JP6617952B2 - Decorative sheet, decorative molded product, and method for producing decorative molded product - Google Patents

Description

  The present invention relates to a decorative sheet, and more specifically, relates to a decorative sheet in which at least a base material layer, an uneven layer, a release layer, and a protective layer are sequentially laminated. The present invention also relates to a decorative molded product including a transfer layer on a transfer target and a manufacturing method thereof.

  Conventionally, in fields such as household appliances, automobile interior parts, and miscellaneous goods, the surface of a resin molded body, which is a transfer object, is decorated with letters and patterns with white, black, and color inks. Has developed functionality and design.

  In particular, an injection molding simultaneous decorating method has been used for decorating a resin molded body having a complicated surface shape such as a three-dimensional curved surface. The injection molding simultaneous decorating method is a resin molded body in which a decorative sheet inserted into an in-mold mold during injection molding is integrated with a molten injection resin injected and injected into a cavity. It is a method of decorating the surface of the. Furthermore, depending on the difference in the configuration of the decorative sheet integrated with the resin molded body, it is generally divided roughly into an injection molding simultaneous laminate decoration method and an injection molding simultaneous transfer decoration method.

  In the injection molding simultaneous transfer decoration method, the decorative sheet is placed with the transfer layer side facing the inside of the mold, heated from the transfer layer side with a heating plate, so that the decorative sheet follows the shape in the mold To form. Next, the molten injection resin is injected into the cavity, and the decorative sheet and the injection resin are integrated. And after cooling a resin molding and taking out from a metal mold | die, the resin molding which has the decorating layer which transferred the transfer layer can be obtained by peeling the base material sheet of this decorating sheet.

  In recent years, the market for resin molded products having a decorative layer (decorated molded products) obtained in this way has expanded in addition to the fields of conventional household appliances, automobile interior products, and miscellaneous goods. In other fields, for example, notebook personal computers including mobile personal computers and mobile phones are also attracting attention. In these fields, it is required to solve a problem that cannot be realized by forming an ink layer by a conventionally known printing method (gravure printing, silk screen printing, etc.).

  For example, there is a demand for moldability that gives a molded product with a more complicated shape while simultaneously imparting excellent surface properties such as high designability and high hardness to the decorative molded product. Protective layer forming layer formed from an ink composition containing a specific polyfunctional radical polymerization type prepolymer, a specific reactive inorganic fine particle, and a polyfunctional isocyanate in order to impart high hardness to the decorative molded product It has been proposed to use a decorative sheet having a thickness (see Patent Document 1). However, there is still a demand for a decorative sheet that can impart high designability.

JP 2012-041479 A

  This invention is made | formed in view of said background art, The objective is to provide the decorating sheet which can provide desired surface characteristics, such as high design property, on the surface of a decorative molded product.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have at least a decorative sheet in which a base material layer, a concavo-convex layer, a release layer, and a protective layer are sequentially laminated. The inventors have found that the above problems can be solved by controlling the surface shape of the transfer layer when transferred, and have completed the present invention.

That is, according to one aspect of the present invention,
At least a decorative sheet in which a base material layer, an uneven layer, a release layer, and a protective layer are sequentially laminated,
Based on JIS B0601: 2001, the cut-off value is 0.8 mm, and the average interval Sm of the irregularities when the surface of the transfer layer is measured when the decorative sheet is transferred to the transfer target is the transfer layer. In at least a partial region of the surface, a decorative sheet that is 0.05 mm or more and 0.20 mm or less is provided.

  In the aspect of the present invention, based on JIS B0601: 2001, the cut-off value is 0.25 mm, and the ten-point average when the surface of the transfer layer is measured when the decorative sheet is transferred to the transfer target The roughness Rz is preferably 0.20 μm or more and 3.50 μm or less in at least a part of the surface of the transfer layer.

  In the aspect of the present invention, it is preferable that a release layer is further provided between the uneven layer and the release layer.

  In the aspect of the present invention, it is preferable that a low refractive index layer is further provided between the release layer and the protective layer.

  In the aspect of the present invention, it is more preferable that an anchor layer is further laminated on the protective layer.

  In the aspect of the present invention, it is preferable that an adhesive layer is further laminated on the anchor layer.

  In the aspect of the present invention, it is preferable that a pattern layer is further provided between the anchor layer and the adhesive layer.

  In the aspect of the present invention, it is preferable that an antistatic layer is further provided on the surface of the base material layer opposite to the uneven layer.

That is, according to another aspect of the present invention,
A decorative molded product comprising a transfer layer on a transfer material,
The transfer layer has at least a protective layer,
Based on JIS B0601: 2001, when the cut-off value is 0.8 mm and the surface of the transfer layer is measured, the average spacing Sm of the unevenness is 0.05 mm in at least a part of the surface of the transfer layer. A decorative molded product having a size of 0.20 mm or less is provided.

That is, according to another aspect of the present invention,
Using a decorative sheet, a transfer layer is formed on a transfer object, a method for producing a decorative molded product,
The transfer layer has at least a protective layer,
Based on JIS B0601: 2001, when the cut-off value is 0.8 mm and the surface of the transfer layer is measured, the average spacing Sm of the unevenness is 0.05 mm in at least a part of the surface of the transfer layer. There is provided a method for producing a decorative molded product that is 0.20 mm or less.

  In the present invention, at least in the decorative sheet in which the base material layer, the uneven layer, the release layer, and the protective layer are sequentially laminated, the surface shape of the transfer layer when the decorative sheet is transferred to the transfer target is controlled. By doing, desired surface characteristics, such as high designability, can be provided to the surface of a decorative molded product.

It is a schematic cross section which shows one embodiment of the decorating sheet by this invention. It is a schematic cross section which shows one embodiment of the decorating sheet by this invention. It is a schematic cross section which shows one embodiment of the decorating sheet by this invention. It is a schematic cross section which shows one embodiment of the decorating sheet by this invention. It is a schematic cross section which shows one embodiment of the decorating sheet by this invention. It is a schematic cross section which shows one embodiment of the decorative molded product using the decorating sheet by this invention. It is the schematic which shows one embodiment of the manufacturing process of the decorative molded product using the decorating sheet by this invention.

<Decoration sheet>
The decorative sheet according to the present invention is obtained by sequentially laminating a base material layer, an uneven layer, a release layer, and a protective layer. The decorative sheet according to the present invention is used as a transfer-type decorative sheet. For example, the decorative sheet is suitably used for in-mold molding of a decorative molded product, but is not limited thereto. The decorative sheet can be peeled at the interface between the uneven layer and the release layer, and at the time of molding, the transfer layer having at least the release layer and the protective layer is peeled from the release sheet having at least the base material and the uneven layer. Then, it is transferred to a transfer object (for example, a resin molded product or a display panel).

  The decorative sheet may further include a release layer between the uneven layer and the release layer, and may further include a low refractive index layer between the release layer and the protective layer. Further, an anchor layer may be further laminated on the protective layer, an adhesive layer may be further laminated on the anchor layer, and a picture layer may be further provided between the anchor layer and the adhesive layer. Furthermore, you may further provide an antistatic layer in the surface on the opposite side to the uneven | corrugated layer of a base material layer.

