabric layer 6 in which the ultraviolet absorbent is extremely uniformly dispersed in the resin composition.
  • the ultraviolet absorber generates bloom (powder spray) or bleed (liquid spray) on the surface of the original fabric layer 6.
  • unnecessary substances are not interposed between the ink layer 5 and the original fabric layer 6, so that the ink layer 5 and the original fabric layer 6 Excellent adhesion can be realized.
  • the outermost layer of the decorative sheet 1 that contacts the original fabric layer 6 is clouded by blooming powder.
  • an ultraviolet absorber is contained in the resin composition as compared with the raw fabric layer 6 produced in the same addition amount as in the past. A large amount remains and is contained, and it is possible to provide a decorative sheet 1 that exhibits high ultraviolet absorption performance and is extremely excellent in weather resistance. And if the weather resistance of the original fabric layer 6 is improved, the discoloration and cracking of the original fabric layer 6 due to oxidative degradation is suppressed, and the surface of the ink layer 5 is whitened due to the separation between the ink layer 5 and the original fabric layer 6. Since the effect of suppression can be acquired, the external appearance change of the decorative sheet 1 can be prevented.
  • the decorative sheet of this embodiment is a decorative sheet comprising a raw fabric layer made of a resin composition containing an olefin resin as a main component, and the raw fabric layer contains an ultraviolet absorber, and the ultraviolet absorber.
  • the ratio of the change of the water droplet contact angle before and after the curing is 30% or less with respect to the water droplet contact angle before curing (one day at a temperature of 60 ° C. and a humidity of 20%).
  • the ultraviolet absorber may be contained in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin material in the resin composition.
  • the UV absorber is dispersed with high dispersibility, and the water repellency of the surface of the original fabric sheet 6 is reduced without causing bleed out due to the aggregated additive. It is possible to consider it higher.
  • the water droplet contact angle before and after the curing of the original fabric sheet 6 is substantially the same value, but has a measurement error, so it is defined as 30% or less.
  • an ultraviolet absorber as an ultraviolet absorber vesicle
  • the decorative sheet 1 having higher weather resistance can be realized.
  • an ultraviolet absorber as an ultraviolet absorber vesicle it is possible to obtain the effect that the flexibility, impact strength and flatness required for the decorative sheet can be maintained.
  • an inorganic ultraviolet absorbent vesicle encapsulating an inorganic ultraviolet absorbent is used as the ultraviolet absorbent vesicle, it is possible to provide a decorative sheet 1 that realizes a stable ultraviolet absorbing performance over a long period of time.
  • the original fabric layer 6 can be colored in a desired manner, so that it is possible to provide a decorative sheet 1 having excellent design.
  • a nano-nucleating agent is added to the transparent resin layer 3. By subjecting the nucleating agent to nano-treatment, the dispersibility of the nucleating agent in the transparent resin layer 3 can be remarkably improved. This makes it possible to improve the transparency while improving the scratch resistance of the surface of the transparent resin sheet, and to improve the post-processability.
  • the preparation is carried out in a high-pressure stainless steel container kept at 60 ° C., 100 parts by mass of methanol, 82 parts by mass of zinc oxide or benzotriazole-based ultraviolet absorber (manufactured by BASF) as an ultraviolet absorber, phosphorus Filled with 5 parts by mass of phosphatidylcholine as lipid and sealed, injected carbon dioxide into a supercritical state so that the pressure in the container was 20 MPa, and injected 100 parts by mass of ion-exchanged water with vigorous stirring and mixing. After stirring and mixing for 15 minutes while maintaining temperature and pressure, zinc oxide liposomes or benzotriazole-based UV absorber liposomes having a monolayer outer membrane made of phospholipid by discharging carbon dioxide and returning to atmospheric pressure Obtained.
  • a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) is applied to one surface of the original sheet 6 as the original fabric layer 6 to provide a hindered amine-based light stability against the binder resin content of the ink.
  • a pattern printing layer 5a is provided by printing with a gravure printing method using an ink to which 0.5% by mass of an agent (Kimasorb 944; manufactured by BASF) is added, and the other surface of the raw fabric layer 6 is provided. Primer coating was applied.
  • the transparent resin layer 3 is placed on the upper surface of the pattern layer 5a formed on the original fabric layer 6 through an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m 2 ). And bonded together by a dry laminating method.
  • embossed pattern 3a is applied to the surface of transparent resin layer 3 of the bonded sheet, a two-component urethane topcoat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 3 g / m 2 to perform wiping.
  • the top coat layer 2 was formed in the recesses of the embossed pattern 3a.
  • a decorative sheet 1 having a total thickness of 155 ⁇ m and the same layer structure as that of FIG. 1 was obtained. And the structure of this decorative sheet was made into the basic structure of each Example and comparative example demonstrated below.
  • Example 1 the zinc oxide liposome prepared by the above-described method is contained in the resin composition at a ratio of 0.2 part by mass with respect to 100 parts by mass of the resin material as the main component of the resin composition.
  • a sheet 6 was produced, and a decorative sheet 1 was produced using the original fabric sheet 6 as an original fabric layer 6.
  • a random polypropylene resin as a main component resin material
  • 0.05 part by mass of a hindered phenol-based antioxidant Irganox 1010; manufactured by BASF
  • hindered amine-based light stabilization A resin prepared by adding 0.2 parts by mass of an agent (Kimasorb 944; manufactured by BASF) and 0.2 parts by mass of zinc oxide liposomes as a raw sheet 6 having a thickness of 60 ⁇ m using a melt extruder What was done was used.
  • Example 2 the benzotriazole-based ultraviolet absorbent liposome prepared by the above-described method is contained in the resin composition at a ratio of 0.2 part by mass with respect to 100 parts by mass of the resin material as the main component of the resin composition.
