WO2026028811A1 - Feuille décorative et procédé de fabrication d'article moulé décoratif - Google Patents

Feuille décorative et procédé de fabrication d'article moulé décoratif

Info

Publication number
WO2026028811A1
WO2026028811A1 PCT/JP2025/025400 JP2025025400W WO2026028811A1 WO 2026028811 A1 WO2026028811 A1 WO 2026028811A1 JP 2025025400 W JP2025025400 W JP 2025025400W WO 2026028811 A1 WO2026028811 A1 WO 2026028811A1
Authority
WO
WIPO (PCT)
Prior art keywords
matte
resin
layer
sheet
decorative sheet
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.)
Pending
Application number
PCT/JP2025/025400
Other languages
English (en)
Japanese (ja)
Inventor
淳 松本
智之 田中
光 西垣
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.)
Nissha Co Ltd
Original Assignee
Nissha Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissha Co Ltd filed Critical Nissha Co Ltd
Publication of WO2026028811A1 publication Critical patent/WO2026028811A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/12—Moulds or cores; Details thereof or accessories therefor with incorporated means for positioning inserts, e.g. labels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—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
    • B32B3/10—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 discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—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 discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties

Definitions

  • This invention relates to a decorative sheet with excellent formability and chemical resistance, a decorated molded product using the same, and a method for manufacturing the decorated molded product.
  • Patent Document 1 discloses a decorative sheet that has a base layer, a first protective layer provided on the base layer, and a second protective layer partially provided on the first protective layer, with a three-dimensional effect created by the difference in gloss and uneven shape between the second protective layer and the first protective layer.
  • the first protective layer is formed from a cured product of an ionizing radiation curable resin composition.
  • ionizing radiation curable resins require a process for irradiating ionizing radiation and requires larger equipment, which can reduce productivity.
  • thermosetting resin is used instead of an ionizing radiation curable resin, although it does not require as large equipment as ionizing radiation curable resins, sufficient moldability and chemical resistance may not be achieved.
  • the present invention was made to solve the above-mentioned problems, and its purpose is to provide a decorative sheet that uses a two-component curing urethane resin, which is a thermosetting resin, and has good formability and chemical resistance, as well as a decorated molded product that uses this decorative sheet.
  • the first invention is a decorative sheet comprising a base sheet having a glass transition temperature of 80 to 110°C and a thickness of 75 to 125 ⁇ m, a matte layer formed on the base sheet, and a matte pattern layer formed on the matte layer, wherein the matte layer contains a first binder resin and a first matte material, and the matte pattern layer contains a second binder resin and a second matte material, the first binder resin and the second binder resin are two-component curing urethane resins that are cured products of polyol and an isocyanate-based curing agent, and the ratio (NCO/OH) of isocyanate groups in the isocyanate-based curing agent to hydroxyl groups in the polyol is 1.1 to 2.0.
  • the base sheet has appropriate bendability, and the two-component curing urethane resin that forms the matte layer and matte pattern layer undergoes an appropriate crosslinking reaction, resulting in a decorative sheet with excellent formability and chemical resistance.
  • the second invention is the first invention, wherein the first matting material is inorganic particles and the second matting material contains resin particles.
  • the inorganic particles that make up the first matte material do not easily repel the binder resin that is applied as an overlay, improving the film-forming properties of the binder resin in the matte pattern layer formed on top of the matte layer, making it possible to provide a decorative sheet with excellent design and chemical resistance. Furthermore, since the second matte material contains resin particles, it is possible to provide a decorative sheet with excellent tactile feel and scratch resistance.
  • the third invention is the first or second invention, wherein the base sheet contains an acrylic resin.
  • This configuration improves the formability and impact resistance of the base sheet, making it possible to provide a decorative sheet with excellent formability.
  • the decorative sheet of the third invention has an Erichsen value of 12.0 to 14.9 mm when measured using the Erichsen test method.
  • the fifth invention is a decorative molded product comprising: a resin molded body; a base sheet formed on the resin molded body, the base sheet having a glass transition temperature of 80 to 110°C and a thickness of 75 to 125 ⁇ m; a matte layer formed on the base sheet; and a matte pattern layer formed on the matte layer, wherein the matte layer contains a first binder resin and a first matte material, and the matte pattern layer contains a second binder resin and a second matte material, the first binder resin and the second binder resin are two-component curing urethane resins that are cured products of polyol and an isocyanate-based curing agent, and the ratio (NCO/OH) of isocyanate groups in the isocyanate-based curing agent to hydroxyl groups in the polyol is 1.1 to 2.0.
  • This configuration allows for the provision of decorative molded products with excellent formability and chemical resistance, as well as excellent productivity.