  1 to 5 are schematic cross-sectional views showing an embodiment of a decorative sheet according to the present invention. A decorative sheet 10 illustrated in FIG. 1 is obtained by sequentially laminating an uneven layer 12, a release layer 13, a protective layer 14, an anchor layer 15, and an adhesive layer 16 on a base material layer 11. That is, the decorative sheet 10 includes a release sheet 17 including a base material layer 11 and an uneven layer 12, and a transfer layer 18 including a release layer 13, a protective layer 14, an anchor layer 15, and an adhesive layer 16.

  The decorative sheet 20 illustrated in FIG. 2 is obtained by sequentially laminating an uneven layer 22, a release layer 23, a protective layer 24, an anchor layer 25, and an adhesive layer 26 on one surface of a base material layer 21. . An antistatic layer 27 is provided on the other surface of the base material layer 21. That is, the decorative sheet 20 includes a release sheet 28 including an antistatic layer 27, a base material layer 21, and an uneven layer 22, and a transfer layer including a release layer 23, a protective layer 24, an anchor layer 25, and an adhesive layer 26. 29.

  The decorative sheet 30 shown in FIG. 3 is obtained by sequentially laminating an uneven layer 32, a release layer 33, a release layer 34, a protective layer 35, an anchor layer 36, and an adhesive layer 37 on a base material layer 31. is there. That is, the decorative sheet 30 includes a release sheet 38 including a base layer 31, an uneven layer 32, and a release layer 33, and a transfer layer including a release layer 34, a protective layer 35, an anchor layer 36, and an adhesive layer 37. 39.

  The decorative sheet 40 illustrated in FIG. 4 is obtained by sequentially laminating an uneven layer 42, a release layer 43, a protective layer 44, an anchor layer 45, a pattern layer 46, and an adhesive layer 47 on a base material layer 41. . That is, the decorative sheet 40 includes a release sheet 48 including a base material layer 41 and an uneven layer 42, and a transfer layer 49 including a release layer 43, a protective layer 44, an anchor layer 45, a pattern layer 46, and an adhesive layer 47. Consists of.

The decorative sheet 50 shown in FIG. 5 has a concavo-convex layer 52, a release layer 53, a low refractive index layer 54, a protective layer 55, an anchor layer 56, and an adhesive layer 57 laminated on a base material layer 51 in this order. It is. That is, the decorative sheet 50 includes a release sheet 58 including a base layer 51 and an uneven layer 52, and a transfer layer including a release layer 53, a low refractive index layer 54, a protective layer 55, an anchor layer 56, and an adhesive layer 57. 59.
Hereinafter, each layer which comprises the decorating sheet by this invention is demonstrated concretely.

  In the present invention, parameters (Sm, θa, Rz, Ra, etc.) that express the surface shape in particular are formed by forming a desired uneven shape on the surface of the transfer layer when the decorative sheet is transferred to the transfer target. By adjusting, surface characteristics such as high designability can be imparted. The surface of the transfer layer has an uneven shape, and preferably the uneven shape is discretely present. For example, when the object to be transferred is a display, antiglare and antireflection properties can be imparted to the display surface.

In the present invention, Sm (mm) represents the average interval of irregularities on the surface of the transfer layer, θa (degree) represents the average inclination angle of the irregularities, and Rz (μm) represents the ten-point average roughness. , Ra (μm) represents the arithmetic mean roughness, Rq (μm) represents the root mean square roughness, Rp (μm) represents the maximum peak height of the roughness curve, and Rv (μm) The maximum valley depth of the roughness curve is represented, RSm (mm) represents the average length of the roughness curve elements, Rsk represents the skewness of the roughness curve, and Rku represents the kurtosis of the roughness curve. These can be defined as those described in the instruction manual (1995, 07, 20 revision) of the surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Ltd.). θa (degrees) is a unit of angle, and when Δa is the inclination expressed as an aspect ratio, θa (degrees) = tan−1Δa = tan−1 (the difference between the minimum and maximum portions of each unevenness (each convex It is calculated by the sum of the height of the part) and the reference length). Here, the “reference length” is the same as the measurement condition 1 below.
When measuring parameters (Sm, θa, Rz, Ra, etc.) representing the surface shape of the transfer layer, it can be measured according to JIS B0601: 2001 using the surface roughness measuring instrument, for example. In particular, the measurement can be performed under the following measurement conditions, and this measurement is preferable in the present invention.
Measurement condition 1: Reference length (cutoff value λc of roughness curve):
Ten-point average roughness (Rz), arithmetic average roughness (Ra), average inclination angle θa, measurement conditions: 0.25 mm
Average interval Sm of unevenness, measurement condition: 0.80 mm
2: Evaluation length (reference length (cutoff value λc) × 5):
Ten-point average roughness (Rz), arithmetic average roughness (Ra), average inclination angle θa, measurement conditions: 1.25 mm
Average interval Sm of unevenness, measurement condition: 4.0 mm
3: Feeding speed of stylus: 0.1 mm / s

  The decorative sheet is based on JIS B0601: 2001. When the surface of the transfer layer is measured when the decorative sheet is transferred to the transfer target, the transfer layer is at least part of the surface of the transfer layer. The surface has the following surface shape. When the cut-off value is 0.8 mm, the average interval Sm between the concaves and convexes is 0.05 mm or more and 0.20 mm or less, preferably 0.06 mm or more and 0.18 mm or less. When the cutoff value is 0.25 mm, the ten-point average roughness Rz is preferably 0.20 μm or more and 3.50 μm or less, more preferably 0.25 μm or more and 3.20 μm or less. When the cut-off value is 0.25 mm, the arithmetic average roughness Ra is preferably 0.02 μm or more and 0.50 μm or less, more preferably 0.04 μm or more and 0.50 μm or less. When the cut-off value is 0.25 mm, the average inclination angle θa is preferably not less than 0.1 degrees and not more than 5.0 degrees, more preferably not less than 0.5 degrees and not more than 4.7 degrees. The cut-off value is 0.8 mm, and the root mean square roughness Rq is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.07 μm or more and 0.8 μm or less. When the cut-off value is 0.8 mm, the maximum peak height Rp of the roughness curve is preferably 0.1 μm or more and 4.0 μm or less, more preferably 0.15 μm or more and 3.5 μm or less. The maximum valley depth Rv of the roughness curve is preferably 0.2 μm or more and 3.5 μm or less, and more preferably 0.25 μm or more and 2.5 μm or less, with a cutoff value of 0.8 mm. The cut-off value is 0.8 mm, and the average length RSm of the roughness curve element is preferably 0.05 mm or more and 0.25 mm or less, more preferably 0.08 mm or more and 0.2 mm or less. When the cutoff value is 0.8 mm, the skewness Rsk of the roughness curve is preferably −1.0 or more and 1.5 or less, more preferably −0.8 or more and 1.25 or less. The cut-off value is 0.8 mm, and the kurtosis Rku of the roughness curve is preferably 3.0 or more and 8.0 or less, more preferably 3.5 or more and 7.0 or less.

