WO2022145137A1 - 化粧シート、及び化粧シートの製造方法 - Google Patents

化粧シート、及び化粧シートの製造方法 Download PDF

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Publication number
WO2022145137A1
WO2022145137A1 PCT/JP2021/041624 JP2021041624W WO2022145137A1 WO 2022145137 A1 WO2022145137 A1 WO 2022145137A1 JP 2021041624 W JP2021041624 W JP 2021041624W WO 2022145137 A1 WO2022145137 A1 WO 2022145137A1
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WIPO (PCT)
Prior art keywords
decorative sheet
protective layer
less
surface protective
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/041624
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English (en)
French (fr)
Japanese (ja)
Inventor
絵理佳 阿久津
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Inc
Original Assignee
Toppan Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Inc filed Critical Toppan Inc
Priority to CN202180019585.XA priority Critical patent/CN115243889A/zh
Priority to US17/908,122 priority patent/US20230025597A1/en
Priority to JP2022520845A priority patent/JPWO2022145137A1/ja
Priority to EP21914998.6A priority patent/EP4101640B1/en
Priority to PL21914998.6T priority patent/PL4101640T3/pl
Priority to EP24219367.0A priority patent/EP4563369B1/en
Priority to KR1020227029806A priority patent/KR20230127867A/ko
Publication of WO2022145137A1 publication Critical patent/WO2022145137A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
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    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
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    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
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    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters

Definitions

  • the present invention relates to a decorative sheet used for surface makeup of interior and exterior of a building, fittings, furniture, building materials, flooring, etc., and a method for manufacturing the decorative sheet.
  • Durability is a comprehensive evaluation of scratch resistance, stain resistance, and whether they are guaranteed for a long period of time, and the requirements differ depending on the environment and circumstances in which the decorative sheet is used.
  • a decorative sheet having high performance In order to impart durability, it is common to form a surface protective layer on the outermost surface of the decorative sheet. Further, in order to adjust the above-mentioned glossiness, in particular, in order to achieve low gloss, it is common to add a gloss adjusting agent (matte additive) in the surface protective layer.
  • the decorative sheet is generally subjected to processing such as cutting or bending in order to form a decorative board or a decorative material, it is preferable that the decorative sheet has workability that can withstand these.
  • designability low gloss
  • scratch resistance scratch resistance
  • stain resistance stain resistance
  • the present invention has excellent design properties with low gloss, and has fingerprint resistance, high durability (particularly scratch resistance and stain resistance), and processability.
  • the purpose is to provide a sheet.
  • the present inventor has optimized the uneven shape of the surface protective layer in order to achieve low gloss, and further conducted experiments to find out the necessary structural elements for the material used for the surface protective layer to achieve low gloss and low gloss. We have found that it is possible to provide a decorative sheet that exhibits fingerprint resistance, high durability (particularly scratch resistance and stain resistance), and processability.
  • the decorative sheet according to one aspect of the present invention includes a raw fabric layer and a surface protective layer provided on one surface of the raw fabric layer, and the surface protective layer is the same.
  • the surface has a ridge-like portion provided in a ridge-like shape, and an uneven shape is formed.
  • the RSm / Ra of the uneven shape of the surface protective layer is in the range of 10 or more and 300 or less.
  • the main material of the surface protective layer is an ionizing radiation curable resin, the ionizing radiation curable resin is a trifunctional acrylic resin whose main component contains a repeating structure, and the repeating structure is ethylene oxide or propylene oxide. , And ⁇ -caprolactone, and the gist is that the number of repetitions of the repeating structure is 3 or more.
