WO2017209240A1 - Feuille décorative et son procédé de fabrication - Google Patents

Feuille décorative et son procédé de fabrication Download PDF

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Publication number
WO2017209240A1
WO2017209240A1 PCT/JP2017/020431 JP2017020431W WO2017209240A1 WO 2017209240 A1 WO2017209240 A1 WO 2017209240A1 JP 2017020431 W JP2017020431 W JP 2017020431W WO 2017209240 A1 WO2017209240 A1 WO 2017209240A1
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WIPO (PCT)
Prior art keywords
transparent resin
decorative sheet
resin layer
intensity ratio
nucleating agent
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PCT/JP2017/020431
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English (en)
Japanese (ja)
Inventor
恵 柏女
真志 服部
達彦 古田
宮本　慎一
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 WO2017209240A1 publication Critical patent/WO2017209240A1/fr

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Classifications

    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a decorative sheet used for a building material used for an exterior or interior of a building, a surface of a fitting, a surface material of a home appliance, and a method for manufacturing the decorative sheet.
  • Patent Documents 1 to 5 many decorative sheets using olefin-based resins have been proposed as decorative sheets that replace polyvinyl chloride decorative sheets. These decorative sheets can suppress the generation of toxic gases during incineration by not using polyvinyl chloride.
  • the decorative sheets described in Patent Documents 1 to 5 use general polypropylene sheets or soft polypropylene sheets, they have poor scratch resistance, which is far greater than the scratch resistance of polyvinyl chloride decorative sheets. It was inferior.
  • Japanese Patent Laid-Open No. 2-128843 Japanese Patent Laid-Open No. 4-083664 JP-A-6-001881 JP-A-6-198831 JP-A-9-328562 Japanese Patent No. 3772634
  • a decorative sheet is a decorative sheet having a transparent resin layer containing an olefin resin, and is a transparent resin measured by Raman spectroscopy in the MD direction of the transparent resin layer.
  • a transparent resin having a first intensity ratio which is a spectral intensity ratio between a crystal part and an amorphous part of a layer, in a range of 0.9 or more and 2.0 or less and measured by Raman spectroscopy in the TD direction of the transparent resin layer
  • the second intensity ratio which is the spectral intensity ratio between the crystal part and the amorphous part of the layer, is in the range of 0.9 to 1.9, and the total value of the first intensity ratio and the second intensity ratio is 1. It is in the range of 9 or more and 3.6 or less.
  • the hardness of the transparent resin layer can be made appropriate, and a decorative sheet excellent in scratch resistance and post-processability can be provided.
  • the decorative sheet 1 of the present embodiment has a pattern layer 5, a transparent resin layer 3, and a surface protective layer 2 laminated in this order on one surface of a base material layer 6.
  • Reference numeral 4 denotes an adhesive layer.
  • the concealing layer 7 and the primer layer 8 are formed in this order on the other surface of the base material layer 6.
  • the masking layer 7 may be formed between the base material layer 6 and the pattern layer 5 or may be omitted.
  • the decorative sheet 1 of this embodiment has illustrated the case where the embossed pattern 3a is formed between the surface protective layer 2 and the transparent resin layer 3.
  • FIG. Note that the embossed pattern 3 a may be formed on the upper surface of the surface protective layer 2.
  • “the upper surface of the surface protective layer 2” means the outermost surface of the decorative sheet 1 of the present embodiment, and means the surface of the surface protective layer 2 opposite to the surface on the transparent resin layer 3 side.
  • the layer thickness of the decorative sheet 1 having the above-described configuration is, for example, 3 ⁇ m or more and 20 ⁇ m or less for the surface protective layer 2, 20 ⁇ m or more and 200 ⁇ m or less for the transparent resin layer 3, and the adhesive layer 4 in consideration of printing workability and cost. Is in the range of 1 ⁇ m to 20 ⁇ m.