(Base material layer)
The base material layer of the decorative sheet according to the present invention is a polyolefin resin such as polyethylene or polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, vinyl such as ethylene / vinyl alcohol copolymer, etc. Resins, polyethylene resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, acrylonitrile butadiene -Styrene copolymers, cellulose triacetate, cellophane, polycarbonate, polyurethane resins and other elastomer resins are used. Of these, polyester resins, particularly polyethylene terephthalate (hereinafter sometimes referred to as “PET”) are preferred from the viewpoint of good moldability and releasability. The thickness of the base material is preferably in the range of 25 to 150 μm, more preferably in the range of 30 to 100 μm, from the viewpoints of moldability, shape followability, and easy handling.

(Uneven layer)
The concavo-convex layer of the decorative sheet according to the present invention has a concavo-convex shape on the surface (the surface on the peeling layer side of the concavo-convex layer), and the desired concavo-convex pattern on the surface of the transfer layer when the decorative sheet is transferred to the transfer target. It is a layer provided to form a shape.

  The concavo-convex layer can be formed using a binder resin and may contain fine particles. Alternatively, the concavo-convex layer may be formed by applying a binder resin to the base material layer and then shaping a release film having concavo-convex on the surface. The concavo-convex layer preferably has discrete concavo-convex shapes. By adjusting the surface shape of the concavo-convex layer (particularly the parameters representing the surface shape (Sm, θa, Rz, Ra, etc.)), the surface of the transfer layer when the decorative sheet is transferred to the transfer material An uneven shape can be formed. Moreover, the uneven layer may contain a release agent such as silicone. When the concavo-convex layer includes a release agent, the transfer layer can be reliably and easily transferred from the decorative sheet to the transfer target, and the release sheet can be reliably peeled off.

  As the binder resin, a translucent ionizing radiation curable resin or a thermosetting resin can be used. In order to form the concavo-convex layer, a resin composition containing an ionizing radiation curable resin or a thermosetting resin is applied to a transparent substrate, and monomers, oligomers and prepolymers contained in the resin composition are crosslinked and / or Alternatively, it can be formed by polymerization. The reactive functional group of the monomer, oligomer, and prepolymer is preferably an ionizing radiation polymerizable one, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Examples of the prepolymer and oligomer include acrylates such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate, unsaturated polyester, and epoxy resin.

  Monomers include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) Acrylate, glycerin propoxytriacrylate, ditrimethylolpropane tetraacrylate, polyethylene glycol di (meth) acrylate, bisphenol Nord F EO modified di (meth) acrylate, bisphenol A EO modified di (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid PO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, Isocyanuric acid PO-modified tri (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc. Two or more acrylic monomers in the molecule such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol Polyol compounds having an all-group, also including two or more urethane (meth) acrylate, polyester (meth) acrylates having an unsaturated bond. In particular, a polyfunctional acrylate is preferable, and among them, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are more preferable. .

  As the fine particles, it is preferable to use diffusing particles, and binder fine particles that are locally concentrated around the diffusing particles may be further contained. The diffusing particles are preferably translucent fine particles, and may be organic particles, inorganic particles, or a mixture of organic particles and inorganic particles. Since the spherical organic particles can easily control the uneven shape, it is preferable to include at least one kind of spherical organic particles. The average particle diameter of the diffusing particles is preferably in the range of 0.1 to 10 μm, more preferably 1 to 9 μm, and most preferably 1.5 to 8.0 μm. The uneven layer may contain two or more kinds of fine particles having different average particle diameters. Within this range, the external diffusion can be adjusted. The average particle diameter can be measured as a weight average diameter (volume average diameter) by a Coulter counter method when the diffusion particles are measured alone. On the other hand, the average particle diameter of the diffusing particles in the concavo-convex layer is obtained as a value obtained by averaging the maximum diameters of 10 particles in the transmission optical microscope observation of the concavo-convex layer. Alternatively, if it is not suitable, the diffusing particles 30 that are observed as an almost the same particle size of the same kind in the electron microscope (transmission type such as TEM, STEM, etc.) observation of the cross section passing through the vicinity of the particle center. This is a value calculated as an average value by selecting the individual particles (increasing the number of n because it is unknown which part of the particle is a cross section) and measuring the maximum particle diameter of the cross section. Since both are determined from the image, the image may be calculated by image analysis software.

  Translucent organic particles include polymethyl methacrylate particles, polyacryl-styrene copolymer particles, melamine resin particles, polycarbonate particles, polystyrene particles, polyvinyl chloride particles, benzoguanamine-melamine formaldehyde particles, silicone particles, fluorine resin particles. Polyester resins and organic particles having hollows or pores are used. In the case of using organic particles, when the binder particles are inorganic fine particles (the surface is hydrophilic when untreated), the binder fine particles can be suitably localized around the organic particles. May be hydrophilized. The hydrophilic treatment is not particularly limited and may be a known method. Examples thereof include a method of copolymerizing a monomer having a functional group such as a carboxylic acid group or a hydroxyl group on the surface of the organic particles. Examples of the light-transmitting inorganic particles include silica particles, alumina particles, zirconia particles, titania particles, talc, mica, kaolin, smectite, bentonite particles, and inorganic particles having hollows and pores.

  Although it does not specifically limit as content of a diffusion particle, It is preferable that it is 0.5-30 mass parts with respect to 100 mass parts of binder resin.

The binder fine particles are preferably 1 nm or more, have a particle size smaller than that of the diffusing particles, easily aggregate in the binder resin, and preferably have a specific gravity greater than that of the binder resin, and the light-transmitting inorganic particles can be used. In particular, layered inorganic compounds such as talc and smectites, fumed silica, and the like can be used, more preferably by subjecting the surface to a hydrophobic treatment. The specific gravity can be measured by a liquid phase substitution method, a gas phase substitution method (pycnometer method) or the like. The binder fine particles are more preferably fumed silica because the coating liquid has high stability. Here, fumed silica refers to amorphous silica having a particle size of 200 nm or less prepared by a dry method, and is obtained by reacting a volatile compound containing silicon in a gas phase. Specifically, for example, a silicon compound, for example, one produced by hydrolyzing SiCl ₄ in a flame of oxygen and hydrogen can be used. Examples of the fumed silica products include Aerosil manufactured by Nippon Aerosil Co., Ltd. The fumed silica preferably has an average primary particle size of 1 to 100 nm from the viewpoint of cohesiveness. The average primary particle size is a value measured from an image of a transmission electron microscope (TEM, STEM) using image processing software. Further, the fumed silica having an average primary particle size in the above range is aggregated and connected in a bead shape to be enlarged. When it is enlarging in this way, the average particle diameter of the maximum part of the aggregate is preferably 20 to 600 nm from the viewpoint of transparency.