  • An original sheet 6 was prepared, and a decorative sheet 1 was prepared using the original sheet 6 as an original layer 6.
  • the content of other functional additives and the film forming method are the same as in Example 1.
  • Comparative Example 1 zinc oxide as an inorganic ultraviolet absorber that has not been vesicled is contained in the resin composition in a proportion of 0.2 part by mass with respect to 100 parts by mass of the resin material as the main component of the resin composition.
  • An original sheet 6 was prepared, and a decorative sheet 1 was prepared using the original sheet 6 as an original layer 6.
  • the content of other functional additives and the film forming method are the same as in Example 1.
  • Comparative Example 2 Nano zinc oxide as an inorganic ultraviolet absorber that has been nano-processed by a solid phase method is added to the resin composition in an amount of 0.000 to 100 parts by mass of the resin material as the main component of the resin composition.
  • Nano-zinc oxide is obtained by subjecting 100 g of isopropyl alcohol and 50 g of zinc oxide to nano-treatment for 60 minutes in a bead mill using 30 ⁇ m stabilized zirconia beads, resulting in zinc oxide nanoparticles having an average particle size of about 1 to 150 nm. Got as.
  • the content of other functional additives and the film forming method are the same as in Example 1.
  • a benzotriazole ultraviolet absorber manufactured by BASF
  • an organic ultraviolet absorber is 0.2 mass relative to 100 mass parts of the resin material as the main component of the resin composition in the resin composition.
  • the raw fabric sheet 6 contained at a ratio of parts was prepared, and the decorative sheet 1 was prepared using the original fabric sheet 6 as the original fabric layer 6.
  • the content of other functional additives and the film forming method are the same as in Example 1.
  • each decorative sheet 1 of Examples 1 and 2 and Comparative Examples 1 to 3 was transparent using a tensile property tester (AGS-X; Shimadzu Corporation).
  • a 90 ° peel test JIS0237 was performed between the resin layer 3 and the original fabric layer 6. The test conditions were a tensile rate of 50 mm / s and the peel strength was evaluated. The obtained results are shown in Table 1.
  • the decorative sheets 1 in Examples 1 and 2 in the visual observation from the surface side of the top coat layer 2 after the super accelerated weather resistance test, the color change and cracks of the raw fabric layer 6 were recognized. I could't. Whitening of the ink layer 5 due to peeling between the original fabric layer 6 and the ink layer 5 was not observed.
  • the decorative sheets 1 in Comparative Examples 1 to 3 have cracks in the raw fabric layer 6 and whitening of the ink layer 5 in visual observation from the surface side of the topcoat layer 2 after the super accelerated weathering test. Admitted.
  • the ultraviolet absorbent is aggregated when the ultraviolet absorbent is added in a vesicle state to the original fabric sheet 6 used as the original fabric layer 6.
  • the bloom (powder spraying) generated by the aggregation of the ultraviolet absorber is suppressed, so that the content of the ultraviolet absorber in the resin composition does not decrease and a large amount in the resin composition.
  • the original fabric layer 6 did not undergo oxidative deterioration by maintaining an excellent ultraviolet absorption performance by the ultraviolet absorber present in the film, and maintained good design properties.
  • no bloom (powder spraying) occurring on the surface of the original fabric layer 6 it was considered that excellent adhesion between the original fabric layer 6 and the ink layer 5 was realized, and whitening of the ink layer 5 was prevented.
  • the decorative sheets 1 in Examples 1 and 2 showed higher values in the peel strength test than the decorative sheets 1 in Comparative Examples 1 to 3, and the transparent resin layer 3 It was revealed that the adhesion between the film and the original fabric layer 6 was excellent.
  • the original fabric sheet 6 used as the original fabric layer 6 in Examples 1 and 2 is made of a resin composition to which an ultraviolet absorber is added in the state of a vesicle, and on the transparent resin layer 3 side of the original fabric sheet 6 This is considered to be because the surface of the transparent resin layer 3 and the surface 6a of the original fabric sheet 6 are in close contact with each other because the ultraviolet absorber that bleeds out from the surface 6a is extremely small.
  • the ratio of the change in the water droplet contact angle before and after curing with respect to the water droplet contact angle before curing is as small as 16.1% in Example 1 and 12.6% in Example 2.
  • the ratio of the change of the water droplet contact angle before and after curing with respect to the water droplet contact angle before curing is suppressed to 30% or less, but a comparative example outside the present invention.
  • the rate of change of the water droplet contact angle before and after curing was 70% or more.
  • the ultraviolet absorber is uniformly dispersed in the resin composition, and the aggregated addition It was found that the water repellency of the surface of the original sheet 6 was maintained high without causing bleed out due to the agent.
  • the decorative sheet 1 in Examples 1 and 2 is provided with the original fabric layer 6 containing an ultraviolet absorber vesicle and causing less bleed out, so that the transparent resin of the decorative sheet 1 in the original fabric layer 6 is obtained.
  • the transparent resin of the decorative sheet 1 in the original fabric layer 6 is obtained.
  • On the surface 6a on the layer 3 side excellent adhesion to the transparent resin layer 3 or the ink layer 5 is realized, and on the surface 6b on the base material B side of the decorative sheet 1 in the raw fabric layer 6, it is in a rolled state.
  • the outermost layer of the decorative sheet 1 in contact with the original fabric layer 6 is clouded and the design properties are not impaired, and the problem of stickiness due to the bleed liquid does not occur. Excellent adhesion can be achieved.
  • the decorative sheets 1 of Examples 1 and 2 having such an original fabric layer 6 are decorative sheets having excellent weather resistance as compared with the decorative sheets of Comparative Examples 1 to 3 as conventional decorative sheets. It became clear that there was.