  • the pattern layer 5 is 3 ⁇ m to 20 ⁇ m
  • the base layer 6 is 20 ⁇ m to 150 ⁇ m
  • the masking layer 7 is 2 ⁇ m to 20 ⁇ m
  • the primer layer 8 is 0.1 ⁇ m to 20 ⁇ m.
  • the total thickness of the decorative sheet 1 shall be in the range of 49.1 micrometers or more and 450 micrometers or less.
  • FIG. 1 the case where the decorative sheet 1 of this embodiment is affixed on the base material B and the decorative board is comprised is illustrated.
  • the base material layer 6 is comprised from paper, a resin sheet, foil, etc.
  • the paper for example, thin paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabric, and synthetic paper can be used.
  • Examples of the resin of the resin sheet include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, foams of these synthetic resins, ethylene- Rubbers such as propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane can be used.
  • metal foil such as aluminum, iron, gold
  • the pattern pattern layer 5 is a layer for applying a pattern pattern to the decorative sheet 1.
  • a gravure printing method is preferable in consideration of productivity and picture quality.
  • the design pattern it is sufficient to adopt an arbitrary design pattern in consideration of the place of use such as flooring or wall material, and various wood grain is often used if it is a wood-based design. It can also be a pattern. For example, if it is an image of a stone floor such as marble, marble stones can be used as a pattern.
  • an artificial pattern such as an artificial pattern or a geometric pattern using these as a motif can also be used.
  • the printing ink is not particularly limited, and an ink corresponding to the printing method can be appropriately selected. In particular, it is preferable to select in consideration of adhesion to the base material layer 6, printability, weather resistance of the decorative material, and the like.
  • colorants such as pigments and dyes, extender pigments, solvents, and binders contained in ordinary inks are added to the printing ink.
  • the pigment for example, pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica can be used.
  • the binder may be, for example, water-based, solvent-based, or emulsion type
  • the curing method is a one-component type, a two-component type composed of a main agent and a curing agent, or a type that is cured by ultraviolet rays, electron beams, or the like.
  • the most general method is a two-component type, which uses a urethane-based main agent and a curing agent made of isocyanate.
  • the design may be applied by vapor deposition or sputtering of various metals.
  • the adhesive layer 4 is a layer for strengthening the adhesion between the base material layer 6 and the pattern layer 5 and the transparent resin layer 3. Thereby, the bending workability which follows a curved surface or a right-angled surface can be provided with respect to the decorative sheet 1.
  • the adhesive layer 4 is preferably transparent.
  • As the adhesive (material) constituting the adhesive layer 4 for example, acrylic, polyester, polyurethane, and epoxy materials can be used.
  • urethane-based material that is a two-component curing type and is obtained by a reaction with a polyol using an isocyanate.
  • the transparent resin layer 3 is a layer for improving the weather resistance and wear resistance of the decorative sheet 1 in addition to providing the decorative sheet 1 with a thickness and depth in a design manner.
  • a transparent olefin resin polyolefin resin
  • the transparent olefin resin include ⁇ -olefin (eg, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene) in addition to polypropylene, polyethylene, polybutene and the like.
  • the olefin resin preferably contains a crystalline polypropylene resin.
  • the crystalline polypropylene resin is contained in an amount of 50% by mass to 100% by mass with respect to the total mass of the transparent resin layer 3.
  • the transparent resin layer 3 can be hardened enough and scratch resistance can be improved.
  • the crystalline polypropylene resin it is more preferable to use a crystalline polypropylene resin that is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more.
  • the transparent resin layer 3 may be added with a nano-sized nucleating agent, that is, a nano-sized nucleating agent, with respect to the olefin resin.
  • a nano-sized nucleating agent that is, a nano-sized nucleating agent
  • the nano-sized nucleating agent is preferably added in the form of a nucleating agent encapsulated in vesicles (hereinafter also referred to as “nucleating agent vesicle”).
  • the nucleating agent vesicle can be prepared by, for example, 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.
  • the supercritical reverse phase evaporation method is particularly preferable in consideration of further improvement in dispersibility of the nucleating agent.
  • 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 a 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 aqueous phase is produced by injecting and stirring the aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipid, and nucleating agent as an inclusion substance. . 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.