  The thickness of the concavo-convex layer is preferably about 3 to 10 μm in order to form a sufficient concavo-convex shape. The average particle diameter R of the diffusing particles and the uneven layer thickness T preferably satisfy 0.35 <R / T <0.65. When the average particle diameter R of the diffusing particles and the uneven layer thickness T are within this numerical range, an appropriate uneven shape can be formed on the surface.

(Release layer)
The release layer of the decorative sheet according to the present invention is a layer provided for the transfer layer to be more easily peeled off from the base material layer. By providing the release layer, the transfer layer can be more reliably and easily transferred from the decorative sheet to the transfer target, and the release sheet can be reliably peeled off.

  The release layer can be formed using an ester group-containing curable resin, and may contain a release agent such as silicone and fine particles. As the ester group-containing curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. The ionizing radiation curable resin may be any ionizing radiation curable resin having an ester group in the side chain, such as acrylic (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate having an ester group in the side chain, And polyether (meth) acrylate. The thermosetting resin may be a resin obtained by reacting an isocyanate group with a polymer having an ester group and a hydroxyl group in the side chain, for example, an acrylic resin, an epoxy resin having an ester group and a hydroxyl group in the side chain, and A resin obtained by reacting a phenol resin and an isocyanate can be used, and it is particularly preferable to use a resin obtained by reacting an acrylic polyol and an isocyanate. The adhesion strength between the release layer and the release layer can be increased by the interaction between the ester group-containing curable resin of the release layer and the acrylic resin of the release layer described later. By such a combination of a release layer and a release layer, the moldability and transferability when producing a decorative molded product can be improved.

  The release layer is prepared by adding an additive, if necessary, to the resin or release agent as described above, and dissolving or dispersing in an appropriate solvent to prepare a release layer ink. Further, it can be formed by applying and drying by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. The thickness after the drying is about 0.3 to 10 μm.

(Antistatic layer)
The decorative sheet of the present invention can be provided with an antistatic layer. The antistatic layer is a layer that is preferably provided in order to prevent adhesion of foreign matter to the decorative sheet, and is provided on the surface opposite to the surface on which the uneven layer of the base film is provided. The surface resistance value of the antistatic layer is preferably 10 ⁹ to 10 ¹² Ω / □. Antistatic agents used for the antistatic layer include anionic surfactants such as carboxylic acid, sulfonic acid, and phosphoric acid; cationic surfactants such as quaternary ammonium; alkylbetaine, alkylimidazoline , Amphoteric surfactants such as alkylalanine; nonionic surfactants such as alkylene oxide polymers, alkylene oxide copolymers, aliphatic alcohol-alkylene oxide adducts; carbon, gold, platinum, silver, copper, Inorganic conductive materials such as various metal powders such as aluminum, nickel, titanium and molybdenum; polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyphenylene vinylene, polyvinylcarbazole, or aminocarboxylic acid, dicarboxylic acid and polyethylene glycol A conductive polymer such as polyether ester amide resin consisting Lumpur are preferably exemplified.

  The antistatic layer is formed by applying a coating material composed of the above-described antistatic agent and an organic solvent by a coating method such as a gravure coating method or a roll coating method, or a printing method such as a gravure printing method or a screen printing method. The thickness of the antistatic layer formed in this manner is usually preferably 0.1 to 5 μm. If the thickness of the antistatic layer is within the above range, excellent antistatic performance can be obtained efficiently.

(Release sheet)
The release sheet of the decorative sheet according to the present invention includes at least a base material layer and a concavo-convex layer, and may include a release layer on the concavo-convex layer or is opposite to the concavo-convex layer of the base material layer. An antistatic layer may be provided on the side.

  In the present invention, since the surface of the release sheet has an uneven shape, it has desired optical characteristics with respect to optical parameters such as haze value, total light transmittance, 60 degree gloss, image definition, and reflectance. When the decorative sheet is transferred to the transfer object, the surface shape of the transfer layer on the transfer object is transferred by inverting the surface shape of the release sheet, and the decorative molded product has the above optical parameters. It will have equivalent optical properties.

  In the present invention, the haze value of the decorative molded product can be measured according to JIS K-7136. As a device used for the measurement, there is a reflection / transmittance meter HR-100 (Murakami Color Research Laboratory). The total light transmittance can be measured with the same measuring device as the haze value according to JIS K-7361. The haze and total light transmittance are measured with the coated surface facing the light source. The 60-degree gloss can be measured using a precision gloss meter (GM-26D manufactured by Murakami Color Research Laboratory) according to JIS Z8741. In order to remove the influence of the back surface reflection of the sample, the measurement is performed in a state where the back surface of the sample and the black cover of the measuring device are attached with a double-sided tape (manufactured by Teraoka Seisakusho). The image definition is based on JISK7105 using a image clarity measuring instrument (Suga Test Instruments Co., Ltd., product number: “ICM-1DP”), and four types of optical combs (0.125 mm, 0.5 mm, 1 mm, And 2 mm).

In the present invention, the reflectance (reflection Y value, omnidirectional reflectance, diffuse reflectance) of the decorative molded product can be measured as follows.
(Reflection Y value)
Using a spectrophotometer (“MPC3100 (model number)”, manufactured by Shimadzu Corporation), the regular reflectance at an incident angle of 5 ° was measured in the wavelength range of 380 to 780 nm. The Y value (%) was calculated using software (“UVPC color measurement software”, manufactured by Shimadzu Corporation) that converts the measurement result of the regular reflectance into the brightness that the human can perceive.
(Omnidirectional reflectance, diffuse reflectance)
The omnidirectional reflectance and diffuse reflectance at a wavelength of 550 nm were measured using a portable spectrocolorimeter (CM-2600d (model number), manufactured by Konica Minolta).

  The haze value of the decorative molded product is preferably 1.0 to 40%, and more preferably 1.0 to 30%. The total light transmittance is preferably 80 to 99%, and more preferably 85 to 95%. The 60 degree gloss is preferably 40 to 250, and more preferably 40 to 200. The 20 degree gloss is preferably 10 to 250, and more preferably 15 to 230. The image definition is preferably 30 to 500%, and more preferably 30 to 350%. The reflection Y value is preferably 1.0 to 5.0%, and more preferably 1.5 to 4.8%. The omnidirectional reflectance is preferably 4.5 to 5.0%. The diffuse reflectance is preferably from 0.1 to 3.5%, and more preferably from 0.2 to 3.0%. If the haze value, total light transmittance, 60-degree gloss, image definition, and reflectance of the release sheet are within the above numerical ranges, the transfer layer when the decorative sheet is transferred to the transfer medium is colored Surface characteristics such as reproducibility, visibility, and antiglare properties are easily obtained. In addition, said value is a value when using the transparent sheet whose total light transmittance when measured according to JISK-7136 is 85% or more as a to-be-transferred body. Examples of the resin used for the transparent sheet include acrylic and polycarbonate.

(Peeling layer)
The release layer of the decorative sheet according to the present invention is a layer provided so that the release sheet can be easily peeled off from the transfer layer. By providing the release layer, the release sheet can be reliably peeled from the decorative sheet, and the transfer layer can be reliably and easily transferred to the transfer target.