  • the decorative sheet 1 of the present embodiment has a pattern layer 3 and an adhesive layer 7 (heat-sensitive adhesive layer, anchor coat layer) on the surface side which is one surface of the raw fabric layer (base material layer) 2. , Dry Lami adhesive layer), transparent resin layer 4 and surface protection layer 5 are laminated in this order. Further, a concealing layer 8 and a primer layer 6 are provided on the back surface side, which is the other surface of the raw fabric layer 2. The pattern layer 3, the adhesive layer 7, the transparent resin layer 4, the concealing layer 8, and the primer layer 6 may be omitted. Then, as shown in FIG. 1, the decorative sheet 1 of the present embodiment constitutes the decorative material 11 by being bonded to the substrate B.
  • the substrate B is not particularly limited, but is composed of, for example, wood boards, inorganic boards, metal plates, a composite plate made of a plurality of materials, and the like.
  • a material arbitrarily selected from paper, synthetic resin, foam of synthetic resin, rubber, non-woven fabric, synthetic paper, metal leaf and the like can be used.
  • the paper include thin paper, titanium paper, resin-impregnated paper and the like.
  • the synthetic resin include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and the like.
  • Examples of the rubber include ethylene-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. It can be exemplified.
  • As the non-woven fabric an organic or inorganic non-woven fabric can be used.
  • Examples of the metal of the metal foil include aluminum, iron, gold, and silver.
  • a prime layer 6 is provided between the raw fabric layer 2 and the base material B. It is preferable to provide it.
  • corona treatment, plasma treatment, ozone treatment, and electron beam treatment are applied to the raw fabric layer 2.
  • UV treatment, heavy chromic acid treatment and other surface modification treatments may be performed.
  • the primer layer 6 the same material as the pattern layer 3 described later can be used.
  • the primer layer 6 is applied to the back surface of the decorative sheet 1, considering that the decorative sheet 1 is wound up in a web shape, the primer layer is used to avoid blocking and to improve the adhesion with the adhesive.
  • An inorganic filler may be added to 6. Examples of the inorganic filler include silica, alumina, magnesia, titanium oxide, barium sulfate and the like.
  • the layer thickness of the raw fabric layer 2 is preferably in the range of 20 ⁇ m or more and 250 ⁇ m or less in consideration of printing workability and cost.
  • the pattern layer 3 is a layer for pattern printing applied to the original fabric layer 2 using ink.
  • the binder of the ink for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester or the like alone or each modified product can be appropriately selected and used.
  • the binder may be an aqueous type, a solvent type, or an emulsion type, and may be a one-component type or a two-component type using a curing agent. Further, a method of using a curable ink and curing the ink by irradiation with ultraviolet rays, an electron beam, or the like may be used.
  • urethane-based ink and cure it with isocyanate.
  • colorants such as dyes, extender pigments, solvents, various additives, and the like are added to the pattern layer 3.
  • highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.
  • a design to the pattern layer 3 by vapor deposition or sputtering of various metals separately from the application of ink.
  • a light stabilizer is added to the ink, whereby deterioration of the decorative sheet 1 itself caused by photodegradation of the ink can be suppressed, and the life of the decorative sheet 1 can be extended.
  • the adhesive layer 7 is a layer also called a heat-sensitive adhesive layer, an anchor coat layer, or a dry lami adhesive layer.
  • the resin material of the adhesive layer 7 is not particularly limited, and for example, it can be appropriately selected from resin materials such as acrylic, polyester, polyurethane, and epoxy. Further, as the resin material of the adhesive layer 7, for example, an ethylene-vinyl acetate copolymer resin-based adhesive can also be used.
  • the coating method can be appropriately selected depending on the viscosity of the adhesive and the like, but generally, a gravure coat is used, and after being applied by the gravure coat to the upper surface of the pattern layer 3, a transparent resin layer is used. It is designed to be laminated with 4.
  • the adhesive layer 7 can be omitted if sufficient adhesive strength between the transparent resin layer 4 and the pattern layer 3 can be obtained.
  • ⁇ Transparent resin layer 4> As the resin material of the transparent resin layer 4, an olefin resin is preferably used.
  • the olefin resin include ⁇ -olefins (eg, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1 and others, in addition to polypropylene, polyethylene, polybutene and the like.