  • 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.
  • Japanese Patent Laid-Open No. 2002-032564, Japanese Patent Laid-Open No. 2003-119120, Japanese Patent Laid-Open No. 2005-298407 have been proposed by the present inventors in the past. And Japanese Patent Application Laid-Open No. 2008-063274.
  • 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 nm or more and 750 nm or less). Considering suppression of light scattering, it is particularly preferable that the thickness be 200 nm or more and 375 nm or less.
  • the nucleating agent vesicle is also present in the resin composition even when the outer membrane of the vesicle is broken and the 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.
  • a phosphoric acid ester metal salt, a benzoic acid metal salt, a pimelic acid metal salt, a rosin metal salt, benzylidene sorbitol, quinacridone, cyanine blue and talc can be used.
  • the material itself can be made transparent by nano-treatment
  • colored quinacridone, cyanine blue, talc and the like can be used.
  • molten benzylidene sorbitol may be appropriately mixed with the non-melting nucleating agent.
  • the said nucleating agent is contained within 0.01 mass part or more and 1.0 mass part or less with respect to 100 mass parts of crystalline polypropylene resin which forms the transparent resin layer 3. FIG. When the content of the nucleating agent is within the above range, the transparency, scratch resistance and post-processability of the transparent resin layer 3 are further enhanced.
  • the transparent resin layer 3 has various existing heat stabilizers, ultraviolet absorbers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusting agents as required. Additives may be added.
  • the method for laminating the transparent resin layer 3 is not particularly limited, and for example, a method applying hot pressure, an extrusion laminating method, a dry laminating method, or the like can be appropriately selected.
  • embossing pattern 3a when embossing pattern 3a is applied, for example, a method in which embossed pattern 3a is later laminated by hot pressure on a sheet once laminated by various methods, or an uneven pattern is provided on a cooling roll, and embossed pattern 3a is provided simultaneously with extrusion lamination.
  • the embossing method is not particularly limited, and a known single-wafer or rotary embossing machine can be appropriately selected.
  • Examples of the concavo-convex shape may include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain texture, a hairline, and a striated groove.
  • the spectral intensity ratio between the crystal part and the amorphous part of the transparent resin layer 3 measured by Raman spectroscopy in the MD direction of the transparent resin layer 3, that is, the flow direction when forming the transparent resin layer 3 (hereinafter, (Also referred to as “first intensity ratio”) is in the range of 0.9 to 2.0.
  • the spectral intensity ratio between the crystal part and the amorphous part the spectral intensity of the crystal part / the spectral intensity of the amorphous part is adopted.
  • the intensity ratio is also in the range of 0.9 to 1.9.
  • the total value of the first intensity ratio and the second intensity ratio is set in the range of 1.9 to 3.6.
  • the peak of the crystal part is observed at 809 cm ⁇ 1 in the spectrum measurement by Raman spectroscopy, as shown in FIG. A peak is observed at 842 cm ⁇ 1 .
  • a small peak of an amorphous part may be observed at 839 cm ⁇ 1 . Therefore, the peak intensity I 809 of the crystal part and the peak intensity (I 839 + I 842 ) of the amorphous part are measured in each of the MD direction and the TD direction, and the ratio I 809 / (I 839 + I 842 ) of the measurement results.
  • the first intensity ratio and the second intensity ratio can be obtained.
  • the “peak intensity” corresponds to the “spectrum intensity” of the present application.
  • the spectral intensity ratio can be kept within the above range by controlling the temperature history at the time of film formation. Specific examples of the temperature history for setting the spectral intensity ratio within the above range are based on an extrusion film forming method using a T-die. When the polypropylene resin melted at 230 ° C. is discharged from the T die, the degree of crystallization can be controlled by the cooling profile gradient of the temperature of the cooling roll immediately below the T die and the resin temperature due to contact with the molten resin.
  • the cooling profile becomes steeper as the temperature difference between the cooling roll and the molten resin increases, and the degree of crystallinity decreases.