  The release layer can be formed using an acrylic resin, and may further include at least one selected from the group consisting of a vinyl resin and a polyester resin. Examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, and the like. Examples of the vinyl resin include polyvinyl acetate, vinyl chloride vinyl acetate copolymer, polyvinyl alcohol, and polyvinyl butyral. A peeling layer can improve adhesion strength with a mold release layer by including acrylic resin and vinyl resin and / or polyester resin in combination.

  The release layer may further contain a release agent. Examples of the release agent include waxes such as synthetic wax and natural wax. The synthetic wax is preferably a polyolefin wax such as polyethylene wax or polypropylene wax. A release layer can improve mold release property by including a mold release agent.

(Low refractive index layer)
The low refractive index layer of the decorative sheet according to the present invention is such that after the transfer layer is transferred from the decorative sheet to the transfer object, external light (for example, fluorescent light, natural light, etc.) is the surface of the decorative molded product. This is for reducing the reflectivity when reflecting at. The low refractive index layer has a lower refractive index than the concavo-convex layer. Specifically, for example, the low refractive index preferably has a refractive index of 1.45 or less, and more preferably has a refractive index of 1.42 or less.

  The thickness of the low-refractive index layer is not limited, but it may be set appropriately from the range of about 30 nm to 1 μm. The thickness dA (nm) of the low refractive index layer preferably satisfies dA = mλ / (4 nA). In this formula, nA represents the refractive index of the low refractive index layer, m represents a positive odd number, preferably 1, and λ is a wavelength, preferably a value in the range of 480 nm to 580 nm. Further, the low refractive index layer preferably satisfies 120 <nAdA <145 from the viewpoint of reducing the reflectance.

  The effect can be obtained with a single layer of the low refractive index layer, but it is also possible to appropriately provide two or more low refractive index layers for the purpose of adjusting a lower minimum reflectance or a higher minimum reflectance. When two or more low refractive index layers are provided, it is preferable to provide a difference in the refractive index and thickness of each low refractive index layer.

  The low refractive index layer is preferably 1) a resin containing low refractive index particles such as silica and magnesium fluoride, 2) a fluorine-based resin which is a low refractive index resin, and 3) fluorine containing silica or magnesium fluoride. 4) It can be composed of any one of a thin film of a low refractive index material such as silica and magnesium fluoride. As for the resin other than the fluorine-based resin, the same resin as the binder resin constituting the uneven layer described above can be used.

  Further, the silica is preferably hollow silica fine particles, and such hollow silica fine particles can be produced by, for example, a production method described in Examples of JP-A-2005-099778.

  As the fluorine-based resin, a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof can be used. Although it does not specifically limit as a polymeric compound, For example, what has hardening reactive groups, such as a photopolymerizable functional group and a thermosetting polar group, is preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

  As the photopolymerizable compound, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, to illustrate fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. As those having a (meth) acryloyloxy group, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, α-trifluoro (Meth) acrylate compounds having a fluorine atom in the molecule, such as methyl methacrylate and α-trifluoroethyl methacrylate; a C 1-14 fluoroalkyl group having at least 3 fluorine atoms in the molecule, fluoro A cycloalkyl group or a fluoroalkylene group and at least two (medium There are also fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

  Preferable examples of the thermosetting polar group include hydrogen bond forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polymerizable compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, and the like. Examples include fluorine-modified products of each resin.

  The polymerizable compound having both the photopolymerizable functional group and the thermosetting polar group includes acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially. Examples thereof include fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

  Examples of the fluorine-based resin include the following. Polymer of monomer or monomer mixture containing at least one fluorine-containing (meth) acrylate compound of a polymerizable compound having an ionizing radiation curable group; at least one fluorine-containing (meth) acrylate compound; and methyl (meth) Copolymers with (meth) acrylate compounds that do not contain fluorine atoms in the molecule such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; fluoroethylene , Fluorine-containing compounds such as vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, hexafluoropropylene Monomer homopolymer or Copolymer such as. Silicone-containing vinylidene fluoride copolymers obtained by adding a silicone component to these copolymers can also be used. The silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, Dimethyl silicone, phenylmethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, acrylic Modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Over emissions, fluorine-modified silicones, polyether-modified silicone and the like. Among these, those having a dimethylsiloxane structure are preferable.

  Furthermore, non-polymers or polymers composed of the following compounds can also be used as the fluororesin. That is, a fluorine-containing compound having at least one isocyanate group in the molecule is reacted with a compound having at least one functional group in the molecule that reacts with an isocyanate group such as an amino group, a hydroxyl group, or a carboxyl group. Compound obtained: a compound obtained by reacting a fluorine-containing polyol such as fluorine-containing polyether polyol, fluorine-containing alkyl polyol, fluorine-containing polyester polyol, fluorine-containing ε-caprolactone-modified polyol with a compound having an isocyanate group Can be used.

  Moreover, each binder resin as described in the said uneven | corrugated layer can also be mixed and used with the polymeric compound and polymer which have the above-mentioned fluorine atom. Furthermore, various additives and solvents can be used as appropriate in order to improve the curing agent for curing reactive groups and the like, to improve the coating property, and to impart antifouling properties.

  In the formation of the low refractive index layer, the viscosity of the composition for the low refractive index layer formed by adding the above-described material is 0.5 to 5 mPa · s (25 ° C.), preferably 0.7, which provides preferable coating properties. It is preferable to be in the range of ˜3 mPa · s (25 ° C.). An antireflection layer excellent in visible light can be realized, a uniform thin film with no coating unevenness can be formed, and a low refractive index layer particularly excellent in adhesion can be formed. Moreover, conventionally known means can be used as the curing means for the composition for the low refractive index layer. When a heating means is used for the curing treatment, for example, radicals are generated by heating, and the polymerization property is increased. It is preferable that a thermal polymerization initiator for initiating polymerization of the compound is added to the fluororesin composition.

(Protective layer)
The protective layer of the decorative sheet according to the present invention is a layer for protecting a molded article or a picture layer from abrasion, light, chemicals, etc. after the transfer layer is transferred from the decorative sheet to the transfer target. The protective layer can be formed using an ionizing radiation curable resin, a thermosetting resin, a thermoplastic resin, or the like. Ionizing radiation curable is one having an energy quantum that can crosslink and polymerize molecules in electromagnetic waves or charged particle beams, that is, it is crosslinked by causing polymerization reaction by being excited by irradiation with ultraviolet rays or electron beams. It is the ability to cure. The ionizing radiation curable functional group is a functional group capable of expressing the ionizing radiation curable property, and is at least selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, and an epoxy group. One type. Alternatively, the protective layer can be formed using a thermoplastic resin.

  When the protective layer is composed of an ionizing radiation curable resin, the protective layer includes an ionizing radiation curable resin, reactive inorganic particles and / or diffusion particles having a reactive functional group on the surface of the inorganic particles, and a polyfunctional isocyanate. It is preferable to form from the ink composition containing these. This ink can be formed by applying and drying by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.