  • the sixth invention comprises a base sheet having a glass transition temperature of 80 to 110°C and a thickness of 75 to 125 ⁇ m, a matte layer formed on the base sheet, and a matte pattern layer formed on the matte layer, wherein the matte layer contains a first binder resin and a first matte material, and the matte pattern layer contains a second binder resin and a second matte material, and the first binder resin and the second binder resin are two-component curing urethane resins that are cured products of polyol and an isocyanate-based curing agent, and the isocyanate in the isocyanate-based curing agent is
  • This method for manufacturing a decorated molded product includes the steps of: preparing a decorative sheet in which the ratio of NCO groups to hydroxyl groups in the polyol (NCO/OH) is 1.1 to 2.0; placing the decorative sheet on the cavity surface of the first or second mold of an injection molding die having a first mold and a second mold that forms a cavity between the first mold and the second mold by clamp
  • This manufacturing method uses insert molding and in-mold molding, making it possible to produce decorative molded products with complex shapes. It also reduces the number of manufacturing processes, making it possible to reduce production costs and time.
  • This invention makes it possible to provide a decorative sheet with good formability and chemical resistance using a two-component curing urethane resin, which is a thermosetting resin.
  • 1 is a perspective view of a decorated molded product according to a first embodiment of the present invention
  • 2 is a schematic cross-sectional view taken along the line II-II shown in FIG. 1.
  • 1 is a cross-sectional view showing a schematic configuration of a decorative sheet according to a first embodiment of the present invention.
  • 1A to 1C are cross-sectional views showing a method for manufacturing a decorated molded product according to a first embodiment of the present invention.
  • the decorative molded product 20 has a rectangular shape in a plan view and includes a flat plate-shaped planar portion 61 and raised portions 62 that rise downward at the same height from two short sides of the planar portion 61.
  • the two opposing raised portions 62 are connected at an obtuse angle to the planar portion 61 so that they move away from each other as they rise downward.
  • the decorative molded product 20 includes a resin molded body 21 and a decorative sheet 10 formed on the resin molded body 21. Referring to FIG.
  • the decorative molded product 20 includes a backer sheet 16, an adhesive layer 15, a pattern layer 14, a base sheet 11, a matte layer 12, and a matte pattern layer 13 laminated in this order on the resin molded body 21.
  • the decorative molded product 20 is formed by insert molding or in-mold molding using the decorative sheet 10 on the resin molded body 21.
  • the decorative sheet 10 has a laminated structure in which a matte layer 12 and a matte pattern layer 13 are laminated in this order on one side of a base sheet 11, and a design layer 14, an adhesive layer 15, and a backer sheet 16 are laminated in this order on the side of the base sheet 11 on which the matte layer 12 is not formed.
  • the matte pattern layer 13 is also partially provided on top of the matte layer 12. An uneven shape is formed on the surface of the matte layer 12 by the areas where the matte pattern layer 13 is provided and the areas where the matte pattern layer 13 is not provided.
  • resin molded body 21 examples include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin, general-purpose engineering resins such as polyphenylene oxide-polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate-modified polyphenylene ether resin, polybutylene terephthalate resin, and ultra-high molecular weight polyethylene resin, and super-engineering resins such as polysulfone resin, polyphenylene sulfide resin, polyphenylene oxide resin, polyarylate resin, polyetherimide resin, polyimide resin, liquid crystal polyester resin, and heat-resistant polyallyl resin. Reinforcing materials such as glass fiber and inorganic fillers may also be added as appropriate.
  • general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin
  • general-purpose engineering resins such as polyphenylene oxide-polyst
  • the base sheet 11 is a layer formed by laminating a matte layer 12 and a matte pattern layer 13 and serving as a support for the decorative sheet.
  • the base sheet 11 is formed of a thermoplastic resin, such as a polycarbonate-based resin, an acrylic-based resin, an ethylene-based resin, a propylene-based resin, a polyolefin-based resin, a polyester-based resin, a polyamide-based resin, polyvinyl chloride, or an ABS resin.
  • the base sheet 11 may be formed by using one of these resins alone or by mixing two or more of them. It may also be formed by stacking multiple sheets of the same or different types.
  • the components of the thermoplastic resin are not particularly limited, but it is preferable that the base sheet contain an acrylic-based resin from the viewpoints of formability and impact resistance. Rubber particles may also be added to the base sheet. The addition of rubber particles can increase toughness.
  • the base sheet 11 may also contain, as appropriate, dispersants, antioxidants, compatibilizers, UV stabilizers, antiblocking agents, antistatic agents, and the like.
  • the glass transition temperature of the base sheet 11 is preferably 80°C or higher and 110°C or lower, and more preferably 90°C or higher and 110°C or lower.
  • a glass transition temperature of 80°C or higher provides excellent bendability, while a glass transition temperature of 90°C or higher provides excellent formability.
  • a glass transition temperature of 110°C or lower provides the strength required for processing and excellent trimming properties.
  • the thickness of the base sheet 11 is preferably 60 ⁇ m or more and 140 ⁇ m or less, and more preferably 75 ⁇ m or more and 125 ⁇ m or less.
  • a thickness of 60 ⁇ m or more provides the strength required for processing, and a thickness of 75 ⁇ m or more provides excellent trimming properties.
  • a thickness of 140 ⁇ m or less provides good formability.
  • a thickness of 125 ⁇ m or less results in a decorative sheet with excellent design when injection molded.