  • 45 ° C. to 80 ° C. is suitable as the cooling roll temperature setting for setting the spectral intensity ratio within the above range.
  • the decorative sheet according to the present embodiment based on the present invention includes a transparent resin layer 3 mainly composed of an olefin resin such as a crystalline polypropylene resin, and the transparent resin layer 3 contains a nano-sized nucleating agent.
  • the transparent resin layer 3 has one feature in that it contains a nano-sized nucleating agent (nucleating agent vesicle) encapsulated in a vesicle.
  • the transparent resin layer contains a nano-sized nucleating agent”.
  • the nucleating agent added to the resin composition (olefin-based resin) in a state where the nucleating agent is encapsulated in the vesicle, the dispersibility of the nucleating agent in the resin material, that is, in the transparent resin layer is dramatically improved.
  • the nucleating agent added in the state of vesicle is in a dispersed state having high dispersibility, and the nucleating agent is highly dispersed in the transparent resin layer even in the state of the produced decorative sheet.
  • the decorative sheet is usually produced by a compression treatment or curing to the laminate.
  • Various treatments such as treatment are performed, but by such treatment, the outer membrane of the vesicle encapsulating the nucleating agent is crushed or chemically reacted, and the nucleating agent is not included (encapsulated) in the outer membrane.
  • the present invention is different from the conventional one in that the nucleating agent is blended in a highly dispersed state, whether or not it is because it is added in the state of a vesicle encapsulating the nucleating agent is a cosmetic. In the state of the sheet, it may be impractical to specify the structure and characteristics within the numerical range analyzed based on the measurement.
  • the surface protective layer 2 is a layer for protecting the surface of the decorative sheet 1 and adjusting the gloss.
  • the material of the surface protective layer 2 for example, polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, and urea materials can be used.
  • the form of the material may be any of aqueous, emulsion and solvent type.
  • a curing method for example, a one-component type, a two-component type, an ultraviolet curing method, or the like can be used.
  • a urethane-based resin using isocyanate is preferable from the viewpoints of workability, cost, cohesion of the resin itself, and the like.
  • the isocyanate include 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
  • HXDI Methylcyclohexanone diisocyanate
  • TMDI trimethylhexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • the concealment layer 7 is a layer for maintaining concealability. For example, it is formed by printing in the same manner as the picture pattern layer 5.
  • the pigment to be included in the ink it is preferable to use an opaque pigment, titanium oxide, iron oxide or the like.
  • a metal such as gold, silver, copper, and aluminum may be added. In general, flaky aluminum is often added.
  • the masking layer 7 can be omitted when the base material layer 6 is opaque and has masking properties.
  • the primer layer 8 is a layer for improving adhesion with the base material B.
  • the resin constituting the primer layer 8 is an ester resin, a urethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride-vinyl acetate copolymer, Polyvinyl butyral resin and nitrocellulose resin can be used. These resins can be used alone or mixed to form an adhesive composition, and the primer layer 8 can be formed by using an appropriate application means such as a roll coating method or a gravure printing method.
  • a resin (urethane-acrylate resin) comprising a copolymer of an acrylic resin and a urethane resin and an isocyanate.
  • the decorative sheet 1 of this embodiment has the transparent resin layer 3 containing an olefin resin.
  • the 1st intensity ratio which is the spectral intensity ratio of the crystal part of the transparent resin layer 3 of the transparent resin layer 3 measured by the Raman spectroscopy in MD direction of the transparent resin layer 3, and an amorphous part is 0.9 or more and 2.0 or less range Is within.
  • the second intensity ratio which is the spectral intensity ratio between the crystal part and the amorphous part of the transparent resin layer 3 measured by Raman spectroscopy in the TD direction of the transparent resin layer 3, is in the range of 0.9 to 1.9. Is within.
  • the total value of the first intensity ratio and the second intensity ratio is in the range of 1.9 to 3.6.
  • the transparent resin layer 3 contains crystalline polypropylene resin in the range of 50 mass% or more and 100 mass% or less, the ratio of crystalline polypropylene resin is made high. Since the transparent resin layer 3 can be sufficiently hardened, scratch resistance can be improved.