  Examples of the polymer having an ionizing radiation curable functional group include acrylic (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate, Urethane (meth) acrylate is preferred. In the present invention, these polymers may be used alone or in combination of two or more.

  The weight average molecular weight of the polymer having an ionizing radiation curable functional group is preferably about 5000 to 150,000, more preferably 20,000 to 100,000. When the number average molecular weight is within the above range, the thixotropy of the ink composition can be obtained, and good moldability can be obtained. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC), and is a value measured under conditions using polystyrene as a standard sample. Moreover, from the viewpoint of obtaining excellent high hardness and scratch resistance, the double bond equivalent of the polymer is 50 to 1000, preferably 100 to 1000, and more preferably 100 to 500. Here, the double bond equivalent means the molecular weight per ionizing radiation-curable functional group.

  The reactive inorganic particle has a reactive functional group on the surface of the inorganic particle. Preferred examples of the reactive functional group include a vinyl group, a (meth) acryloyl group, an allyl group, an epoxy group, and a silanol group. From the viewpoint of improving high hardness and scratch resistance, a vinyl group, (meth) An acryloyl group and an allyl group are more preferable.

  Preferred inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, etc., and high hardness and scratch resistance. From the viewpoint of improving the properties, silica particles are preferred.

  Examples of the shape of the inorganic particles include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. These shapes are preferably uniform and sized, and the inorganic particles have a weak interaction with each other. Monodispersed particles are preferred. The average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer formed from the ink composition, but is usually preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.1 μm. Here, the average particle diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a cumulative distribution. It can be measured using a meter (manufactured by Nikkiso Co., Ltd.).

  Among inorganic particles, irregularly shaped inorganic particles are preferable from the viewpoint of high hardness. The irregular shaped inorganic particles are composed of a group of inorganic particles in which the inorganic particles are connected and aggregated with an average number of connections of 2 to 40, and are included in the inorganic particles in the present invention. Connected aggregation may be regular or irregular. As the inorganic particles forming the inorganic particle group, inorganic particles composed of metal oxides such as silica (colloidal silica, fumed silica, precipitated silica, etc.), alumina, zirconia, titania, zinc oxide are preferably mentioned. From the viewpoint of improving hardness and scratch resistance, inorganic particles made of silica are preferable. That is, it is preferable that the irregular shaped inorganic particle is composed of a silica particle group in which silica particles are connected and aggregated having an average number of connections of 2 to 40.

  Preferred examples of such reactive irregularly shaped inorganic particles include irregularly shaped inorganic particles whose surface is decorated with a silane coupling agent. Examples of the silane coupling agent include known silane coupling agents having an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group, and the like, and more specifically, γ-aminopropyltriethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like are preferable, and γ-methacryloxypropyltrimethoxysilane is more preferable. Γ-methacryloxypropylmethyldimethoxysilane and γ-methacryloxypropyldimethylmethoxysilane.

  There are no particular restrictions on the method of decorating the irregularly shaped inorganic particles with the silane coupling agent, and any known method may be used. A dry method in which the silane coupling agent is sprayed, or after the irregularly shaped inorganic particles are dispersed in the solvent, Examples thereof include a wet method in which a coupling agent is added and reacted.

  The protective layer may contain diffusing particles. As the diffusing particles, the same diffusing particles as those used for the uneven layer can be used. The protective layer can impart internal diffusibility by containing diffusing particles. For example, from the viewpoint of surface glare, the internal haze value hi in the protective layer is preferably adjusted so that 1 <hi <15, more preferably 2 ≦ hi <15, and even more preferably 3 ≦ hi ≦ 12. It is preferable.

  A polyfunctional isocyanate or a compound having two or more isocyanate groups. Examples of the polyfunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate ( HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other polyisocyanates such as aliphatic (or alicyclic) isocyanates. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers, etc., blocked isocyanate compounds, and the like are also included.

  Of the polyfunctional isocyanates, those having at least one selected from a vinyl group, a (meth) acryloyl group, an allyl group and an epoxy group as the ionizing radiation-curable functional group are particularly preferred from the viewpoint of high hardness. Specifically, a polyfunctional isocyanate having at least one functional group having an ethylenically unsaturated bond and two or more isocyanate groups, such as “Laromer LR9000 (trade name)” (manufactured by BASF), is preferable.

  The content of reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is preferably 15 to 60% by mass, more preferably 20 to 50% by mass. Here, the content of the reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is such that the reactive inorganic particles and / or the reaction with respect to the total of the polymer and the reactive inorganic particles and / or reactive irregularly shaped inorganic particles. The polymer is a solid content. When the content of the reactive inorganic particles is within the above range, excellent high hardness and scratch resistance can be obtained.

  The ink composition may contain a solvent for the purpose of adjusting the viscosity. Solvents include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone, diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide; Ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dioxolane; methylene chloride, chloroform Preferred are halogenated hydrocarbons such as chloromethane, trichloroethane and tetrachloroethane; other substances such as dimethyl sulfoxide and propylene carbonate; or a mixture thereof. More preferred solvents include methyl ethyl ketone and methyl isobutyl ketone.

  The amount of the solvent in the ink composition may be appropriately selected according to the viscosity of the composition, but the solid content of the polymer, reactive inorganic particles and reactive irregularly shaped inorganic particles, and other photopolymerization initiators described later. The amount of the solid content is generally about 10 to 50% by mass, preferably 20 to 40% by mass.

  The ink composition can contain a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenone series, ketone series, benzophenone series, benzoin series, ketal series, anthraquinone series, disulfide series, thioxanthone series, thiuram series, and fluoroamine series. Of these, acetophenone, ketone, and benzophenone are preferred. These photopolymerization initiators can be used alone or in combination of two or more.

  The content of the photopolymerization initiator is preferably about 0.5 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 3 to 8%, based on the total of the above polymer and inorganic particles. The polymer and inorganic particles are based on solid content.

  The ink composition may contain various additives depending on the desired physical properties to be obtained. Examples of additives include ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, and antifoaming agents. Agents, fillers and the like.

  When the protective layer is composed of a thermosetting resin, the thermosetting resin includes phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, resin obtained by curing acrylic polyol with isocyanate, and polyester polyol. A resin cured with isocyanate, a resin cured with acrylic acid with melamine, or the like can be used. Furthermore, when the protective layer is composed of a thermosetting resin, inorganic particles may be added to the thermosetting resin. As the inorganic particles added to the thermosetting resin, the above-described inorganic particles can be used as in the case where the protective layer is made of an ionizing radiation curable resin.

  Further, when the protective layer is composed of a thermoplastic resin, an acrylic resin, a vinyl resin, a polyester resin, or the like can be used as the thermoplastic resin. Furthermore, when the protective layer is composed of a thermosetting resin, inorganic particles may be added to the thermoplastic resin. As the inorganic particles to be added to the thermoplastic resin, the above-described inorganic particles can be used as in the case where the protective layer is made of an ionizing radiation curable resin.

