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
  • 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
  • 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
  • B32B3/26—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
• • 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
  • B32B7/023—Optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
  • B44C3/02—Superimposing layers
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F13/00—Illuminated signs; Luminous advertising
  • G09F13/04—Signs, boards or panels, illuminated from behind the insignia

Definitions

• the present invention relates to a laminate and a decorative article.
• a molding method is used in which a decorative sheet with a pre-designed design is integrated with the resin by injection molding.
• a typical example of such a molding method is the insert molding method, in which the decorative sheet is molded into a three-dimensional shape in advance using a vacuum forming mold, the decorative sheet is inserted into an injection molding mold, and the resin in a fluid state is injected into the mold to integrate the resin with the decorative sheet.
• the decorated resin molded products obtained by such molding methods are used in a variety of applications, such as vehicle interior and exterior parts, as described above.
• diverse design sensibilities are also required in line with the diversification of consumer tastes in recent years. For example, developments have been made to impart texture to resin molded products by giving them a matte finish or unevenness to match specific parts of a pattern (e.g., Patent Document 1).
• synthetic resin molded parts with changing design surfaces have been proposed as products with diverse design sensibilities (e.g., Patent Document 2).
• laminates are known that exhibit different designs when the light source is on and off.
• Patent Document 4 discloses a laminate that has a first main surface arranged on the observer side and a second main surface arranged on the light source side, and that, in order from the second main surface side, has at least a first design layer, a second design layer, and a transparent base layer, and the transparent base layer has an uneven shape on the surface on the second design layer side.
• This laminate is excellent in that the design that appears when the light source is turned on is not visible when the light source is turned off, and the design is visible only when the light source is turned on.
• the main object of the present invention is to provide a laminate that presents a different design when the light source is on and when it is off, in which the design that appears when the light source is off is difficult to see when the light source is on, and the design is visible when the light source is off. Furthermore, the present invention also aims to provide a decorative article that utilizes the laminate.
• the present invention is an invention that was
• a liquid crystal display comprising a first main surface disposed on the viewer side and a second main surface disposed on the light source side, The first main surface has an uneven shape
• a laminate including, in order from the first main surface side, at least a first design layer, a transparent resin layer, and a second design layer, A third design layer is further provided on the first main surface side or the second main surface side of the second design layer, The surface of the second design layer on the first main surface side is relatively flatter than the uneven shape of the first main surface, The third design layer is provided partially on the laminate.
• Item 2 The laminate according to item 1, wherein a surface on the first main surface side of the transparent resin layer has an uneven shape corresponding to the uneven shape of the first main surface.
• Item 3 The laminate according to item 1 or 2, further comprising a surface protective layer on an outermost surface on the first main surface side.
• Item 4. The laminate according to any one of Items 1 to 3, further comprising a transparent substrate layer on the second main surface side of the second design layer and the third design layer.
• Item 5. The laminate according to any one of Items 1 to 4, wherein the laminate is in the form of a sheet.
• Item 6. The laminate according to any one of items 1 to 5, comprising, in order from the second main surface side, at least a transparent molded resin layer, the second design layer, the transparent resin layer, and the first design layer.
• Item 7. The laminate according to any one of items 1 to 6, A light source disposed on a second main surface side of the laminate;
• a decorative article comprising:
• the present invention can provide a laminate that presents a different design when the light source is on and when it is off, in which the design that appears when the light source is off is difficult to see when the light source is on, and the design is visible when the light source is off. Furthermore, the present invention can also provide a decorative article that uses the laminate.
• FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention.
• FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention.
• FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention.
• FIG. 1 is a schematic cross-sectional view of an example of a decorated article using the laminate of the present invention.
• FIG. 2 is an example of an image diagram of the laminate of the present invention when observed from the first main surface side (observer side) when a light source 30 is turned on.
• FIG. 2 is an example of an image diagram of the laminate of the present invention when observed from the first main surface side (observer side) when a light source 30 is turned on.
• the laminate of the present invention has a first main surface arranged on the observer side and a second main surface arranged on the light source side, the first main surface has an uneven shape, and is a laminate having at least a first design layer, a transparent resin layer, and a second design layer in order from the first main surface side, and further has a third design layer on the first main surface side or the second main surface side of the second design layer, the surface of the first main surface side of the second design layer is relatively flatter than the uneven shape of the first main surface, and the third design layer is partially provided.
• the laminate of the present invention expresses a different design when the light source is turned on and off, and when the light source is turned on, the design that appears when the light source is turned off (specifically, the design based on the uneven shape of the first main surface side surface of the laminate and the design by the first design layer) is difficult to see, and when the light source is turned off, the design is visible.
• the laminate of the present invention can be suitably used to decorate the surfaces of resin molded products such as vehicle interior and exterior parts, building materials, and home appliance housings. Therefore, the laminate of the present invention can be suitably used as a decorative sheet for three-dimensional molding.
• the laminate of the present invention when it is in the form of a sheet, it can be molded as a decorative sheet for three-dimensional molding and laminated with the molded resin layer 5 described below to suitably produce a decorated resin molded product.
• the laminate 10 of the present invention has a first main surface 11 arranged on the viewer side and a second main surface 12 arranged on the light source side, as shown in, for example, Figures 1 to 5.
• the first main surface 11 is arranged on the viewer side and the second main surface 12 is arranged on the light source side.
• the laminate 10 of the present invention is a laminate comprising, in order from the first main surface side 11, at least a first design layer 21, a transparent resin layer 1, and a second design layer 22, and further comprising a third design layer 23 on the first main surface 11 side or the second main surface 12 side of the second design layer 22. Furthermore, in the laminate 10 of the present invention, the first main surface 11 has an uneven shape.
• the laminate 10 When observed from the first main surface 11 side, the laminate 10 exhibits different designs when the light source 30 is on and off. When the light is off, the design based on the uneven shape of the surface on the first main surface 11 side and the design based on the first design layer 21 are visible. When the light is on, the designs based on the second design layer 22 and the third design layer 23 are visible. In the laminate 10 of the present invention, when the light source 30 is on, the design that appears when the light source 30 is off is difficult to see, but when the light source is off, the design is visible.
• a transparent resin layer 1 is disposed between the first design layer 21 and the second design layer 22, and further, it is important that the surface 22a of the second design layer 22 on the first main surface 11 side is made relatively flatter than the uneven shape of the first main surface 11.