  • Copolymer ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer
  • examples thereof include those obtained by copolymerizing ethylene or ⁇ -olefin with other monomers such as a coalescence, an ethylene / butyl acrylate copolymer, and the like.
  • the resin of the transparent resin layer 4 in order to improve the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene as the resin of the transparent resin layer 4.
  • various additives such as a heat stabilizer, a light stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster are added to the transparent resin layer 4. You can also do it.
  • a phenol-based, sulfur-based, phosphorus-based, hydrazine-based or the like is added as the heat stabilizer, and a hindered amine-based or the like is added as the light stabilizer in any combination.
  • the surface protective layer 5 has a core portion 5A and a ridge-shaped portion 5B provided so as to project in a ridge shape from one surface of the core portion 5A. As a result, an uneven shape is formed on the surface of the surface protective layer 5.
  • the "ridge-shaped” means a shape that is elongated and raised and is linearly connected in a plan view.
  • the ridge-shaped portion 5B may be curved or linear in a plan view, but is preferably curved from the viewpoint of fingerprint resistance on the surface of the decorative sheet 1.
  • the ridge-shaped portion 5B is, for example, a portion from the lowest portion to the tip of the uneven shape provided on the surface of the surface protection layer 5, and the core portion 5A is the ridge-shaped portion of the surface protection layer 5. It shall refer to the part excluding 5B.
  • FIG. 2 is a cross-sectional view schematically showing a cross section of a ridge-shaped portion 5B of the surface protective layer 5 (a cross section in the thickness direction of the surface protective layer 5), and FIG. 3 shows a configuration of the surface of the surface protective layer 5.
  • FIG. 3 is a plan photograph obtained by a laser microscope (OLS-4000 manufactured by Olympus).
  • the ridge-shaped portion 5B has a shape that is elongated and swells and is linearly connected in a plan view.
  • the ridged portion 5B is formed by irradiating the surface of the ionizing radiation curable resin with light having a specific wavelength to shrink the surface of the ionizing radiation curable resin, as will be described later.
  • the shape of such a ridged portion 5B is an index RSm ( ⁇ m) of the surface roughness in the horizontal direction (the plane direction of the surface protective layer 5 and the left-right direction in FIG. 2) and the vertical direction (the ridged portion 5B).
  • RSm / Ra can be indicated by the ratio RSm / Ra of the index Ra ( ⁇ m) of the surface roughness in the depth direction and the thickness direction of the surface protective layer 5 (upper and lower direction in FIG. 2). It is preferably 10 or more and 300 or less. More preferably, it is 10 or more and 250 or less.
  • RSm / Ra is less than 10
  • the shape of the ridge-shaped portion 5B is too fine, so that it becomes difficult to wipe off dirt and the stain resistance becomes poor.
  • RSm / Ra is larger than 300, the spacing between the ridges is too wide, so that the gloss is not low.
  • RSm / Ra is more preferably 50 or more and 200 or less.
  • the spacing between the ridges is moderately wide, so that the affinity for water or a detergent (water containing a surfactant or alcohol) is improved. Therefore, if the decorative sheet has RSm / Ra within the numerical range, even if the surface of the decorative sheet becomes dirty, it is easy to wipe off the stain with water or a cleaning agent.
  • RSm / Ra is most preferably 80 or more and 150 or less. If RSm / Ra is within this numerical range, a commercially available cleaning sponge can easily penetrate between the ridges, and even if the surface of the decorative sheet becomes dirty, it is generally commercially available. It becomes easy to wipe off the dirt by using the cleaning sponge that has been used.
  • Ra and RSm are measured values when measured using a line roughness meter (based on JIS B0601).
  • the residual oxygen concentration in the reaction atmosphere is preferably suppressed to 2000 ppm or less. More preferably, the residual oxygen concentration in the reaction atmosphere is 1000 ppm or less.