  • the matte layer 12 is a layer that gives the decorative sheet 10 a three-dimensional appearance by virtue of the difference in gloss from the matte pattern layer 13 and its uneven shape, and is provided on the base sheet 11.
  • the matte pattern layer 13 is partially provided on the matte layer 12. Therefore, the matte pattern layer 13 becomes the outermost layer of the decorative sheet 10 in the area where the matte pattern layer 13 is provided, and the matte layer 12 becomes the outermost layer in the area where the matte pattern layer 13 is not provided.
  • the matte layer 12 includes a first binder resin and a first matting material.
  • the first binder resin is a two-component curing urethane resin, which is a thermosetting resin.
  • Two-component curing urethane resins are cured by adding an isocyanate curing agent to a polyol base resin. Hydroxyl groups in the polyol and isocyanate groups in the isocyanate curing agent form urethane bonds, forming a crosslinked structure.
  • the two-component curing urethane resin is not particularly limited, but examples include those containing a polyol component (e.g., acrylic polyol, polyester polyol, polyether polyol, epoxy polyol) having hydroxyl groups as the base resin and an isocyanate component (e.g., tolylene diisocyanate, hexamethylene diisocyanate, meta-xylene diisocyanate) as the curing agent.
  • a polyol component e.g., acrylic polyol, polyester polyol, polyether polyol, epoxy polyol
  • an isocyanate component e.g., tolylene diisocyanate, hexamethylene diis
  • the first binder resin may be a two-component curing urethane resin alone or may be a mixture of two-component curing urethane resin and other resins.
  • examples of other resins include acrylic resins, urethane resins, thermoplastic polyester resins, and soluble nitrocellulose. Plasticizers, stabilizers, catalysts, and curing agents may also be added as needed.
  • the NCO/OH ratio which is the ratio of isocyanate groups in the isocyanate curing agent to hydroxyl groups in the polyol, of the two-component curing urethane resin that forms the matte layer 12 is 1.1 to 2.0. If the NCO/OH ratio is 2.0 or less, excessive progress of the crosslinking reaction is suppressed, the matte layer does not become too hard, and the decorative sheet is less likely to crack during three-dimensional molding. On the other hand, if the NCO/OH ratio is 1.1 or more, the progress of the crosslinking reaction is promoted, improving the chemical resistance of the matte layer. By allowing the crosslinking reaction of the two-component curing urethane resin to proceed appropriately, a decorative sheet with excellent moldability and chemical resistance can be provided.
  • the first matting material can be inorganic particles or resin particles.
  • the first matting material can adjust the gloss and create a gloss difference between the matte layer 12 and the matte pattern layer 13. It can also improve scratch resistance.
  • Inorganic particles that can be used include amorphous silica, spherical silica, alumina, kaolinite, calcium carbonate, barium sulfate, and glass. Of these, amorphous silica is preferred from the standpoint of scratch resistance and printability.
  • One type of inorganic particle may be used alone, or two or more types may be used in combination.
  • the content of inorganic particles is not particularly limited, but is preferably 20 to 70 parts by weight, and more preferably 40 to 60 parts by weight, per 100 parts by weight of the first binder resin described above. 20 parts by weight or more improves scratch resistance. 40 parts by weight or more allows the inorganic particles to permeate the entire surface, resulting in a good matte effect. 70 parts by weight or less suppresses cracking during shaping, and 60 parts by weight or less maintains good moldability.
  • the particle size of the inorganic particles is preferably 1 ⁇ m or more and 10 ⁇ m or less, and more preferably 2 ⁇ m or more and 8 ⁇ m or less. If it is 1 ⁇ m or more, some of the inorganic particles are likely to be exposed from the surface of the matte layer, resulting in a good matte effect. If it is 2 ⁇ m or more, scratch resistance is improved. If it is 10 ⁇ m or less, excellent moldability is achieved, and if it is 8 ⁇ m or less, the inorganic particles are distributed throughout the entire surface, resulting in a good matte effect and improved scratch resistance.
  • the average particle size is the volume-based average arithmetic value obtained by laser diffraction/scattering method, and includes not only the primary particle size but also the secondary particle size, which is agglomeration of particles.
  • the resin particles can be organic beads such as urethane resin, acrylic resin, polycarbonate resin, polyamide (nylon) resin, urea resin, silicon-based resin, etc.
  • One type of resin particle can be used alone, or two or more types can be used in combination.
  • the content of the resin particles is not particularly limited, but may be, for example, in the range of 5 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the first binder resin. If the content is 5 parts by mass or more, the tactile feel is good, and if the content is 25 parts by mass or less, good moldability is obtained.
  • the average particle size of the resin particles is, for example, in the range of 5 ⁇ m to 30 ⁇ m.
  • inorganic particles for the first matting material.
  • inorganic particles which can be easily adjusted to a small particle size, are used, the inorganic particles that make up the first matting material are less likely to repel the binder resin that is applied as an overcoat, improving the film-forming properties of the binder resin for the matte pattern layer formed on top of the matte layer, resulting in a decorative sheet with excellent design and chemical resistance.
  • the thickness of the matte layer 12 is preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • a thickness of 1 ⁇ m or more provides good scratch resistance, and a thickness of 2 ⁇ m or more provides good chemical resistance.