• the surface 22a of the second design layer 22 on the first main surface 11 side may have a shape that is relatively flatter than the uneven shape of the first main surface 11.
• the depth of the recesses of the surface 22a of the second design layer 22 on the first main surface 11 side is relatively smaller than the depth of the recesses of the uneven shape of the first main surface 11.
• the surface 22a of the second design layer 22 on the first main surface 11 side is substantially flat.
• the uneven shape of the first main surface 11 is not reflected in the shape of the surface 22a of the second design layer 22 on the first main surface 11 side, and even in this case, it is acceptable to have a slightly uneven shape.
• the surface of the second design layer 22 on the second main surface 12 side is also preferably flatter than the uneven shape of the first main surface 11, and is more preferably approximately flat.
• a surface protective layer 3 may be further provided on the first design layer 21 (first main surface 11 side) for the purpose of imparting surface protection performance such as scratch resistance and chemical resistance to the surface.
• a primer layer (not shown) may be provided as necessary for the purpose of increasing the adhesion between the surface protective layer 3 and the layer located thereunder (such as the first design layer 21).
• an adhesive layer (not shown) may be provided on at least one surface of the second design layer 22.
• a back adhesive layer (not shown) may be provided on the second main surface 12 side of the transparent substrate layer 4 (back surface side of the transparent substrate layer 4) as necessary for the purpose of increasing the adhesion between the laminate 10 of the present invention and the molded resin layer 5.
• the laminate of the present invention may further include one or more other layers depending on the function to be imparted to the laminate or the decorative article.
• the laminate structure of the laminate of the present invention includes, in order from the first main surface side, a laminate structure in which a first design layer/transparent resin layer 1/second design layer/third design layer are laminated; a laminate structure in which a first design layer/transparent resin layer 1/third design layer/second design layer are laminated; a laminate structure in which a first design layer/transparent resin layer 1/second design layer/third design layer/transparent substrate layer are laminated; a laminate structure in which a first design layer/transparent resin layer 1/third design layer/second design layer/transparent substrate layer are laminated.
• FIG. 1 shows a schematic cross-sectional view of an example of a laminate in which a first design layer/transparent resin layer 1/second design layer/third design layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 2 shows a schematic cross-sectional view of an example of a laminate in which a first design layer/transparent resin layer 1/third design layer/second design layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 2 shows a schematic cross-sectional view of an example of a laminate in which a first design layer/transparent resin layer 1/third design layer/second design layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 3 shows a schematic cross-sectional view of an example of a laminate in which a first design layer/transparent resin layer/second design layer/third design layer/transparent substrate layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 4 shows a schematic cross-sectional view of an example of a laminate in which a surface protective layer/first design layer/transparent resin layer/second design layer/third design layer/transparent substrate layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 4 shows a schematic cross-sectional view of an example of a laminate in which a surface protective layer/first design layer/transparent resin layer/second design layer/third design layer/transparent substrate layer are laminated in order from the first main surface side as one embodiment of the laminate structure of the laminate of the present invention.
• FIG. 5 shows a schematic cross-sectional view of an example of a laminate having a laminate structure of the present invention, in which a surface protective layer/first design layer/transparent resin layer 1/second design layer/third design layer/transparent substrate layer/molded resin layer are laminated in this order from the first main surface side.
• the surface of the first design layer 21 on the first main surface 11 side has an uneven shape 21a. It is preferable that the uneven shape of the first main surface 11 of the laminate 10 and the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21 correspond to each other. As shown in Figures 1 and 2, when the first design layer 21 constitutes the first main surface 11 of the laminate 10, the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21 matches the uneven shape of the first main surface 11.
• the surface of the first design layer 21 on the second main surface 12 side has an uneven shape. As shown in Figures 1 and 2, it is preferable that the uneven shape 21a on the surface of the first design layer 21 on the first main surface 11 side and the uneven shape on the second main surface 12 side have corresponding shapes.
• the transparent resin layer 1 may have an uneven shape.
• the uneven shape is preferably provided on the first main surface 11 side (i.e., the transparent resin layer 1 has an uneven shape 1a on the first main surface 11 side) as shown in Figures 1 to 5.
• the uneven shape 1a on the first main surface side of the transparent resin layer 1 corresponds, for example, to the uneven shape 21a on the surface on the first main surface 11 side of the first design layer 21. That is, in the laminate 10 of the present invention, an uneven shape corresponding to the uneven shape of the first main surface 11 can be provided, for example, from the first main surface 11 to the transparent resin layer 1 (particularly, to the surface on the first main surface 11 side of the transparent resin layer 1).
• the ratio of the depth D of the recesses of the uneven shape of the first main surface 11 to the thickness of the transparent resin layer 1 is preferably 60% or less, and preferably 10% or more, with the preferred range being 10 to 60%.
• the depth D of the recesses of the uneven shape of the first main surface 11 in the laminate 10 of the present invention is preferably 10 ⁇ m or more and 100 ⁇ m or less.
• the depth of the recess can be measured, for example, by observing the cross section with a microscope.
• the depth D of the recess is the height from the recess to the protrusion of the uneven shape of the first main surface 11, as shown in Figures 1 to 3.
• the width W of the recesses in the uneven shape of the first main surface 11 is preferably about 30 to 500 ⁇ m, and more preferably about 100 to 300 ⁇ m.
• the width W of the recesses can be measured, for example, by observing the cross section with a microscope.
• the width W of the recesses is the distance between adjacent protrusions in the uneven shape of the first main surface 11, as shown in Figures 1 to 3.
• the uneven shape of the first main surface 11 can be suitably formed, for example, by embossing.
• embossing For example, a laminate in which at least the first design layer 21 and the transparent resin layer 1 are laminated is prepared, and an embossing process is carried out from the first main surface 11 side, thereby forming an uneven shape on the first main surface 11 side of the first design layer 21.
• embossing process by adjusting the depth of the recesses formed by the embossing process, it is also possible to form an uneven shape in the first design layer 21 and the transparent resin layer 1 by a single embossing process.
• Embossing is a known method, for example, by pressing a heated and softened layer with an embossing plate, imprinting the embossed pattern on the surface of the laminate, and then cooling and fixing the pattern.
• a known sheet-fed or rotary embossing machine can be used for embossing.
• the uneven shape can be formed in these layers as well by, for example, forming an uneven shape by embossing a laminate in which these layers and the first design layer 21 are laminated on the transparent resin layer 1.
• the uneven shapes formed in each layer can be made to match.