  • the integrated light amount of the first irradiation light is 0.5 mJ / cm 2 or more and 200 mJ / cm 2 or less. More preferably, the integrated light amount is 1 mJ / cm 2 or more and 100 mJ / cm 2 or less. More preferably, the integrated light amount is 3 mJ / cm 2 or more and 50 mJ / cm 2 or less. Most preferably, the integrated light amount is 5 mJ / cm 2 or more and 30 mJ / cm 2 or less.
  • a xenon lamp that emits excima light having a center wavelength of 172 nm as a light source.
  • a xenon lamp as a light source in consideration of the cost for maintaining the equipment and the availability of materials.
  • the integrated light amount of the second irradiation light is 10 mJ / cm 2 or more and 500 mJ / cm 2 or less. More preferably, the integrated light amount is 50 mJ / cm 2 or more and 400 mJ / cm 2 or less. More preferably, the integrated light amount is 100 mJ / cm 2 or more and 300 mJ / cm 2 or less.
  • the integrated light amount is less than 10 mJ / cm 2 , the curing reaction is weak and sufficient strength cannot be imparted to the entire surface protective layer 5, so that the scratch resistance tends to decrease. Further, when the integrated light amount is more than 200 mJ / cm 2 , the curing reaction tends to be too strong and the surface condition tends to be deteriorated.
  • the integrated light amount of the second irradiation light is more than 50.0 times the integrated light amount of the first irradiation light, the curing reaction to the entire surface protective layer 5 becomes too strong, and the shape of the ridge-shaped portion 5B becomes large. It may be deformed.
  • the irradiation light amount of the first irradiation light may gradually increase with the lapse of the irradiation time and then gradually decrease with the lapse of the irradiation time. Further, as shown in FIG. 5C, the irradiation light amount of the first irradiation light may gradually decrease with the lapse of the irradiation time. Further, as shown in FIG. 5 (e), the irradiation light amount of the first irradiation light may gradually increase with the lapse of the irradiation time. Further, as shown in FIG.
  • the surface protective layer 5 covers the entire surface of the surface side of the raw fabric layer 2, for example, various coating methods such as a roll coating method, a knife coating method, a microgravure coating method, and a die coating method can be used. Can be formed. These printing methods or coating methods may be selected separately depending on the layer to be formed, or the same method may be selected and batch processed.
  • the pattern layer 3 and the surface protection layer 5 may be synchronized from the viewpoint of design. In the case of synchronization, it is necessary to collectively form the surface protective layer 5 after forming the pattern layer 3, so it is preferable to use the gravure printing method. In addition, the gravure printing method is advantageous in terms of cost because it can handle relatively high speeds, which is preferable.
  • tuning means that 50% or more, preferably 70% or more, most preferably 90% or more of the portion where the surface protective layer 5 is formed overlaps with the design portion of the design layer 3 in a plan view. do.
  • the amount of the particles added is 2 parts by mass or more and 8 parts by mass or less, more preferably 2 parts by mass or more and 6 parts by mass or less, and most preferably 4 parts by mass or more and 5 parts by mass or less.
  • the surface protective layer 5 is preferable because a uniform surface state can be formed by containing the particles in the above-mentioned addition amount.
  • the photoinitiator is not particularly limited, and examples thereof include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based.
  • the surface protective layer 5 can optionally be added with functional additives such as an antibacterial agent and an antifungal agent in order to impart the required functions. Further, an ultraviolet absorber and a light stabilizer can be added to the surface protective layer 5 as needed.
  • the concealing layer 8 can be basically composed of the same material as the pattern layer 3, but since the purpose is concealment, for example, an opaque pigment, titanium oxide, iron oxide or the like is used as the pigment. Is preferable. Further, in order to improve the concealment property, for example, a metal such as gold, silver, copper or aluminum can be added. Generally, flake-shaped aluminum is often added.
  • a resin film is used as the raw fabric layer 2, and the surface protective layer 5 is formed by printing on the upper surface of the raw fabric layer 2.