  • a thickness of 20 ⁇ m or less provides good formability, and a thickness of 10 ⁇ m or less allows part of the first matte material to be exposed from the surface of the matte layer, resulting in a good matte effect.
  • the thickness of the matte layer 12 refers to the thickness of the portion where the first matte material is not located on the surface of the matte layer 12.
  • the matte pattern layer 13 is a layer that imparts a three-dimensional feel and a tactile sensation to the decorative sheet by virtue of its difference in gloss from the matte layer 12 and its uneven shape, and is partially provided on the matte layer 12.
  • the matte pattern layer 13 can be made less matte (matte feel) than the matte layer 12.
  • the matte pattern layer 13 may be partially provided so as to match the pattern of the design layer 14.
  • By matching the uneven shape of the matte pattern layer 13 to the pattern of the design layer 14, a three-dimensional feel and a tactile sensation that are in harmony with the design can be imparted.
  • “In harmony with the pattern of the design layer 14" does not necessarily mean that the outer shape of the matte pattern layer 13 matches the outer shape of the design layer 14.
  • the matte pattern layer 13 may have convex portions inside the pattern formed by the design layer 14, or the matte pattern layer 13 may have convex portions outside the pattern formed by the design layer 14. Furthermore, the matte pattern layer 13 may have an uneven shape that is in sync with only a specific pattern (color or shape) among the patterns formed by the design layer 14 .
  • the matte pattern layer 13 includes a second binder resin and a second matting material.
  • the second binder resin is a two-component curing urethane resin, which is a thermosetting resin.
  • the NCO/OH ratio which is the ratio of the isocyanate groups in the isocyanate-based curing agent to the hydroxyl groups in the polyol, is 1.1 to 2.0.
  • the two-component curing urethane resin used for the second binder resin can be the same material as the first binder resin for the matte layer 12. From the viewpoint of achieving both light resistance and processability, it is preferable to use an acrylic polyol as the base resin and meta-xylene diisocyanate as the curing agent.
  • the second binder resin may be a two-component curing urethane resin alone or may be mixed with other resins. Examples of other resins include acrylic resins, urethane resins, thermoplastic polyester resins, and soluble nitrocellulose. Plasticizers, stabilizers, catalysts, and curing agents may also be added as appropriate.
  • the second binder resin and the first binder resin may have the same or different base resins and curing agents, and may also have the same or different NCO/OH ratios.
  • Resin particles or inorganic particles can be used as the second matting material.
  • the second matting material can adjust the gloss and create a gloss difference between the matte layer 12 and the matte pattern layer 13. It is also preferable that the second matting material contains resin particles. The resin particles can improve the feel and scratch resistance.
  • the resin particles can be made of the same material as the first matte material of the matte layer 12 described above.
  • the amount of resin particles is not particularly limited, but from the perspective of imparting a tactile feel, it is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of the second binder resin described above. 5 parts by mass or more improves scratch resistance, and 10 parts by mass or more allows the resin particles to permeate the entire surface, resulting in a good matte effect and tactile feel. 30 parts by mass or less suppresses cracking during shaping, and 20 parts by mass or less maintains good moldability.
  • the particle diameter of the resin particles is preferably between 5 ⁇ m and 50 ⁇ m, and more preferably between 10 ⁇ m and 30 ⁇ m.
  • a particle diameter of 5 ⁇ m or greater provides a good matte effect. If it is 10 ⁇ m or greater, some of the resin particles will be exposed from the surface of the matte layer, providing a good tactile feel.
  • the particle diameter is 50 ⁇ m or less, a good coating appearance will be obtained, and if it is 30 ⁇ m or less, the resin particles will be distributed throughout the entire surface, providing a good matte effect and improved scratch resistance.
  • the content of the resin particles is 10 to 20 parts by mass per 100 parts by mass of the second binder resin, and the average particle diameter of the resin particles is 10 to 30 ⁇ m, the resin particles will be more likely to localize on the surface of the matte pattern layer 13, and an uneven surface that feels smooth to the touch can be imparted to the surface of the decorative sheet.
  • the second matte material contains inorganic particles in addition to resin particles. By adding inorganic particles in addition to resin particles, the scratch resistance of the matte pattern layer 13 can be further improved.
  • the inorganic particles may be made of the same material as the first matting material of the matte layer 12 described above.
  • the content of the inorganic particles is not particularly limited, but may be, for example, in the range of 5 parts by mass to 25 parts by mass relative to 100 parts by mass of the second binder resin.
  • the average particle size of the inorganic particles can be, for example, in the range of 1 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the matte pattern layer 13 is preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • a thickness of 1 ⁇ m or more provides good scratch resistance, and a thickness of 2 ⁇ m or more provides good chemical resistance.
  • a thickness of 20 ⁇ m or less provides good formability, and a thickness of 10 ⁇ m or less allows part of the second matte material to be exposed from the surface of the matte layer, resulting in a good matte effect.
  • the thickness of the matte pattern layer 13 refers to the thickness of the portion where the second matte material is not located on the surface of the matte pattern layer 13.