• the uneven shape of the surface protective layer 3 corresponds to the uneven shape of the first design layer 21.
• the first design layer 21 is a layer provided on the first main surface 11 side of the transparent resin layer 1 for the purpose of imparting decorativeness to the laminate.
• the design of the first design layer 21 is a design that is visible when the light source 30 on the second main surface 12 side is turned off.
• the design of the first design layer 21 is difficult to see from the first main surface 11 side, and the designs of the second design layer 22 and the third design layer 23 are visible.
• the light source 30 is turned off, when the laminate 10 of the present invention is observed from the first main surface 11 side, the designs of the second design layer 22 and the third design layer 23 are difficult to see.
• FIGS. 6 and 7 show conceptual diagrams of the laminate 10 of the present invention when observed from the first main surface 11 side (observer side) when the light source 30 is turned on.
• the black part is the design of the third design layer 23, and the three rectangular parts therein (geometric pattern in Fig. 6, gray gradation pattern in Fig. 7) are the design of the second design layer 22.
• the third design layer 23 functions as a light-shielding layer that blocks light transmission, while the second design layer functions as a pattern layer that transmits light.
• the design of the first design layer 21 is difficult to see from the first main surface 11 side. That is, for example, in Fig. 6, the observer can see three rectangles that shine with a geometric pattern. Also, for example, in Fig. 7, the observer can see three rectangles that shine with a gradation.
• the surface of the first design layer 21 on the first main surface 11 side has an uneven shape 21a. Furthermore, it is preferable that the uneven shape of the first main surface 11 and the uneven shape 21a of the surface of the first design layer 21 on the first main surface 11 side correspond to each other. As shown in Figures 1 and 2, when the first design layer 21 constitutes the first main surface 11 of the laminate 10, the uneven shape 21a of the surface of the first design layer 21 on the first main surface 11 side matches the uneven shape of the first main surface 11.
• the surface of the first design layer 21 on the second main surface 12 side has an uneven shape. As shown in Figures 1 and 2, it is preferable that the uneven shape 21a on the surface of the first design layer 21 on the first main surface 11 side and the uneven shape on the second main surface 12 side have corresponding shapes.
• the first design layer 21 which has an uneven shape, scatters light, it becomes easier to achieve the effect of making the designs based on the second design layer 22 and the third design layer 23 less visible when the light is off.
• the uneven shape may be provided only on the first main surface 11 side, or as shown in Figures 1 to 5, it may also be provided on the second main surface 12 side.
• the first design layer 21 can be, for example, a layer on which a desired pattern is formed using an ink composition.
• the first design layer 21 has a monochrome design over the entire surface, and the second design layer 22 and the third design layer 23 have patterned designs, it is possible to configure the first design layer 21 so that when the light source is turned off, the monochrome design over the entire surface is visible, and the designs of the second design layer 22 and the third design layer 23 are not visible, and when the light source is turned on, the patterned designs of the second design layer 22 and the third design layer 23 (for example, the aforementioned patterns such as symbols and text information) are visible.
• the first design layer 21 may be provided partially on the transparent resin layer 1 or may be provided over the entire surface, and it is preferable that it is provided over the entire surface.
• the first design layer 21 can be formed, for example, by printing an ink for forming the first design layer onto the transparent resin layer 1 using a conventionally known printing method such as gravure printing, silk screen printing, or offset printing.
• a conventionally known printing method such as gravure printing, silk screen printing, or offset printing.
• the ink composition used to form the first design layer 21 include the same ones as those exemplified for the second design layer 22 described below, including binders, colorants, etc.
• the patterns formed by the first design layer 21 may be the same as those exemplified for the second design layer 22 described below, but as mentioned above, it is preferable for the first design layer 21 to have a monochrome design across the entire surface.
• the first design layer 21 may also include a portion formed of a metal thin film.
• the metals and methods for forming the metal thin film are the same as those exemplified for the second design layer 22.
• the thickness of the first design layer 21 is not particularly limited, but the lower limit is preferably 1 ⁇ m or more, and the upper limit is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, with preferred ranges being approximately 1 to 20 ⁇ m, and approximately 1 to 10 ⁇ m. Note that if the first design layer 21 has an uneven shape, the thickness of the first design layer 21 is the thickness at the position of the convex parts of the uneven shape.
• the optical density (OD value) of the first design layer 22 is preferably 2.5 or less, and preferably 0.3 or more, with a preferred range being 0.3 to 2.5. It is preferable that the sum of the OD value of the first design layer and the OD value of the second design layer described below is less than 3.5.
• the transparent resin layer 1 is provided between the first design layer 21 and the second and third design layers 22 and 23, and when the light source 30 is turned on, it exerts a function of making the design (for example, the design of the first design layer 21) that appears when the light source 30 is turned off difficult to see, while making the design by the second design layer 22 and the third design layer 23 easy to see, and when the light source 30 is turned off, it exerts a function of making the design (for example, the design of the first design layer 21) that appears when the light source 30 is turned off easy to see, while making the design by the second design layer 22 and the third design layer 23 difficult to see.
• the design for example, the design of the first design layer 21
• the design for example, the design of the first design layer 21
• the design that appears when the light source 30 is turned off is visible together with the design by the second design layer 22 and the third design layer 23, making it difficult to achieve the object of the present invention.
• the transparent resin layer 1 is transparent enough to transmit light from the light source 30 (transparent in the present invention includes translucency). That is, the transparent resin layer 1 is usually transparent (colorless transparent, colored transparent, translucent), and may be colored as long as the design based on the second design layer 22 and the third design layer 23 is visible when the laminate 10 of the present invention is observed from the first main surface 11 side when it is turned on.
• the transparent resin layer 1 may contain a matting agent such as silica or a coloring agent.
• the coloring agent the coloring agent exemplified for the second design layer 22 described later can be used.
• the transparent resin layer 1 may be painted to adjust the color, or a pattern may be formed to impart design.
• the transparent resin layer 1 may have an uneven shape.
• the transparent resin layer 1 has an uneven shape
• it is preferable that the uneven shape is provided on the first main surface 11 side (having an uneven shape 1a on the first main surface 11 side of the transparent resin layer 1) as shown in Figures 1 to 5.
• the uneven shape 1a on the first main surface 11 side of the transparent resin layer 1 corresponds to, for example, the uneven shape of the first main surface 11 described above and the uneven shape of the first design layer 21. That is, in the laminate 10 of the present invention, the uneven shape can be provided so as to extend from the first main surface 11 to the transparent resin layer 1.