  • the crystalline polypropylene resin is a crystalline polypropylene resin having an isotactic pentad fraction of 95% or more, the stereoregularity of the crystalline polypropylene resin is improved. The scratch resistance and post-workability can be further improved.
  • the transparent resin layer 3 since the transparent resin layer 3 was made to contain a nanosized nucleating agent, the scattering of the light which arises by addition of a nucleating agent can be suppressed, and the transparent resin layer 3 Scratch resistance and post-processability can be further improved without impairing the transparency of the film.
  • the transparent resin layer 3 since the transparent resin layer 3 is formed by adding a nano-sized nucleating agent to an olefin resin, light scattering caused by the addition of the nucleating agent is performed. Scratch resistance and post-processability can be further improved without impairing the transparency of the transparent resin layer 3.
  • the nano-sized nucleating agent is included in the vesicle, the dispersibility of the nano-sized nucleating agent can be improved, and the transparent resin layer 3 is configured. In the resin, aggregation of the nucleating agent can be suppressed and uniformly dispersed, and transparency can be further improved.
  • the nano-sized nucleating agent is encapsulated in the vesicle by the supercritical reverse phase evaporation method, so that the dispersibility of the nucleating agent is more appropriately improved.
  • the transparent resin layer 3 is 0.01 mass part or more and 1.0 mass part or less of nanosize nucleating agent with respect to 100 mass parts of olefin resin. Since it contains within the range, scratch resistance and post-processability can be further improved. (9) Moreover, in the manufacturing method of the decorative sheet 1 of this embodiment, since the transparent resin layer 3 is formed by adding a nano-sized nucleating agent to an olefin-based resin, light generated by the addition of the nucleating agent is formed. Scattering can be suppressed, and scratch resistance and post-workability can be further improved without impairing the transparency of the transparent resin layer 3.
  • the nano-sized nucleating agent is added to the olefin resin in a state in which the vesicle is encapsulated, the dispersibility of the nano-sized nucleating agent is improved. It is possible to suppress the aggregation of the nucleating agent in the resin constituting the transparent resin layer 3 and uniformly disperse it, and the transparency can be further improved.
  • the nano-sized nucleating agent is vesicled by the supercritical reverse phase evaporation method, so that the dispersibility of the nucleating agent is more appropriately improved. Can do.
  • Example 1 a crystalline polypropylene resin having an isotactic pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3 (Crystalline homopolypropylene resin) Hindered phenol antioxidant (Irganox 1010: manufactured by BASF) 500PPM and benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) with respect to 100% by mass of resin.
  • MFR melting rate
  • MWD molecular weight distribution MWD
  • Hindered phenol antioxidant Irganox 1010: manufactured by BASF
  • benzotriazole ultraviolet absorber Tinuvin 328: manufactured by BASF
  • Both surfaces of the formed transparent resin layer 3 were subjected to corona treatment, and the wet tension of the transparent resin sheet surface was set to 40 dyn / cm or more. Further, a 70 ⁇ m polyethylene sheet having a concealing property was used as the base material layer 6.
  • a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) is used to stabilize the hindered amine based on the total mass of the binder resin of the two-component ink.
  • the pattern layer 5 was formed by performing pattern printing using an ink provided by adding 0.5% by mass of an agent (Kimasorb 944; manufactured by BASF). A gravure printing method was used as a printing method for the pattern layer 5.
  • a concealing layer 7 and a primer layer 8 were formed on the other surface of the base material layer 6.
  • the transparent resin layer 3 is pasted on the upper surface of the pattern layer 5 via the adhesive layer 4 made of an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m 2 ). Combined.
  • an adhesive for dry lamination Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m 2 .
  • a dry lamination method was used.
  • the embossed pattern 3a is applied to the upper surface of the bonded transparent resin layer 3, and then a two-component curable urethane topcoat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 6 g / m 2.