  • the height of the convex portions of the matte pattern layer 13 is preferably 5 ⁇ m or more and 20 ⁇ m or less. If the height of the convex portions is 5 ⁇ m or more, changes in the feel of the surface will be more noticeable, and if it is 20 ⁇ m or less, good formability will be maintained.
  • the height of the convex portions is the height from the surface of the matte layer 12 to the highest point of each convex portion.
  • the area of the convex portions of the matte pattern layer 13 relative to the total area of the decorative sheet is preferably 30% or more and 70% or less. If the area of the convex portions relative to the total area of the decorative sheet is 30% or more, a good tactile feel can be imparted. Furthermore, if the area of the convex portions relative to the total area of the decorative sheet is 70% or less, the difference in gloss between the matte layer 12 and the matte pattern layer 13 becomes clear, resulting in a three-dimensional design.
  • the pattern layer 14 is a layer that imparts decorative properties to the decorative sheet and is formed by printing a pattern or color.
  • the pattern formed on the pattern layer 14 is not particularly limited and may be a pattern that imparts a glossy texture to the decorated molded product or a pattern that imparts a matte texture. Woodgrain, leather, metallic, and other patterns are also possible.
  • the pattern layer 14 may be formed by printing directly onto the base sheet 11, or by laminating a sheet with a printed pattern onto the base sheet 11. When printing on a sheet other than the base sheet 11, the sheet that serves as the printing base may be made of, for example, an acrylic resin, a urethane resin, a vinyl chloride-vinyl acetate copolymer resin, or a polyester resin.
  • the sheet that serves as the printing base contain an acrylic resin.
  • the pattern layer 14 may be formed over the entire surface or in any pattern.
  • the pattern layer 14 may be formed to a thickness of, for example, 1 ⁇ m or more and 20 ⁇ m or less, and preferably to a thickness of 2 ⁇ m or more and 7 ⁇ m or less. If the thickness is 2 ⁇ m or more, the strength is suitable for processing, and if it is 7 ⁇ m or less, the moldability is good.
  • the wood grain pattern can be formed by vascular and non-vascular portions.
  • the vascular portions of the pattern layer 14 may also be formed to match the matte pattern layer 13.
  • the design ink used for the design layer 14 is a binder containing a colorant such as a pigment or dye, as well as an appropriate blend of solvents, plasticizers, stabilizers, catalysts, hardeners, etc.
  • a colorant such as a pigment or dye
  • solvents plasticizers, stabilizers, catalysts, hardeners, etc.
  • binder or colorant there are no particular restrictions on the binder or colorant, and known binder resins and colorants can be used.
  • the adhesive layer 15 is an optional layer for bonding the base sheet 11 to the backer sheet 16.
  • Known heat- or pressure-sensitive materials can be used for the adhesive layer 15. Examples include acrylic, polystyrene, polyamide, polyolefin, and vinyl chloride-vinyl acetate copolymer resins.
  • the adhesive layer 15 can be formed to a thickness of 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 5 ⁇ m. A thickness of 1 ⁇ m or greater improves adhesion between the base sheet 11 and the backer sheet 16. A thickness of 20 ⁇ m or less prevents the adhesive layer from extending beyond the adhesive area between the backer sheet 16 and the base sheet 11, thereby impairing the adhesion between the two layers. A thickness of 5 ⁇ m or less improves formability.
  • the backer sheet 16 serves as a support and is adjacent to the molding resin during insert molding or in-mold molding.
  • the material of the backer sheet 16 is not particularly limited, and a thermoplastic resin, for example, can be used.
  • thermoplastic resins include polycarbonate-based resins, acrylic-based resins, ethylene-based resins, propylene-based resins, polyolefin-based resins, polyester-based resins, polyamide-based resins, polyvinyl chloride, and ABS resins.
  • the base sheet 11 may contain two or more of these materials or may be a laminate of these materials. The material can be selected appropriately based on compatibility with the molding resin used in injection molding and three-dimensional molding.
  • the thickness of the backer sheet 16 is, for example, 200 ⁇ m or more and 600 ⁇ m or less, more preferably 300 ⁇ m or more and 450 ⁇ m or less. A thickness of 300 ⁇ m or more improves the supportability of the decorative sheet, while a thickness of 450 ⁇ m or less ensures good moldability.
  • a primer layer may be provided between the base sheet 11 and the matte layer 12, or between the base sheet 11 and the pattern layer 14.
  • a primer layer By providing a primer layer, it is possible to improve adhesion between the base sheet 11 and the adjacent layer and to improve the formability of the decorative sheet.
  • a concealing layer may be provided between the base sheet 11 and the pattern layer 14. By providing a concealing layer, it is possible to suppress color changes and variations in the base sheet 11.
  • a backer sheet adhesive layer may be provided to improve adhesion with the resin molded body 21.
  • the primer layer is a layer provided for the purpose of increasing the adhesion of each layer and improving the formability of the decorative sheet, and may be provided, for example, between the base sheet 11 and an adjacent layer.