  • the surface protective layer 5 irradiates the surface of the coated ionizing radiation curable resin with light having a wavelength of 200 nm or less (first irradiation light) to shrink the surface of the ionizing radiation curable resin.
  • first irradiation light light having a wavelength of 200 nm or less
  • UV light having a wavelength longer than that of ionizing radiation or light having a wavelength of 200 nm or less, which is the first irradiation light, is irradiated.
  • the decorative sheet 1 having the surface protective layer 5 having the core portion 5A and the ridge-shaped portions 5B provided so as to project from one surface (upper surface) of the core portion 5A in a ridge shape is formed.
  • the present embodiment is not limited to the above-described embodiment.
  • ionizing radiation or light having a wavelength of 200 nm or less which is the first irradiation light
  • UV light having a longer wavelength than that may be irradiated only once.
  • the integrated light amount of the first irradiation light having a wavelength of 200 nm or less may be 0.5 mJ / cm 2 or more and 200 mJ / cm 2 or less.
  • the decorative sheet 1 according to the present embodiment includes a surface protective layer 5 having an uneven shape formed on the surface. According to this configuration, the gloss (glossiness) of the surface protective layer can be adjusted even if the surface protective layer does not contain a gloss adjuster (matte additive).
  • the gloss adjuster reduces the oil repellency of the layer formed of the resin material, so that fingerprints are easily attached. Since the surface protective layer 5 according to the present embodiment does not contain a gloss adjusting agent, it does not absorb oil and its oil repellency is relatively improved. For this reason, fingerprints are less likely to adhere to the decorative sheet 1 having the surface protective layer 5 in various situations such as on-site construction, furniture assembly, and daily life of residents.
  • the layer located on the original fabric layer 2 side (that is, the layer located below the outermost layer of the surface protective layer 5) is not particularly limited.
  • Example 1 An olefin film having a thickness of 55 ⁇ m (manufactured by RIKEN TECHNOS) was used as the raw fabric layer, one surface of the raw fabric layer was subjected to corona treatment, and the following coating liquid for a surface protective layer was applied to one surface.
  • the layer thickness of the coating liquid for the surface protective layer was 5 ⁇ m.
  • the surface of the coating liquid for the surface protective layer was irradiated with a Xe excimer lamp having a wavelength of 172 nm so that the integrated light amount was 100 mJ / cm 2 , and the surface was shrunk.
  • the surface protective layer 5 was formed by irradiating 100 kGy of ionizing radiation and curing the coating liquid for the surface protective layer to obtain a decorative sheet of Example 1 having a total thickness of 60 ⁇ m.
  • the coating liquid for the surface protective layer was composed by blending the following particles with the following ionizing radiation curable resin.
  • -Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (with 6 mol of EO added)
  • Particle size 5 ⁇ m
  • Formulation 0.5 parts by mass
  • Example 2 A decorative sheet of Example 2 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (with 15 mol of EO added)
  • Product name: SR9035 manufactured by Sartomer
  • Example 3> A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Trimethylolpropane EO-modified triacrylate (with 3 mol of EO added)
  • Product name: Miramer M3130 (manufactured by Miwon)
  • Example 4 A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Trimethylolpropane PO-modified triacrylate (with 6 mol of PO added)
  • Product name NK Ester A-TMPT-6PO (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Example 5> A decorative sheet of Example 5 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Caprolactone-modified trisoo (2-acryloxyethyl) isocyanurate (caprolactone (CL) added with 3 mol)
  • Product name NK Ester A-9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Example 6> A decorative sheet of Example 6 having a total thickness of 56 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the coating liquid for the surface protective layer of Example 1 was 1 ⁇ m.
  • Example 7> A decorative sheet of Example 7 having a total thickness of 57 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the coating liquid for the surface protective layer of Example 1 was 2 ⁇ m.
  • Example 8> A decorative sheet of Example 8 having a total thickness of 75 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the coating liquid for the surface protective layer of Example 1 was 20 ⁇ m.