• the surface on the second main surface 12 side of the transparent resin layer 1 is preferably flatter than the uneven shape of the first main surface 11 of the laminate 10, and is more preferably approximately flat.
• the layer in contact with the surface on the second main surface 12 side of the transparent resin layer 1 is preferably flatter than the uneven shape of the first main surface 11 of the laminate 10, and more preferably approximately flat.
• the maximum height roughness Rz of the surface on the second main surface 12 side of the transparent resin layer 1 is preferably 50% or less of the Rz of the uneven shape of the first main surface 11.
• Rz is measured in accordance with JIS B0601 (1996).
• the transparent resin layer 1 can be made of a transparent resin from the viewpoint of making the laminate 10 suitable for three-dimensional molding while suitably expressing a design that differs when the light source is on and off.
• the transparent resin is preferably made of a transparent thermoplastic resin.
• Transparent thermoplastic resins are not particularly limited, but include transparent acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylic resin; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylic ester resin, etc.
• the transparent resin layer 1 is preferably made of a transparent acrylic resin.
• the resin forming the transparent resin layer 1 may be one type or two or more types.
• the thickness of the transparent resin layer 1 is not particularly limited, but from the viewpoint of making the laminate 10 suitable for three-dimensional molding and suitably expressing a design that differs between when the light source is on and when it is off, the lower limit is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and the upper limit is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and preferred ranges include about 50 to 200 ⁇ m, about 50 to 150 ⁇ m, about 70 to 200 ⁇ m, and about 70 to 150 ⁇ m. Note that when the transparent resin layer 1 has an uneven shape, the thickness of the transparent resin layer 1 is the thickness at the positions of the convex parts of the uneven shape.
• the transparent resin layer 1 may be subjected to physical or chemical surface treatment such as oxidation or roughening on one or both sides as necessary to improve adhesion with adjacent layers.
• oxidation methods used as surface treatments of the transparent resin layer 1 include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone ultraviolet treatment.
• roughening methods used as surface treatments of the transparent resin layer 1 include sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of resin that constitutes the transparent resin layer 1, but from the standpoint of effectiveness and operability, corona discharge treatment is preferred.
• the total light transmittance of the transparent resin layer 1 is preferably about 70% or more, more preferably about 80% or more, and even more preferably about 90% or more.
• the total light transmittance is measured using a haze meter in accordance with JIS K7361-1.
• the second design layer 22 is a layer provided on the second main surface 12 side of the transparent resin layer 1 for the purpose of imparting decorativeness to the laminate 10.
• the design of the second design layer 22 is a design that is visible from the first main surface 11 side when the light source on the second main surface 12 side is turned on, and when the light source 30 is turned off, the design of the second design layer 22 is difficult to see from the first main surface 11 side, and the design of the first design layer 21 is visible.
• the second design layer 22, together with the third design layer 23 described below is provided so as to reveal a design when the light source 30 is turned on.
• the first design layer 21 described above has a monochrome design
• the patterned design of the second design layer 22 and the third design layer 23 is visible.
• the second design layer 22 may be provided partially or entirely, and is preferably provided entirely.
• the optical density (OD value) of the second design layer 22 is preferably 3.0 or less, and preferably 0.5 or more, with a preferred range of 0.5 to 3.0.
• the second design layer 22 can be, for example, a layer in which a desired pattern is formed using an ink composition.
• the second design layer 22 can be formed, for example, by printing an ink for forming the second design layer using a conventionally known printing method such as gravure printing, silk screen printing, or offset printing.
• the ink composition used to form the second design layer 22 is an appropriate mixture of a binder, a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, etc.
• the binder used in the ink composition is not particularly limited, but examples include polyurethane resin, vinyl chloride/vinyl acetate copolymer resin, vinyl chloride/vinyl acetate/acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc. These binders may be used alone or in combination of two or more.
• the colorants used in the ink composition are not particularly limited, but examples include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments made of scaly flakes such as aluminum and brass; and pearlescent pigments made of scaly flakes such as titanium dioxide-coated mica and basic lead carbonate.
• inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue
• organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue
• metal pigments made of scaly flakes such as aluminum and brass
• pearlescent pigments made of scaly flakes such as titanium dioxide-
• the pattern formed by the second design layer 22 is not particularly limited, but examples include symbols and text information, as well as geometric patterns such as dot patterns, line patterns, and carbon patterns, gradation patterns, wood grain patterns, stone patterns that imitate the surface of rocks such as marble patterns (e.g., travertine marble patterns), fabric patterns that imitate cloth grain or cloth-like patterns, tile patterns, brickwork patterns, and the like. These may also be combined to form patterns such as marquetry and patchwork, or may be a single solid color (so-called solid color on the entire surface). These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but can also be formed by multi-color printing using special colors, which is performed by preparing plates of the individual colors that make up the pattern.
• geometric patterns such as dot patterns, line patterns, and carbon patterns, gradation patterns, wood grain patterns, stone patterns that imitate the surface of rocks such as marble patterns (e.g., travertine marble patterns), fabric patterns that imitate cloth grain or cloth-like patterns
• the second design layer 22 may also include a portion composed of a metal thin film.
• metals that form the metal thin film include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these.
• deposition methods such as vacuum deposition using the above metals, sputtering, and ion plating.
• a primer layer made of a known resin may be provided on the front and back surfaces of the metal thin film.
• the surface 22a on the first main surface 11 side of the second design layer 22 is relatively flatter than the uneven shape of the first main surface 11.
• the surface 22a on the first main surface 11 side of the second design layer 22 may have a shape that is relatively flatter than the uneven shape of the first main surface 11.
• the depth of the recesses on the surface 22a on the first main surface 11 side of the second design layer 22 is relatively smaller than the depth of the recesses of the uneven shape of the first main surface 11. From the viewpoint of more suitably exerting the effects of the present invention, it is preferable that the surface 22a on the first main surface 11 side of the second design layer 22 is approximately flat.
• the uneven shape of the first main surface 11 is flat to the extent that it is not reflected in the shape of the surface 22a on the first main surface 11 side of the second design layer 22, and even in this case, it is acceptable to have a slight uneven shape.
• the maximum height roughness Rz of the surface on the first main surface 11 side of the second design layer 22 be 50% or less of the Rz of the uneven shape of the first main surface 11.