  • the resin forming the primer layer is not particularly limited, but examples include thermosetting resins such as urethane resin, acrylic resin, and polyester resin. These may be used alone or in a mixture of two or more types. From the viewpoint of suppressing cracking during shaping, it is preferable to provide the primer layer between the base sheet 11 and the matte layer 12. Furthermore, from the viewpoint of good formability, it is preferable to use a two-component curing urethane resin.
  • the thickness of the primer layer is preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 5 ⁇ m or less. A thickness of 1 ⁇ m or more provides adequate strength for processing, while a thickness of 20 ⁇ m or less, especially 5 ⁇ m or less, provides good formability.
  • the concealing layer is a layer provided to prevent the color of the resin molded body 21 from showing through and causing changes or variations in the color of the decorative sheet when the decorative sheet 10 is attached to the resin molded body 21 for use. For example, it can be provided as needed between the base sheet 11 and the design layer 14.
  • the ink used for the concealing layer is an ink in which a binder is appropriately blended with a colorant such as a pigment or dye, a solvent, a plasticizer, a stabilizer, a catalyst, a hardener, etc.
  • the materials for the binder and the colorant are not particularly limited, and known materials can be used.
  • the backer sheet adhesive layer is a layer provided for the purpose of increasing the adhesion between the backer sheet 16 and the resin molded article 21, and can be provided as needed on the surface of the backer sheet 16 opposite the surface on which the base sheet 11 and the design layer 14 are laminated.
  • Known materials having heat-sensitive or pressure-sensitive adhesive properties can be used as the backer sheet adhesive layer.
  • the backer sheet adhesive layer can be formed to a thickness of, for example, 1 ⁇ m to 10 ⁇ m.
  • the decorative sheet 10 preferably has an Erichsen value measured by the Erichsen test method of 12.0 mm or more and 14.9 mm or less, more preferably 12.4 mm or more and 14.3 mm or less, and even more preferably 12.7 mm or more and 14.3 mm or less.
  • An Erichsen value of 12.0 mm or more provides good bendability, and an Erichsen value of 12.4 mm or more provides excellent formability.
  • an Erichsen value of 12.7 mm or more provides good trimmability.
  • An Erichsen value of 14.9 mm or less provides the strength required for processing.
  • An Erichsen value of 14.3 mm or less provides good durability.
  • the Erichsen value of the decorative sheet 10 can be adjusted mainly by the material constituting the base sheet 11, the thickness of the base sheet 11, the materials constituting the matte layer and matte pattern layer (type of resin, NCO/OH ratio), the thickness of the matte layer and matte pattern layer, and the contents of the first matte material and the second matte material. Furthermore, when layers other than the base sheet 10, the matte layer 11, and the matte pattern layer 12 are provided, it is also possible to adjust the materials and thicknesses of these layers.
  • the Erichsen test method refers to a test in which a decorative sheet (dimensions: 70 mm ⁇ 70 mm) is pressed into the base sheet side with a spherical punch (diameter: 20 mm) using an Erichsen tester (manufactured by Yasuda Seiki Seisakusho) at a moving speed of 12 mm/min, and the Erichsen value refers to the penetration depth of the punch at which microcracks occur in the decorative sheet in the Erichsen test method.
  • a method for manufacturing the decorative sheet 10 will be described. First, a sheet having a glass transition temperature of 80 to 110° C. and a thickness of 75 to 125 ⁇ m is prepared as the base sheet 11. The above-mentioned thermoplastic resins can be used for the base sheet.
  • a matte layer 12 is formed on the base sheet 11.
  • a first matte material is mixed with a first binder resin.
  • a two-component curing urethane resin is used for the first binder resin, and isocyanate and polyol are blended so that the NCO/OH ratio is 1.1 to 2.0.
  • An ink is obtained by mixing the first binder resin and the first matte material. This mixture is layered on the base sheet 11 to form the matte layer 12.
  • the matte layer 12 can be formed using standard printing methods such as gravure printing, screen printing, and offset printing, or coating methods such as gravure coating, roll coating, and die coating.
  • a matte pattern layer 13 is partially laminated on the matte layer 12.
  • a second matte material is mixed into a second binder resin.
  • a two-component curing urethane resin is used for the second binder resin, and isocyanate and polyol are blended so that the NCO/OH ratio is 1.1 to 2.0.
  • the ink mixed with the second binder resin and second matte material can be laminated using a known printing or coating method, just like the matte layer 12.
  • a design layer 14 is formed on the surface of the base sheet 11 opposite the surface on which the matte layer 12 is formed.
  • a known binder resin and colorant are mixed and laminated using a known printing or coating method.
  • the design layer 14 may be formed by printing directly onto the base sheet 11, or by laminating a sheet with a printed design onto the base sheet 11.
  • an adhesive layer 15 is formed on the pattern layer 14.
  • a heat-sensitive adhesive or pressure-sensitive adhesive is laminated on the matte pattern layer 13 and the pattern layer 14.
  • a backer sheet 16 is formed on the adhesive layer 15.
  • the sheet used as the backer sheet 16 is laminated on top of the adhesive layer 15.
  • the decorative sheet 10 is prepared.