  • Example 9> A decorative sheet of Example 9 having a total thickness of 80 ⁇ m was obtained in the same manner as in Example 1 except that the layer thickness of the coating liquid for the surface protective layer of Example 1 was 25 ⁇ m.
  • Example 10> A decorative sheet of Example 10 was obtained in the same manner as in Example 9 except that the particles of Example 9 were not blended.
  • Example 11> A decorative sheet of Example 11 was obtained in the same manner as in Example 3 except that the particles of Example 3 were not blended.
  • Example 12 A decorative sheet of Example 12 was obtained in the same manner as in Example 1 except that the particles of Example 1 were replaced with the following.
  • Example 13 A decorative sheet of Example 13 was obtained in the same manner as in Example 1 except that the particles of Example 1 were replaced with the following.
  • ⁇ Comparative Example 1> A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the excimer lamp irradiation of Example 1 was eliminated and the blending amount of the particles was 15 parts by mass.
  • ⁇ Comparative Example 2> A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Ethylene glycol diacrylate (with 9 mol of EO added)
  • Product name Light acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.)
  • ⁇ Comparative Example 3> A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Pentaerythritol tetraacrylate (with 35 mol of EO added)
  • ⁇ Comparative Example 4> A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin of Example 1 was replaced with the following.
  • -Ionizing radiation curable resin Type Trimethylolpropane Triacrylate Product name: NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • ⁇ Stain resistance> As an evaluation of stain resistance, a line with a width of 10 mm was drawn with blue ink, black quick-drying ink, and red crayon according to the contamination A test specified in the Japanese Agricultural Standards (JAS), and after leaving for 4 hours, ethanol was used. Was soaked in a cloth and the lines of blue ink, black quick-drying ink and red crayon were wiped off, and the stain resistance by the ink was evaluated.
  • the evaluation criteria are as follows. ⁇ : Lines of each color could be easily wiped off ⁇ : Part of the line of each color could be wiped off, but some stains remained ⁇ : Lines of each color could not be wiped off
  • ⁇ Scratch resistance test Steel wool rubbing test> After the obtained decorative sheet was attached to the wood substrate B using a urethane-based adhesive, a steel wool rubbing test was carried out as a scratch resistance evaluation. A load of 100 g was applied to the steel wool and rubbed 20 times, and scratches and changes in gloss generated on the surface of the decorative sheet were visually confirmed.
  • the evaluation criteria are as follows. ⁇ : No scratches or changes in gloss on the surface ⁇ : Minor scratches or changes in gloss occurred on the surface ⁇ : Significant scratches or changes in gloss occurred on the surface
  • ⁇ Bending workability test> The obtained decorative sheet is attached to the wood substrate B with a urethane-based adhesive so that the surface on the raw fabric layer side (that is, the back surface of the decorative sheet) faces the wood substrate B, and then the decorative sheet is applied. Insert a V-shaped groove up to the boundary where the wood substrate B and the decorative sheet 1 are bonded so that the sheet is not scratched. Next, the wood substrate B is bent up to 90 degrees along the V-shaped groove so that the surface of the decorative sheet on the surface protective layer side (that is, the surface of the decorative sheet) is folded in a mountain shape, and the surface of the decorative sheet is bent. The state of bending workability was evaluated by observing whether whitening or cracks were generated in the part using an optical microscope. The evaluation criteria are as follows. ⁇ : No whitening or cracks are seen ⁇ : Whitening is seen in part ⁇ : Whitening is seen in the entire surface or cracks are seen in some parts The evaluation results are shown in Tables 1 and 2.

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US12594741B2 (en) * 2021-11-26 2026-04-07 Toppan Holdings Inc. Decorative sheet, and method for producing decorative sheet
JP7852767B1 (ja) 2025-03-03 2026-04-28 大日本印刷株式会社 化粧シートの製造方法、化粧シート、化粧材および樹脂組成物

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