• Rz is measured in accordance with JIS B0601 (1996).
• the shape of the surface on the second main surface side of the transparent resin layer and the shape of the surface on the first main surface side of the second design layer are complementary to each other.
• the surface on the second principal surface 12 side of the second design layer 22 is also preferably flatter than the uneven shape of the first principal surface 11, and is more preferably approximately flat. Although there are no particular restrictions on “relatively flat,” it is preferable that the maximum height roughness Rz of the surface on the second principal surface 12 side of the second design layer 22 is 50% or less of the Rz of the uneven shape of the first principal surface 11. Rz is measured in accordance with JIS B0601 (1996).
• the thickness of the second design layer 22 is not particularly limited, but the lower limit is preferably 1 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, with preferred ranges being approximately 1 to 30 ⁇ m, and approximately 1 to 20 ⁇ m. Note that if the second design layer 22 has an uneven shape, the thickness of the second design layer 22 is the thickness at the position of the convex parts of the uneven shape.
• the third design layer 23 is a layer provided on the first main surface 11 or the second main surface 12 of the second design layer 22 for the purpose of providing decorativeness to the laminate 10. Specifically, as shown in Fig. 2, when the third design layer 23 is provided on the first main surface 11 of the second design layer 22, the third design layer 23 exists between the transparent resin layer 1 and the second design layer 22. Also, as shown in Fig. 3, when the laminate 10 includes a transparent substrate layer 4 described later and the third design layer 23 is provided on the second main surface 12 of the second design layer 22, the third design layer 23 exists between the second design layer 22 and the transparent substrate layer 4.
• the surface on the first main surface side of the second design layer may be relatively flatter than the uneven shape of the first main surface.
• the surface on the first main surface side of the second design layer may be relatively flatter than the uneven shape of the first main surface.
• the third design layer 23 is provided partially when the main surface of the laminate 10 is the entire surface. When the laminate 10 of the present invention is observed from the first main surface 11 side, the third design layer 23 is provided together with the second design layer 22 described above so as to express a design when the light source 30 is turned on.
• the second design layer 22 and the third design layer 23 have a patterned design and the first design layer 21 described above has a monochromatic design
• the monochromatic design of the first design layer 21 is visible, and the designs of the second design layer 22 and the third design layer 23 are not visible
• the patterned design of the second design layer 22 and the third design layer 23 (for example, a pattern such as a symbol or text information, which will be described later) can be configured to be visible.
• the optical density (OD value) of the third design layer 23 is preferably 3.5 or more and preferably 7.0 or less, with a preferred range being 3.5 to 7.0.
• the third design layer 23 can be formed, for example, by printing an ink for forming the third design layer using a conventionally known printing method such as gravure printing, silk screen printing, offset printing, etc.
• a conventionally known printing method such as gravure printing, silk screen printing, offset printing, etc.
• the ink composition used to form the third design layer 23 include the same ones as those exemplified for the second design layer 22 described above, including binders, colorants, etc.
• the patterns formed by the third design layer 23 may be the same as those exemplified for the second design layer 22 described above, but as mentioned above, it is preferable that the third design layer 23 is formed partially and, together with the second design layer 22, expresses the desired design.
• the third design layer 23 may also include a portion formed of a metal thin film.
• the metals and methods for forming the metal thin film may be the same as those exemplified for the second design layer 22.
• the thickness of the third design layer 23 is not particularly limited, but the lower limit is preferably 1 ⁇ m or more, and the upper limit is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, with preferred ranges being approximately 1 to 20 ⁇ m, and approximately 1 to 10 ⁇ m.
• the transparent substrate layer 4 is a layer that is provided as necessary on the second main surface 12 side of the second design layer 22 and the third design layer 23 in order to provide rigidity and maintain the shape of the laminate 10.
• the transparent substrate layer 4 is provided to make the laminate suitable for vacuum molding (three-dimensional molding) by insert molding or the like.
• the transparent substrate layer 4 is transparent enough to transmit light from the light source (as mentioned above, in the present invention, transparent includes translucency). That is, the transparent substrate layer 4 is usually transparent (colorless transparent, colored transparent, translucent), and may be colored as long as the design based on the second design layer 22 and the third design layer 23 is visible when the laminate 10 of the present invention is observed from the first main surface 11 side when the laminate 10 is turned on.
• the transparent substrate layer 4 may contain a matting agent such as silica, a coloring agent, etc.
• the coloring agent the coloring agents exemplified for the second design layer 22 mentioned above can be used.
• the transparent substrate layer 4 can be made of a transparent resin, a paper substrate, or the like, from the viewpoint of making the laminate 10 suitable for three-dimensional molding while suitably expressing a design that differs when the light source is on and off.
• the transparent resin is preferably made of a transparent thermoplastic resin.
• Transparent thermoplastic resins are not particularly limited, but include transparent acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylic resin; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylic ester resin, and the like.
• the transparent substrate layer 4 is preferably made of a transparent ABS resin.
• the resin forming the transparent substrate layer 4 may be one type or two or more types.
• the thickness of the transparent substrate layer 4 is not particularly limited, but from the viewpoint of making the laminate 10 suitable for three-dimensional molding and suitably expressing a design that differs between when the light source is on and when it is off, the lower limit is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and the upper limit is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, with preferred ranges being around 50 to 1000 ⁇ m and around 100 to 500 ⁇ m. More specifically, if a transparent ABS resin is used as the transparent substrate layer 4, the preferred range is around 100 to 500 ⁇ m, and even more preferably 200 to 400 ⁇ m.
• the transparent substrate layer 4 may be subjected to physical or chemical surface treatment such as oxidation or roughening on one or both sides as necessary to improve adhesion with adjacent layers.
• oxidation methods used as surface treatments of the transparent substrate layer 4 include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone ultraviolet treatment.
• roughening methods used as surface treatments of the transparent substrate layer 4 include sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of resin that constitutes the transparent substrate layer 4, but from the standpoint of effectiveness and operability, corona discharge treatment is preferred.
• the surface protective layer 3 is a layer that is provided as necessary in order to protect the surface of the laminate 10. In the laminate 10, the surface protective layer 3 is provided on the outermost surface on the first main surface 11 side.
• the surface protective layer 3 can be formed with a concave-convex shape by embossing the laminate together with the first design layer 21, the transparent resin layer 1, etc., to form a concave-convex shape.
• the surface protective layer 3 may have a concave-convex shape 3a.