  • FIG. 4( a) A manufacturing method for the decorative molded product 20 will be described with reference to FIG. 4 .
  • the decorative sheet 10 is placed on a jig 72 and preheated using a heat source 71 (see FIG. 4( a)).
  • the heat source 71 include an infrared heater, an electric heater, high-frequency induction, a halogen lamp, microwaves, high-temperature induction such as steam, and a laser.
  • the heat temperature applied to the decorative sheet 10 by the heat source 71 can be 100 to 250°C.
  • the decorative sheet 10 softened by heating is brought into close contact with the jig 72 and shaped (see FIG. 4( b)).
  • Examples of methods for bringing the decorative sheet 10 into close contact include sucking air between the decorative sheet 10 and the jig 72 through suction holes (not shown) in the jig 72, or blowing compressed air from the decorative sheet 10 side to bring the decorative sheet 10 into close contact with the jig 72.
  • unnecessary portions of the decorative sheet 10 are trimmed (see FIG. 4( c)). This allows for the production of a decorative sheet 10 shaped to the outer surface of the decorative molded article.
  • the trimmed decorative sheet 10 is placed with the matte pattern layer 13 facing the cavity surface of the first mold 81, and the decorative sheet 10 is fixed in place by, for example, sucking air through suction holes (not shown) provided in the first mold 81 (see FIG. 4(d)).
  • the first mold 81 and the second mold 82 are clamped together to form a cavity between the first mold and the second mold.
  • Molten resin is injected into the cavity through a gate 83 to form a resin molded body 21, and at the same time, the resin molded body 21 and the surface of the decorative sheet 10 facing the backer sheet 16 are fixed together (see FIG. 4(e)).
  • the same resin as used for the resin molded body 21 described above can be used as the molten resin.
  • the mold is then opened, and the decorative molded article 20, in which the decorative sheet 10 and the resin molded body 21 are integrated, is removed (see FIG. 4(f)).
  • the decorative sheet 10 is shaped by adhering it to the jig 72 and then trimmed before injection molding, but trimming of the decorative sheet 10 may be performed after injection molding.
  • the decorative sheet 10 is shaped by adhering it to the molding surface of the first mold 81, a resin molded product in which the decorative sheet 10 and the resin molded body 21 are integrated by injection molding is taken out, and unnecessary portions of the decorative sheet are trimmed.
  • air can be sucked between the decorative sheet 10 and the molding surface through suction holes provided in the first mold 81.
  • the gate 83 is positioned in the second mold 82, but the gate 83 may also be positioned in the first mold, and the decorative sheet 10 may be positioned on either the cavity surface of the first mold 81 or the second mold 82.
  • Example 1 A base sheet was prepared consisting of an acrylic resin sheet (glass transition temperature: 90°C, thickness: 75 ⁇ m) containing acrylic resin with added rubber particles.
  • a design layer (thickness: 2-5 ⁇ m) consisting of an acrylic resin/vinyl chloride-vinyl acetate copolymer, an adhesive layer (thickness: 2-5 ⁇ m) consisting of a vinyl chloride-vinyl acetate copolymer, and a backer sheet (thickness: 430 ⁇ m) consisting of an ABS resin were laminated on one side of the base sheet in this order.
  • a two-component curing urethane resin (acrylic polyol, meta-xylene diisocyanate) was blended as the first binder resin to an NCO/OH ratio of 1.1, and silica (average particle size: 4 ⁇ m) was mixed as the first matting agent in an amount of 50 parts by weight per 100 parts by weight of the first binder resin.
  • the matting layer was then formed on the base sheet by gravure printing.
  • a two-component curing urethane resin (acrylic polyol, metaxylene diisocyanate) was blended as the second binder resin so that the NCO/OH ratio was 1.1, and 12 parts by mass of acrylic resin (average particle diameter: 20 ⁇ m) was mixed as the second matting agent for every 100 parts by mass of the second binder resin.
  • a matte pattern layer was partially formed on the matte layer by gravure printing. In this way, a decorative sheet having the layer structure shown in Figure 3 was produced.
  • the Erichsen value of the decorative sheet of Example 1 was 13.6 mm.
  • Examples 2 to 6 and Comparative Examples 1 to 5 A decorative sheet having the layer structure shown in Fig. 3 was produced under the production conditions shown in Table 1 and in the same manner as in Example 1. The Erichsen values of the decorative sheets obtained in the examples and comparative examples were measured.
  • the decorative sheet was heated to 120-150°C and fitted into a jig for shaping. Those that could be shaped over the entire temperature range were marked with a ⁇ , those that could only be shaped under specific temperature conditions were marked with a ⁇ , and those that could not be shaped were marked with an ⁇ .
  • the decorative sheet was trimmed using a trimming mold heated to room temperature or 50° C.
  • the decorative sheet that did not break when using the room temperature trimming mold was marked with an ⁇
  • the decorative sheet that broke at room temperature but not when using a mold heated to 50° C was marked with an ⁇
  • the decorative sheet that broke even when using a mold heated to 50° C was marked with an ⁇ .