  • a protective layer 2 was formed. Thereby, the decorative sheet 1 having a total thickness of 170 ⁇ m was formed.
  • the “upper surface of the pattern layer 5” means a surface opposite to the surface of the pattern layer 5 on the base material layer 6 side.
  • the “upper surface of the transparent resin layer 3” means a surface opposite to the surface of the transparent resin layer 3 on the adhesive layer 4 side.
  • Example 1 as shown in Table 1, the spectral intensity ratio (first intensity ratio) between the crystal part and the amorphous part of the transparent resin layer 3 measured by the Raman spectroscopy in the MD direction of the transparent resin layer 3 is expressed as follows. 2.0. The spectral intensity ratio (second intensity ratio) between the crystal part and the amorphous part of the transparent resin layer 3 measured by Raman spectroscopy in the TD direction was set to 1.5. The total sum of the first intensity ratio and the second intensity ratio was 3.5. Note that no nucleating agent was added to the transparent resin layer 3.
  • Example 1 the spectral intensity ratio (first intensity ratio) in the MD direction of the transparent resin layer 3 and the spectral intensity ratio (second intensity ratio) in the TD direction are expressed as follows using Raman spectroscopy.
  • the measurement equipment, measurement conditions, and sample setting method were used.
  • Sample installation method Sample is installed so that the MD direction and TD direction of the transparent resin layer 3 coincide with the laser emission direction.
  • Example 2 In Example 2, the first intensity ratio was 1.9, the second intensity ratio was 1.3, and the sum of these intensity ratios was 3.2. Otherwise, the configuration was the same as in Example 1. (Example 3) In Example 3, the first intensity ratio was 1.9, the second intensity ratio was 1.0, and the sum of these intensity ratios was 2.9. Otherwise, the configuration was the same as in Example 1.
  • Example 4 In Example 4, the first intensity ratio was 1.4, the second intensity ratio was 1.8, and the sum of these intensity ratios was 3.2. Otherwise, the configuration was the same as in Example 1. (Example 5) In Example 5, the first intensity ratio was 1.4, the second intensity ratio was 1.4, and the sum of these intensity ratios was 2.8. Otherwise, the configuration was the same as in Example 1.
  • Example 6 In Example 6, the first intensity ratio was 1.4, the second intensity ratio was 1.0, and the sum of these intensity ratios was 2.4. Otherwise, the configuration was the same as in Example 1. (Example 7) In Example 7, the first intensity ratio was 1.0, the second intensity ratio was 1.4, and the sum of these intensity ratios was 2.4. Otherwise, the configuration was the same as in Example 1.
  • Example 8 In Example 8, the first intensity ratio was 1.0, the second intensity ratio was 1.0, and the sum of these intensity ratios was 2.0. Otherwise, the configuration was the same as in Example 1.
  • Example 9 In Example 9, the first intensity ratio was 1.9, the second intensity ratio was 1.3, and the sum of these intensity ratios was 3.2. Further, it contains an untreated nucleating agent, that is, a nucleating agent that has not been subjected to either nano-treatment or vesicle formation. Otherwise, the configuration was the same as in Example 1.
  • Example 10 In Example 10, the transparent resin layer 3 contained 50% by mass of the crystalline polypropylene resin and 50% by mass of the random polypropylene resin with respect to the total mass of the transparent resin layer 3. Otherwise, the configuration was the same as in Example 8.
  • Example 11 In Example 11, the transparent resin layer 3 contained 90% by mass of crystalline polypropylene resin and 10% by mass of random polypropylene resin with respect to the total mass of the transparent resin layer 3.
  • the crystalline polypropylene resin contains a nano-sized nucleating agent. Otherwise, the configuration was the same as in Example 2.
  • Example 12 the nano-sized nucleating agent was vesicled by the supercritical reverse phase evaporation method and included in the vesicle. Otherwise, the configuration was the same as in Example 11.
  • a phosphate ester metal salt nucleating agent (Adeka Stub NA-11, manufactured by ADEKA) as a nucleating agent, After putting 5 parts by mass of phosphatidylcholine as a substance constituting the outer membrane in a high-pressure stainless steel container kept at 60 ° C.