• the concave-convex shape 3a may be provided on the first main surface 11 side, or may be provided on the second main surface 12 side.
• the surface on the first main surface 11 side of the surface protective layer 3 has an uneven shape 3a. Furthermore, it is preferable that the uneven shape of the first main surface 11 and the uneven shape 3a of the surface on the first main surface 11 side of the surface protective layer 3 have corresponding shapes. As shown in Figures 4 and 5, when the surface protective layer 3 constitutes the first main surface 11 of the laminate 10, the uneven shape 3a of the surface on the first main surface 11 side of the surface protective layer 3 matches the uneven shape of the first main surface 11.
• the surface protective layer 3 may be provided over the entire surface of the first main surface 11, or may be provided partially. However, from the viewpoint of optimally protecting the surface of the laminate 10, it is preferable that the surface protective layer 3 be provided over the entire surface of the first main surface 11.
• the surface protective layer 3 is usually transparent (colorless transparent, colored transparent, translucent), but may be colored or may contain a matting agent such as silica, as long as the design of the second design layer 22 and the third design layer 23 is visible when the light source 30 is turned on when the laminate 10 of the present invention is observed from the first main surface 11 side.
• a matting agent such as silica
• the colorant the colorants exemplified for the first design layer 21 described above can be used.
• the material constituting the surface protective layer 3 is not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and ionizing radiation curable resins. Among these, from the viewpoint of improving scratch resistance, it is preferable that the surface protective layer 3 is composed of a cured product of an ionizing radiation curable resin composition.
• the ionizing radiation curable resin used to form the surface protective layer 3 is described in detail below.
• the ionizing radiation curable resin used in the formation of the surface protective layer 3 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically includes a suitable mixture of at least one of prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule.
• the ionizing radiation means electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, but also includes electromagnetic waves such as X-rays and ⁇ -rays, charged particle beams such as ⁇ -rays and ion beams.
• UV ultraviolet rays
• EB electron beams
• electron beam curable resins are preferably used in the formation of the surface protective layer 3 because they can be made solvent-free, do not require a photopolymerization initiator, and have stable curing properties.
• a (meth)acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable, and among these, a polyfunctional (meth)acrylate monomer is preferred.
• the polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more), polymerizable unsaturated bonds in the molecule.
• polyfunctional (meth)acrylate examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylol propionate, and the like.
• Examples of the monomer include propane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. These monomers may be used alone or in combination of two or more.
• a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferred, and among these, a polyfunctional (meth)acrylate oligomer having two or more polymerizable unsaturated bonds (bifunctional or more) in the molecule is preferred.
• polyfunctional (meth)acrylate oligomers examples include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, and oligomers having a cationic polymerizable functional group in the molecule (e.g., novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.).
• oligomers having a cationic polymerizable functional group in the molecule e.g., novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.
• the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group at the end or side chain, and can be obtained, for example, by esterifying a polycarbonate polyol with (meth)acrylic acid.
• the polycarbonate (meth)acrylate may be, for example, a urethane (meth)acrylate having a polycarbonate skeleton.
• the urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyvalent isocyanate compound and a hydroxy (meth)acrylate.
• the acrylic silicone (meth)acrylate can be obtained by radical copolymerization of a silicone macromonomer with a (meth)acrylate monomer.
• the urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth)acrylic acid.
• Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin to esterify it.
• a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic anhydride can also be used.
• Polyester (meth)acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth)acrylic acid, or by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid.
• Polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid.
• Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer.
• Silicone (meth)acrylates can be obtained by adding (meth)acrylic acid to the end or side chain of a silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.
• polycarbonate (meth)acrylate from the viewpoint of obtaining excellent three-dimensional moldability while further improving the appearance of the design, abrasion resistance, and moldability. It is also preferable to use a combination of polycarbonate (meth)acrylate and urethane (meth)acrylate.
• additives can be blended into the surface protective layer 3 according to the desired physical properties to be provided to the surface protective layer 3.
• the additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants, and the like.
• weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants, and the like.
• reactive ultraviolet absorbers and light stabilizers having a polymerizable group such as a (meth)acryloy
• the surface protection layer 3 can be formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the composition to form an uncured resin layer, and crosslinking and curing the uncured resin layer.
• the viscosity of the ionizing radiation curable resin composition may be any viscosity that allows the formation of an uncured resin layer using the coating method described below.
• the prepared resin is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating, preferably gravure coating, to form an uncured resin layer.
• the uncured resin layer thus formed is then irradiated with ionizing radiation such as electron beams or ultraviolet rays to cure the uncured resin layer and form the surface protection layer 3.
• ionizing radiation such as electron beams or ultraviolet rays
• the acceleration voltage can be appropriately selected depending on the resin used and the thickness of the layer, but typically the acceleration voltage is about 70 to 300 kV.
• the acceleration voltage is selected so that the penetration depth of the electron beam is substantially equal to the thickness of the surface protective layer 3. This makes it possible to prevent excess irradiation of the electron beam to the layer located under the surface protective layer 3, and to minimize the deterioration of each layer due to excess electron beams.
• the exposure dose is preferably an amount at which the crosslink density of the surface protective layer 3 becomes saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
• electron beam accelerators there are no particular limitations on the electron beam source, and various types of electron beam accelerators can be used, such as Cockroft-Walton type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.
• ultraviolet light When ultraviolet light is used as the ionizing radiation, light containing ultraviolet light with a wavelength of 190 to 380 nm may be emitted.
• the ultraviolet light source There are no particular limitations on the ultraviolet light source, but examples include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.
• the surface protective layer 3 thus formed may be treated with various additives to impart functions such as a hard coat function, an anti-fogging coat function, an anti-soiling coat function, an anti-glare coat function, an anti-reflection coat function, an ultraviolet shielding coat function, an infrared shielding coat function, etc.
• the thickness of the surface protective layer 3 is not particularly limited, but from the viewpoint of imparting surface protective performance such as scratch resistance and chemical resistance, the lower limit is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, with preferred ranges being about 5 to 20 ⁇ m, about 5 to 10 ⁇ m, and about 5 to 15 ⁇ m.
• the primer layer is a layer that is provided, if necessary, between the surface protective layer 3 and the first design layer 21 so as to be in contact with the surface on the second main surface 12 side of the surface protective layer 3, for the purpose of increasing adhesion between the surface protective layer 3 and the layer located below it.