  Usually, the thickness of the protective layer is preferably in the range of 0.5 to 30 μm, and more preferably in the range of 1 to 15 μm. When the thickness of the protective layer is within the above range, surface properties such as excellent high hardness, scratch resistance, chemical resistance, and contamination resistance can be obtained, and further excellent moldability and shape followability can be obtained. Can be obtained.

(Anchor layer)
The anchor layer of the decorative sheet according to the present invention can be formed using a curable resin, and is a layer provided to improve heat resistance at high temperatures in in-mold molding. As the curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. As the ionizing radiation curable resin, a polymer having at least one ionizing radiation curable functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, and an epoxy group can be used. Examples include acrylic (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate, and urethane (meth) acrylate is particularly preferable. Thermosetting resins include phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, resin obtained by curing acrylic polyol with isocyanate, resin obtained by curing polyester polyol with isocyanate, and acrylic acid cured with melamine. Resin.

  Moreover, it is preferable that an anchor layer contains resin formed by reacting acrylic polyol and isocyanate. When the anchor layer contains a resin obtained by reacting an acrylic polyol and an isocyanate, and the picture layer or the adhesive layer contains an acrylic polyol, the adhesion of the picture layer or the adhesive layer can be improved. In addition, the affinity between the protective layer resin and the anchor layer resin obtained by reacting the acrylic polyol and isocyanate can improve the adhesion between the protective layer, the anchor layer, and the pattern layer or adhesive layer. it can.

  Furthermore, the anchor layer is prepared by dissolving or dispersing the above-mentioned resin with the necessary additives in an appropriate solvent, and using the gravure coating method, roll coating method, comma coating method, gravure printing method, screen It can be formed by applying and drying by known means such as a printing method and a gravure reverse roll coating method. Usually, the thickness of the anchor layer is preferably in the range of 0.1 to 6 μm, and more preferably in the range of 1 to 5 μm.

(Picture layer)
The pattern layer is a layer for imparting a desired design to the decorative molded product, and is a layer provided as desired. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and the like can be mentioned. Moreover, the pattern layer can be provided with the pattern pattern layer and the whole surface solid layer which express the said pattern individually or in combination, and a whole surface solid layer is normally used as a concealment layer, a coloring layer, a coloring concealment layer, etc.

  The pattern layer is usually a binder such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin on the protective layer or the anchor layer formed as described above. And formed by printing with a printing ink containing a pigment or dye of an appropriate color as a colorant. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing. The thickness of the pattern layer is preferably 5 to 40 μm, more preferably 5 to 30 μm from the viewpoint of design.

  Colorants used in the above inks include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone yellow, hansa yellow A, quinacridone red, and permanent. Red 4R, organic pigments (including dyes) such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments made of metal powders such as aluminum and brass, titanium dioxide-coated mica, foil powders such as basic lead carbonate A pearl luster (pearl) pigment, a fluorescent pigment, or the like made of can be used alone or in combination of two or more.

  The pattern layer may be a metal thin film layer or the like. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. Alternatively, a combination thereof may be used. The metal thin film layer may be provided on the entire surface or partially in a pattern.

(Adhesive layer)
The adhesive layer is a layer formed in order to transfer the transfer layer to the transfer target with good adhesiveness. For this adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer object is appropriately used. For example, when the material of the transfer object is an acrylic resin, it is preferable to use an acrylic resin. If the material of the transfer object is polyphenylene oxide / polystyrene resin, polycarbonate resin, or styrene resin, use an acrylic resin, polystyrene resin, polyamide resin, or the like that is compatible with these resins. Is preferred. Further, when the material of the transfer object is a polypropylene resin, it is preferable to use a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin.

  Examples of the method for forming the adhesive layer include a coating method such as a gravure coating method and a roll coating method, a printing method such as a gravure printing method and a screen printing method. In addition, when the pattern layer has sufficient adhesiveness to the transfer target, the adhesive layer may not be provided. The thickness of the adhesive layer is usually preferably about 0.1 to 5 μm.

  In the present invention, various known solvents can be used for the ink for forming each layer, and they can be appropriately selected and combined according to the properties such as the target viscosity. Examples of the solvent include hydrocarbons such as toluene and xylene, methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve and other alcohols, acetone, methyl ethyl ketone, Contains ketones such as methyl isobutyl ketone, cyclohexanone, diacetone alcohol, esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, nitrogen such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide Compounds, ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dioxolane, methylene chloride, chloroform , Trichloroethane, halogenated hydrocarbons such as tetrachloroethane, dimethylsulfoxide, other solvents such as propylene carbonate or mixtures thereof. In particular, methyl ethyl ketone and methyl isobutyl ketone are preferable.

<Decorated molded products>
The decorative molded product according to the present invention includes a transfer layer on a transfer target. The transfer layer can be formed using the decorative sheet. The surface shape of the transfer layer is as described above. Manufacturing efficiency can be improved by manufacturing a decorative molded product using the decorative sheet according to the present invention.

  FIG. 6 is a schematic cross-sectional view showing an embodiment of a decorative molded product according to the present invention. The decorative molded product 61 includes a transfer layer including the adhesive layer 16, the anchor layer 15, the protective layer 14, and the release layer 13 on one surface of the transfer object 62.

The decorative molded product according to the present invention can be formed by in-mold molding (injection molding simultaneous transfer decoration method) using the decorative sheet. FIG. 7 is a schematic view showing one embodiment of a process for producing a decorative molded product using the decorative sheet according to the present invention. As shown in FIG. 7, the manufacturing process of the decorative molded product includes steps (a) to (d):
(A) inserting the above decorative sheet into an in-mold mold, and arranging the transfer layer side of the decorative sheet toward the inside of the mold;
(B) a step of injecting a molten injection resin into the mold;
(C) a step of integrating the decorative sheet and the injection resin to form a decorative layer on the surface of the resin molded body; (d) cooling the resin molded body with a mold as needed; After removing from, the process of peeling the release sheet of the decorative sheet,
Is included. By manufacturing a decorative molded product by such a manufacturing process, a complicated design such as gradation can be expressed on the surface of the resin molded body.

  The injection resin used when the decorative molded product is manufactured by in-mold molding may be any thermoplastic resin that can be injection molded, and various known resins can be used. Examples of such thermoplastic resins include polystyrene resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not construed as being limited to the contents of the following examples.

[Example 1]
<Preparation of decorative sheet>
First, the uneven layer ink 1 having the following composition was applied to one side of a PET film substrate (Toray Industries, A4300, thickness 50 μm) as a substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. The binder resin was cured to form a concavo-convex layer having a thickness of 2 μm to obtain a release sheet 1. Next, a release layer was formed on the release sheet 1 by a gravure printing method using a release layer ink having the following composition, and dried to 0.5 g / m ² . Next, the protective layer was formed on the release layer by a gravure printing method using a protective layer ink having the following composition, and dried to 5 g / m ² . Next, an anchor layer was formed on the protective layer by gravure printing using an anchor layer ink having the following composition, and 3 g / m ² after drying. Next, an adhesive layer was formed on the anchor layer by a gravure printing method using an adhesive layer ink having the following composition, and 2 g / m ² after drying. In addition, the following ink was diluted with an organic solvent so as to have a viscosity that can be easily applied.