  • nucleating agent liposome A nucleating agent for a vesicle having a monolayer outer membrane made of phospholipid by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure.
  • a vesicle-containing nucleating agent (nucleating agent liposome) was obtained.
  • a crystalline polypropylene resin having an isotactic pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3.
  • Example 13 In Example 13, the first intensity ratio was 1.8, the second intensity ratio was 1.1, and the sum of these intensity ratios was 2.9. Further, the transparent resin layer 3 contained 40% by mass ( ⁇ 50% by mass) of the crystalline polypropylene resin and 60% by mass of the random polypropylene resin with respect to the total mass of the transparent resin layer 3. Otherwise, the configuration was the same as in Example 1. (Example 14) In Example 14, the first intensity ratio was 1.3, the second intensity ratio was 1.2, and the sum of these intensity ratios was 2.5. In addition, the transparent resin layer 3 had an isotactic pentad fraction of 92% ( ⁇ 95%). Otherwise, the configuration was the same as in Example 1.
  • Example 1 In Comparative Example 1, the first intensity ratio was 2.1, the second intensity ratio was 2.0, and the sum of these intensity ratios was 4.1 (> 3.6). Otherwise, the configuration was the same as in Example 1.
  • Comparative Example 2 In Comparative Example 2, the first intensity ratio was 2.1, the second intensity ratio was 1.7, and the sum of these intensity ratios was 3.8 (> 3.6). Otherwise, the configuration was the same as in Example 1.
  • Example 3 In Comparative Example 3, the first intensity ratio was 1.9, the second intensity ratio was 1.9, and the sum of these intensity ratios was 3.8 (> 3.6). Otherwise, the configuration was the same as in Example 1.
  • Comparative Example 4 In Comparative Example 4, the first intensity ratio was 0.9, the second intensity ratio was 0.9, and the sum of these intensity ratios was 1.8 ( ⁇ 1.9). Otherwise, the configuration was the same as in Example 1.
  • Comparative Example 5 In Comparative Example 5, the first intensity ratio was 0.9, the second intensity ratio was 0.8, and the sum of these intensity ratios was 1.7 ( ⁇ 1.9). Otherwise, the configuration was the same as in Example 1.
  • Comparative Example 6 In Comparative Example 6, the first intensity ratio was 0.8, the second intensity ratio was 0.7, and the sum of these intensity ratios was 1.5 ( ⁇ 1.9). Further, the transparent resin layer 3 contained 40% by mass ( ⁇ 50% by mass) of the crystalline polypropylene resin and 60% by mass of the random polypropylene resin with respect to the total mass of the transparent resin layer 3. Otherwise, the configuration was the same as in Example 1.
  • Example 7 In Comparative Example 7, the first intensity ratio was 1.2, the second intensity ratio was 2.3, and the sum of these intensity ratios was 3.5. Otherwise, the configuration was the same as in Example 1.
  • Comparative Example 8 In Comparative Example 8, the first intensity ratio was 2.4, the second intensity ratio was 1.1, and the sum of these intensity ratios was 3.5. Otherwise, the configuration was the same as in Example 1.
  • the scratch resistance was evaluated using a pencil hardness test in accordance with JIS-K5600.
  • the maximum hardness of the transparent resin layer 3 with no dent is HB or more, “ ⁇ ”, when it is 2B or more, “ ⁇ ”, when it is 3B or more, “ ⁇ ”, when it is less than 3B, “ ⁇ ” "
  • the acceptance criteria in this scratch resistance test is 3B or more.
  • each decorative sheet 1 produced by the above method is attached to one surface of the medium fiberboard (MDF) constituting the base material B using a urethane-based adhesive, With respect to the other surface of the base material B, a V-shaped groove is inserted to the boundary where the base material B and the decorative sheet 1 are bonded together so that the decorative sheet 1 on the opposite side is not scratched.