• the primer composition constituting the primer layer those using urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, etc. as a binder resin are preferably used, and these resins can be used alone or in a mixture of two or more kinds.
• urethane resin, (meth)acrylic resin, and (meth)acrylic-urethane copolymer resin are preferred.
• polyurethane resin polyurethane can be used, which uses polyol (polyhydric alcohol) as the main component and isocyanate as the crosslinking agent (curing agent).
• polyol polyhydric alcohol
• isocyanate crosslinking agent
• the polyol one having two or more hydroxyl groups in the molecule, such as polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc., can be used.
• the isocyanate a polyisocyanate having two or more isocyanate groups in the molecule, an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, or an aliphatic (or alicyclic) isocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, or hydrogenated diphenylmethane diisocyanate can be used. It is also possible to compose the resin by mixing urethane resin and butyral resin.
• an acrylic polyol or polyester polyol as the polyol with hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as the crosslinking agent, and it is particularly preferable to use a combination of an acrylic polyol and hexamethylene diisocyanate.
• (Meth)acrylic resins include homopolymers of (meth)acrylic acid esters, copolymers of two or more different (meth)acrylic acid ester monomers, or copolymers of (meth)acrylic acid esters and other monomers.
• (meth)acrylic resins made of homopolymers or copolymers containing (meth)acrylic acid esters, such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, polypropyl(meth)acrylate, polybutyl(meth)acrylate, methyl(meth)acrylate-butyl(meth)acrylate copolymer, ethyl(meth)acrylate-butyl(meth)acrylate copolymer, ethylene-methyl(meth)acrylate copolymer, and styrene-methyl(meth)acrylate copolymer, are preferably used.
• the (meth)acrylic-urethane copolymer resin for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferred.
• the various isocyanates mentioned above are used.
• the acrylic/urethane ratio (mass ratio) of the acrylic-urethane (polyester urethane) block copolymer resin is preferably adjusted within the range of 9/1 to 1/9, more preferably 8/2 to 2/8.
• the thickness of the primer layer is not particularly limited, but is, for example, about 0.5 to 20 ⁇ m, and preferably about 1 to 5 ⁇ m.
• the primer layer is formed using a primer composition by a conventional coating method such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, solid coating by silk screen, wire bar coating, flow coating, comma coating, pouring coating, brush coating, spray coating, or a transfer coating method.
• the transfer coating method is a method in which a coating film of the primer layer or adhesive layer is formed on a thin sheet (film substrate), and then coated on the target layer surface in the laminate.
• the adhesive layer (not shown) is a layer that is provided as necessary for the purpose of bonding each layer.
• the adhesive layer is provided on at least one side of the second design layer 22, and can bond the second design layer 22 to the transparent resin layer 1, the third design layer 23, the transparent substrate layer 4, or the like.
• the adhesive layer may be made of a thermoplastic resin, a curable resin, or the like, depending on the type of layer being bonded.
• Thermoplastic resins used to form the adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber-based resins, etc. These thermoplastic resins may be used alone or in combination of two or more.
• Thermosetting resins used to form the adhesive layer include, for example, urethane resins and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.
• the thickness of the adhesive layer can be, for example, about 0.1 to 20 ⁇ m.
• the back surface adhesive layer (not shown) is a layer that is provided, if necessary, on the second main surface 12 side (the side opposite the first design layer 21) of the transparent substrate layer 4 for the purpose of increasing adhesion with the molded resin layer 5 when the laminate 10 is molded, when the laminate 10 is provided with a molded resin layer 5.
• the back adhesive layer is made of a thermoplastic resin or a curable resin, depending on the type of molded resin layer 5 used in the laminate 10.
• Thermoplastic resins used to form the backside adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber-based resins, etc. These thermoplastic resins may be used alone or in combination of two or more.
• Thermosetting resins used to form the backside adhesive layer include, for example, urethane resins, epoxy resins, etc. These thermosetting resins may be used alone or in combination of two or more.
• the thickness of the back surface adhesive layer is not particularly limited as long as it can adhere the molded resin layer 5, and may be, for example, about 0.1 to 20 ⁇ m.
• a transparent molded resin layer 5 may be integrally molded on the second main surface 12 side. That is, as shown in FIG. 5, the laminate 10 of the present invention is a laminate including at least the molded resin layer 5, the second design layer, the transparent resin layer 1, and the first design layer 21 in this order, and further including a third design layer 23 on the first main surface 11 side or the second main surface 12 side of the second design layer 22.
• the molded resin layer 5 is transparent to the extent that light from the light source can be transmitted when the light source 30 is arranged on the second main surface 12 side, similar to the transparent substrate layer 4.
• the molded resin layer 5 is usually transparent (colorless transparent, colored transparent, translucent), and may be colored as long as the design of the second design layer 22 and the third design layer 23 can be visually recognized when the laminate 10 of the present invention is observed from the first main surface 11 side.
• the molded resin layer 5 may contain a matting agent such as silica, a colorant, or the like.
• the colorant the colorants exemplified for the second design layer 22 described above can be used.
• the molded resin layer 5 can be made of a transparent resin or the like.
• the transparent resin is preferably made of a transparent thermoplastic resin.
• transparent thermoplastic resin There are no particular limitations on the transparent thermoplastic resin, but examples include transparent acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylic resin, polyolefin resins such as polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) resin, and acrylonitrile-styrene-acrylic ester resin.
• the molded resin layer 5 is preferably made of polycarbonate resin because of its excellent transparency.
• the resin forming the molded resin layer 5 may be one type or two or more types.
• examples of the shape of the molded resin layer 5 include a plate-like body and a molded body.
• the laminate 10 having the molded resin layer 5 is produced by laminating the molded resin layer 5 using a known method. If the molded resin layer 5 is a resin molded body, it may be produced by an injection molding method such as an insert molding method.
• the laminate before laminating the molded resin layer 5 i.e., a laminate having, in order from the second main surface 12 side, at least the second design layer 22, the transparent resin layer 1, and the first design layer 21, and further having the third design layer 23 on the first main surface 11 side or the second main surface 12 side of the second design layer 22
• the laminate before laminating the molded resin layer 5 i.e., a laminate having, in order from the second main surface 12 side, at least the second design layer 22, the transparent resin layer 1, and the first design layer 21, and further having the third design layer 23 on the first main surface 11 side or the second main surface 12 side of the second design layer 22
• the laminate before laminating the molded resin layer 5 i.e., a laminate having, in order from the second main surface 12 side, at least the second design layer 22, the transparent resin layer 1, and the first design layer 21, and further having the third design layer 23 on the first main surface 11 side or the second main surface 12 side of the second design layer 22
• offline preforming into the molded product surface shape
• This molded sheet is inserted into an injection mold, the injection mold is clamped, and a resin in a fluid state is injected into the mold from the transparent substrate layer 4 side of the laminate and solidified, and the molded sheet is integrated with the outer surface of the resin molded product at the same time as the injection molding, thereby manufacturing a laminate 10 with the molded resin layer 5.