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  • Laminated Bodies (AREA)

Abstract

La présente invention vise à fournir une feuille cosmétique dans laquelle, même lorsqu'une couche de tissu brut contient un absorbeur d'UV, l'agrégation de l'absorbeur d'UV est inhibée, ce qui permet d'assurer une excellente adhérence entre la couche de tissu brut et une autre couche de résine, une excellente résistance aux intempéries étant présentée par la feuille cosmétique. Cette feuille cosmétique (1) comporte une couche de tissu brut (6) comprenant une composition de résine ayant une résine d'oléfine comme constituant principal. La couche de tissu brut (6) comporte un absorbeur d'UV. L'absorbeur d'UV est ajouté à la composition de résine constituant la couche de tissu brut (6) en tant que vésicules d'absorption d'UV dans lesquelles l'absorbeur d'UV est enfermé dans des vésicules.
PCT/JP2017/004928 2016-02-12 2017-02-10 Feuille cosmétique et son procédé de fabrication WO2017138635A1 (fr)

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JP2020062775A (ja) * 2018-10-16 2020-04-23 凸版印刷株式会社 エンボス化粧シート

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JP2007100045A (ja) * 2005-10-07 2007-04-19 Masamitsu Nagahama ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用
JP2008062416A (ja) * 2006-09-05 2008-03-21 Toppan Printing Co Ltd 化粧シート
JP2008080601A (ja) * 2006-09-27 2008-04-10 Dainippon Printing Co Ltd 化粧シート及びその製造方法
JP2013008825A (ja) * 2011-06-24 2013-01-10 Mitsubishi Rayon Co Ltd ナノ凹凸構造用樹脂組成物、およびそれを用いた自動車メータカバー用透明部材とカーナビゲーション用透明部材
JP2014037124A (ja) * 2012-08-20 2014-02-27 C I Kasei Co Ltd 成形品の製造方法
JP2016117280A (ja) * 2014-12-19 2016-06-30 凸版印刷株式会社 化粧シート

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JPH1067081A (ja) * 1996-04-08 1998-03-10 Tokuyama Corp 化粧シート
JPH11207876A (ja) * 1998-01-29 1999-08-03 Dainippon Printing Co Ltd 化粧シート
JPH11235804A (ja) * 1998-02-23 1999-08-31 Dainippon Printing Co Ltd 化粧シート
JP2011089101A (ja) * 2009-09-26 2011-05-06 Ko Tamihiro 吸湿性樹脂ペレット

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JP2007100045A (ja) * 2005-10-07 2007-04-19 Masamitsu Nagahama ポリオレフィン樹脂製品、ポリオレフィン樹脂製品の製造方法、粒状物の使用
JP2008062416A (ja) * 2006-09-05 2008-03-21 Toppan Printing Co Ltd 化粧シート
JP2008080601A (ja) * 2006-09-27 2008-04-10 Dainippon Printing Co Ltd 化粧シート及びその製造方法
JP2013008825A (ja) * 2011-06-24 2013-01-10 Mitsubishi Rayon Co Ltd ナノ凹凸構造用樹脂組成物、およびそれを用いた自動車メータカバー用透明部材とカーナビゲーション用透明部材
JP2014037124A (ja) * 2012-08-20 2014-02-27 C I Kasei Co Ltd 成形品の製造方法
JP2016117280A (ja) * 2014-12-19 2016-06-30 凸版印刷株式会社 化粧シート

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