  • the base material B is bent to 90 degrees along the V-shaped groove so that the surface of the decorative sheet 1 is mountain-folded, and no whitening or cracks occur in the bent portion of the surface of the decorative sheet 1.
  • the first strength ratio is in the range of 0.9 to 2.0
  • the second strength ratio is in the range of 0.9 to 1.9
  • the crystal part and the non-crystal part of the transparent resin layer 3 are set to appropriate amounts, and the transparent resin layer 3 Is considered to have good scratch resistance and post-workability.
  • the scratch resistance is inferior compared with the case where the ratio of the random polypropylene resin is high. It is thought that it became.
  • the scratch resistance is higher than when the isotactic pentad fraction is high. Is considered to be inferior.
  • the scratch resistance is good. It is thought that it sometimes whitened and became inferior in post-processability.
  • the decorative sheet 1 of the comparative examples 4 and 5 since there are too many amorphous parts in the transparent resin layer 3, that is, crystallization is not progressing and it does not become hard enough, post-processability becomes favorable. It is thought that it was inferior in scratch resistance.
  • the decorative sheet 1 of the comparative example 6 since the ratio of the random polypropylene resin of the transparent resin layer 3 is high and it is not hard enough, it is thought that it became inferior to scratch resistance.
  • the decorative sheets 1 of Comparative Examples 7 and 8 are greatly oriented in the MD direction or the TD direction, so that the scratch resistance is good, but since it becomes too hard, the post-processability is considered to be inferior. It is done. From the above evaluation results, it was revealed that the decorative sheet 1 of the present invention shown in Examples 1 to 14 is a decorative sheet 1 excellent in scratch resistance and post-processing properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

L'objet de la présente invention est de produire une feuille décorative qui présente une meilleure résistance aux rayures et une meilleure aptitude à un post-traitement; et mettre en oeuvre un procédé de production de ladite feuille décorative. La feuille décorative (1) selon la présente invention comporte une couche de résine transparente (3) contenant une résine à base d'oléfine. Un premier rapport d'intensité qui est un rapport d'intensité spectrale entre une partie cristalline et une partie non cristalline de la couche de résine transparente (3) tel que mesuré dans le sens machine de la couche de résine transparente (3) par spectroscopie Raman se situe dans la plage de 0,9 à 2,0. De plus, un second rapport d'intensité qui est un rapport d'intensité spectrale entre la partie cristalline et la partie non cristalline de la couche de résine transparente (3) tel que mesuré dans le sens travers de la couche de résine transparente (3) par spectroscopie Raman se situe dans la plage de 0,9 à 1,9. La somme du premier rapport d'intensité et du second rapport d'intensité s'inscrit dans la plage comprise entre 1,9 et 3,6.
PCT/JP2017/020431 2016-06-01 2017-06-01 Feuille décorative et son procédé de fabrication WO2017209240A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218587A (ja) * 2016-06-01 2017-12-14 凸版印刷株式会社 化粧シート及び化粧シートの製造方法
US11660836B2 (en) * 2018-04-25 2023-05-30 Toppan Printing Co., Ltd. Decorative sheet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016068496A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 積層フィルム
JP2016068495A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 積層フィルム
WO2016076360A1 (fr) * 2014-11-11 2016-05-19 株式会社トッパン・コスモ Feuille décorée

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JP2011074203A (ja) * 2009-09-30 2011-04-14 Toyobo Co Ltd 表面保護用ポリプロピレン系樹脂フィルムおよび表面保護フィルム
JP6963273B2 (ja) * 2016-06-01 2021-11-05 凸版印刷株式会社 化粧シート及び化粧シートの製造方法

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2016068496A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 積層フィルム
JP2016068495A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 積層フィルム
WO2016076360A1 (fr) * 2014-11-11 2016-05-19 株式会社トッパン・コスモ Feuille décorée

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218587A (ja) * 2016-06-01 2017-12-14 凸版印刷株式会社 化粧シート及び化粧シートの製造方法
US11660836B2 (en) * 2018-04-25 2023-05-30 Toppan Printing Co., Ltd. Decorative sheet

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