• the laminate 10 including the molded resin layer 5 is manufactured by an insert molding method including the following steps. a vacuum forming process in which the laminate before the molded resin layer 5 is laminated is preformed into a three-dimensional shape using a vacuum forming mold; a trimming process in which excess portions of the vacuum formed laminate are trimmed off to obtain a molded sheet; and an integration process in which the molded sheet is inserted into an injection mold, the injection mold is closed, and a flowable resin is injected into the injection mold from the transparent substrate layer 4 side to integrate the resin and the molded sheet.
• the laminate may be heated and molded.
• the heating temperature at this time is not particularly limited and may be selected appropriately depending on the type of resin that constitutes the laminate and the thickness of the laminate, but is usually about 120°C to 200°C.
• the temperature of the resin in a fluid state is not particularly limited, but is usually about 180°C to 320°C.
• the molded resin layer 5 may be formed by selecting a resin appropriate for the application.
• the molded resin forming the molded resin layer 5 may be the thermoplastic resin described above, or may be a thermosetting resin.
• thermosetting resins examples include urethane resins and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.
• the laminate 10 of the present invention expresses a different design when the light source is on and off, and therefore, when used in combination with a light source, can be used as, for example, interior or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; housings for home appliances such as television sets and air conditioners; containers, etc.
• the decorative article 20 of the present invention utilizes the laminate 10 of the present invention, and includes the laminate 10 and a light source 30. As shown in Fig. 5, the light source 30 is disposed on the second main surface 12 side of the laminate 10. Details of the laminate 10 of the present invention are as described above.
• the type of light source is not particularly limited, but examples include light-emitting diode (LED) bulbs, incandescent bulbs, fluorescent lights, and natural light.
• LED light-emitting diode
• the decorative article of the present invention exhibits a different design when the light source is on and off, and can therefore be used, for example, as interior or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home appliances such as television sets and air conditioners; containers, etc.
• a laminate (decorative sheet) was manufactured by the following procedure.
• a geometric patterned picture layer made of acrylic resin containing carbon black (ink) as a colorant was formed as a second design layer on the second main surface side of a transparent resin layer made of acrylic resin with a thickness of 125 ⁇ m and a total light transmittance of 90%.
• a haze/transmittance meter HM-150L2N manufactured by Murakami Color Research Institute was used to measure the total light transmittance.
• a striped design layer made of acrylic resin containing carbon black (ink) as a colorant was printed as a third design layer.
• a monochromatic solid layer made of acrylic resin containing aluminum metal pigment was formed as a first design layer on the first main surface side of the transparent resin layer.
• a transparent substrate layer made of ABS resin was thermally laminated to the third design layer side to obtain a laminate in which the first design layer/transparent resin layer/second design layer/third design layer/transparent substrate layer were laminated in this order.
• the first design layer side of the obtained laminate was embossed using an embossing plate with a geometric pattern and an embossing plate depth of 60 ⁇ m to form a concave-convex shape on the first design layer.
• the decorative sheet of the embodiment has a first main surface arranged on the observer side and a second main surface arranged on the light source side, the first main surface has a concave-convex shape, and is a laminate having at least a first design layer, a transparent resin layer, and a second design layer in order from the first main surface side, and further has a third design layer on the second main surface side of the second design layer, the surface of the first main surface side of the second design layer is relatively flatter than the concave-convex shape of the first main surface, and the third design layer is partially provided.
• the obtained decorative sheet had a transparent resin layer thickness of 125 ⁇ m, an embossed recess depth of 60 ⁇ m, a transparent substrate layer thickness of 400 ⁇ m, an OD value of the first design layer of 0.8, an OD value of the second design layer of 1.2, and an OD value of the third design layer of 6.0.
• a transmittance meter X-rite 341C was used to measure the OD value.
• the Rz of the uneven shape on the first main surface side measured in accordance with JIS B0601 (1996) was 55 ⁇ m.
• the Rz of the surface on the second main surface side of the transparent resin layer was 3 ⁇ m.
• the cutoff value ⁇ c was set to 0.8 mm.
• the transparent resin layer and the second design layer are in contact with each other over the entire surface, and the shape of the surface on the second main surface side of the transparent resin layer and the shape of the surface on the first main surface side of the second design layer are complementary to each other.
• Comparative Example A laminate (decorative sheet) was manufactured by the following procedure. On the first main surface side of a transparent substrate layer having a thickness of 475 ⁇ m made of ABS resin, a striped design layer made of acrylic resin containing carbon black (ink) as a colorant was printed as the third design layer, and then a geometric patterned picture layer made of acrylic resin containing carbon black (ink) as a colorant was formed as the second design layer. Furthermore, as the first design layer, a monochromatic solid layer made of acrylic resin containing aluminum metal pigment was formed, and a laminate in which the first design layer / second design layer / third design layer / transparent substrate layer were laminated in order was obtained.
• the first design layer side of the obtained laminate was embossed using an embossing plate with a geometric pattern and an embossing plate depth of 60 ⁇ m, and a concave and convex shape was formed on the first design layer.
• the decorative sheet of the comparative example does not have a transparent resin layer between the first design layer and the second design layer.
• the resulting decorative sheet had an embossed recess depth of 60 ⁇ m, a transparent substrate layer thickness of 475 ⁇ m, a second design layer OD value of 2.2, and a third design layer OD value of 6.0.
• An X-rite 341C transmittance meter was used to measure the OD values.
• the decorative sheet of the embodiment is a laminate that presents different designs when the light source is on and off, and when the light source is on, the design that appears when the light source is off (the design based on the first design layer) is difficult to see, while the designs based on the second and third design layers are visible. Also, when the light source is off, the design based on the first design layer is visible, while the designs based on the second and third design layers are difficult to see.

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• 2023
  • 2023-05-24 JP JP2023085106A patent/JP2024066410A/ja active Pending
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