  • the trimmed decorative sheet was set in a decorative molding die heated to room temperature or 50°C. If the decorative sheet did not crack in the die at room temperature, it was marked with an ⁇ , if it cracked at room temperature but not in a die heated to 50°C, it was marked with an ⁇ , and if it cracked even in a die heated to 50°C, it was marked with an ⁇ .
  • the decorative sheet was used for injection molding, and the decorative molded product was visually inspected for wrinkles and cracks. Those with no abnormalities were marked with ⁇ , and those with wrinkles or cracks were marked with ⁇ .
  • Examples 1 to 6 the evaluations of formability, trimming ability, cracking during shaping, and design of injection-molded products were all rated as ⁇ or ⁇ , indicating good formability. Furthermore, the evaluations of chemical resistance were all rated as ⁇ or ⁇ , indicating excellent chemical resistance. In particular, the decorative sheets of Examples 1 and 3 to 6 exhibited excellent trimming ability. In contrast, in Comparative Examples 1 to 5, the evaluations of formability, trimming ability, cracking during shaping, design of injection-molded products, and chemical resistance were all rated as ⁇ .
  • a pattern layer, adhesive layer, and backer sheet are formed on top of a base sheet, but it is sufficient for the decorated molded product to have a matte layer and matte pattern layer formed; it is not necessary to form the pattern layer, adhesive layer, and backer sheet.
  • the decorated molded product according to the first embodiment was manufactured by simultaneously molding the resin molded body 21 and laminating the decorative sheet 10, these steps may also be performed separately. In other words, a preformed decorative sheet 10 may be attached to the molded resin molded body 21.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Le problème à résoudre par la présente invention est de fournir une feuille décorative qui présente une excellente aptitude au moulage et une excellente résistance chimique et dans laquelle une résine d'uréthane durcissable à deux composants constituant une résine thermodurcissable est utilisée, et un article moulé décoratif dans lequel la feuille décorative est utilisée. La solution selon l'invention porte sur un article moulé décoratif (20) qui comprend un corps moulé en résine (21), comporte une feuille décorative (10) formée sur le corps moulé en résine (21), et est tel qu'une feuille de support (16), une couche adhésive (15), une couche de motif (14), une feuille de base (11), une couche mate (12) et une couche de motif mat (13) sont empilées dans l'ordre à partir du côté du corps moulé en résine (21). La feuille de base présente une température de transition vitreuse de 80 à 110 °C et une épaisseur de 75 à 125 µm. La couche mate (12) comprend une première résine liante et un premier matériau mat. La couche de motif mat (13) comprend une seconde résine liante et un second matériau mat. La première résine liante et la seconde résine liante constituent des résines à base d'uréthane durcissables à deux composants qui sont des produits durcis d'un polyol et d'un agent de durcissement à base d'isocyanate, et le rapport (NCO/OH) des groupes isocyanate de l'agent de durcissement à base d'isocyanate aux groupes hydroxyle du polyol est de 1,1 à 2,0.
PCT/JP2025/025400 2024-07-30 2025-07-16 Feuille décorative et procédé de fabrication d'article moulé décoratif Pending WO2026028811A1 (fr)

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JP2024123773A JP2026022261A (ja) 2024-07-30 2024-07-30 加飾シート及び加飾成形品の製造方法
JP2024-123773 2024-07-30

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WO2026028811A1 true WO2026028811A1 (fr) 2026-02-05

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000109773A (ja) * 1998-10-01 2000-04-18 Nissha Printing Co Ltd 耐候性、耐磨耗性および耐薬品性に優れた成形品の製造方法
JP2000117909A (ja) * 1998-10-15 2000-04-25 Dainippon Printing Co Ltd 化粧シート
JP2001310436A (ja) * 2000-04-28 2001-11-06 Dainippon Printing Co Ltd 化粧シート
JP2002144485A (ja) * 2000-11-17 2002-05-21 Dainippon Printing Co Ltd 化粧シート
WO2015046568A1 (fr) * 2013-09-30 2015-04-02 大日本印刷株式会社 Feuille décorative, article décoratif moulé en résine, et procédé de fabrication pour article décoratif moulé en résine
JP2017065261A (ja) * 2015-09-28 2017-04-06 大日本印刷株式会社 化粧シート、化粧板及び加飾樹脂成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000109773A (ja) * 1998-10-01 2000-04-18 Nissha Printing Co Ltd 耐候性、耐磨耗性および耐薬品性に優れた成形品の製造方法
JP2000117909A (ja) * 1998-10-15 2000-04-25 Dainippon Printing Co Ltd 化粧シート
JP2001310436A (ja) * 2000-04-28 2001-11-06 Dainippon Printing Co Ltd 化粧シート
JP2002144485A (ja) * 2000-11-17 2002-05-21 Dainippon Printing Co Ltd 化粧シート
WO2015046568A1 (fr) * 2013-09-30 2015-04-02 大日本印刷株式会社 Feuille décorative, article décoratif moulé en résine, et procédé de fabrication pour article décoratif moulé en résine
JP2017065261A (ja) * 2015-09-28 2017-04-06 大日本印刷株式会社 化粧シート、化粧板及び加飾樹脂成形品

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