(Composition of ink 1 for uneven layer)
-Binder resin (pentaerythritol triacrylate) 98.8 parts by mass-Cellulose acetate propionate 1.2 parts by mass-Photopolymerization initiator (Irgacure 1 8 4; manufactured by Ciba Geigy) 2.7 parts by mass-Photopolymerization initiator ( Benzophenone) 2.7 parts by mass, fine particles (silica coupling-treated silica, average particle size 1.5 μm) 5.6 parts by mass, additive (ether-modified silicone) 0.1 parts by mass, diluting solvent (toluene) 106.4 Part by mass / diluent solvent (ethyl acetate) 5.0 parts by mass (composition of ink for release layer)
Polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd., trade name: Thermolac LP45M):
100 parts by mass (composition of protective layer ink)
・ UV curable acrylic acrylate, silica particles, photopolymerization initiator (DNP Fine Chemical Co., Ltd., trade name: KYK coating agent (82L)) 100 parts by mass. ・ Hexanemethylene diisocyanate (Nihon Polyurethane Industry Co., Ltd. : Coronate 2203): 2 parts by mass / diluent solvent: methyl ethyl ketone, methyl isobutyl ketone (composition of ink for anchor layer)
・ Acrylic polyol (manufactured by Taisei Fine Chemical Co., Ltd., trade name: ACRYT 6RH084T): 100 parts by mass Toluene (adhesive layer ink composition)
-Vinyl chloride vinyl acetate copolymer (manufactured by DNP Fine Chemical Co., Ltd., trade name: ST-PA A varnish): 100 parts by mass-Diluting solvent: methyl ethyl ketone, toluene

Further, an antistatic layer was formed on the other surface of the base material layer by gravure printing using an antistatic layer ink having the following composition, and 3 g / m ² after drying. By the above, the decorating sheet 1 laminated | stacked in order of the antistatic layer, the base material layer, the uneven | corrugated layer, the peeling layer, the protective layer, the anchor layer, and the contact bonding layer was produced. In addition, the following ink was diluted with an organic solvent so as to have a viscosity that can be easily applied.

(Composition of ink for antistatic layer)
-Cationic surfactant (quaternary ammonium salt, manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: SP-V antistatic agent (K)) 100 parts by mass-Diluting solvent: methyl ethyl ketone, toluene

[Example 2]
<Preparation of decorative sheet>
First, the uneven layer ink 2 having the following composition was applied to one side of a PET film substrate (Toray Industries, A4300, thickness 50 μm) as a substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. The binder resin was cured to form an uneven layer having a thickness of 3 μm, whereby a release sheet 2 was obtained. Next, the decorative sheet 2 (the order of the layer configuration: antistatic layer, base material layer, concavo-convex layer, release) is the same as in Example 1 except that the release sheet 2 is used instead of the release sheet 1. Layer, protective layer, anchor layer, adhesive layer).

(Composition of ink 2 for uneven layer)
-Binder resin (pentaerythritol triacrylate (product name PET30; Nippon Kayaku)) 3.04 g
・ Diffusion particles (styrene bead paste (product name SX-130; Soken Chemical, particle size 1.3 μm, bead content 40%)) 1 g
10% cellulose acetate propionate (ethyl acetate dilution; polymer content 10%) 3.64 g
・ Diluting solvent (toluene, butyl acetate, isobutyl alcohol) 7.21 g
Photopolymerization initiator: Irgacure 651 (Ciba Geigy) 0.11 g
・ Filler / binder ratio 10/100

[Example 3]
<Preparation of decorative sheet>
First, the uneven layer ink 3 having the following composition was applied to one side of a PET film substrate (Toray, A4300, thickness 50 μm) as a substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. The release resin 3 was obtained by curing the binder resin and forming a concavo-convex layer having a thickness of 5.5 μm. Next, the decorative sheet 3 (the order of the layer configuration: antistatic layer, base material layer, uneven layer, release) was the same as in Example 1 except that the release sheet 3 was used instead of the release sheet 1. Layer, protective layer, anchor layer, adhesive layer).

(Composition of ink 3 for uneven layer)
-Binder resin (pentaerythritol tetraacrylate (PETTA, product name: M-451, manufactured by Toa Gosei Co., Ltd.) 70 parts by mass, and isocyanuric acid PO-modified triacrylate (product name: M-313, manufactured by Toa Gosei Co., Ltd.) ) 30 parts by mass of mixture) 100 parts by mass / diffusing particles (styrene acrylic copolymer particles (refractive index 1.56, average particle size 3.5 μm, manufactured by Sekisui Plastics)) 5 parts by mass / binder fine particles (talc ( Nanotalc D-1000, average particle size 1.0 μm, manufactured by Nippon Talc)) 4 parts by mass, photopolymerization initiator Irgacure 184 (made by BASF Japan) 5 parts by mass, leveling agent polyether-modified silicone (TSF4460, manufactured by Momentive Performance Materials) ) 0.04 parts by mass / diluent: toluene, isopropanol, and cyclohexa A mixed solvent of emissions (mass ratio 7: 2: 1) 190 parts by diluting solvent: toluene

[Example 4]
<Preparation of decorative sheet>
The release sheet 1 was coated with a release layer ink 1 having the following composition by a gravure printing method, and after forming a release layer so as to be 0.5 g / m ² after drying, a release layer was formed. Except that a release layer was formed on the mold layer, the decorative sheet 4 (layer order: antistatic layer, base material layer, uneven layer, release layer, release layer, protective layer, Anchor layer, adhesive layer).
(Composition of release layer ink 1)
Acrylic polyol (manufactured by Soken Chemical Co., Ltd., trade name: Thermolac SU-100)
100 parts by mass-Isocyanate (Mitsui Chemicals, trade name: Takenate D-110N) 75 parts by mass-Diluting solvent: methyl ethyl ketone, toluene

[Example 5]
<Preparation of decorative sheet>
On the release sheet 2, the release layer ² was applied by gravure printing using the release layer ink 1 having the above composition, and after forming a release layer so as to be 0.5 g / m ² after drying, a release layer was formed. Except that a release layer was formed on the mold layer, a decorative sheet 5 (layer order: antistatic layer, base material layer, uneven layer, release layer, release layer, protective layer, Anchor layer, adhesive layer).

[Example 6]
<Preparation of decorative sheet>
On the release sheet 3, the release layer 3 was applied by gravure printing using the release layer ink 1 having the above composition, and after forming a release layer so as to be 0.5 g / m ² after drying. A decorative sheet 6 (layer order: antistatic layer, base material layer, concavo-convex layer, release layer, release layer, protective layer, as in Example 3 except that a release layer was formed on the mold layer) Anchor layer, adhesive layer).

<Performance evaluation of decorative sheet>
About the decorating sheet produced in said Examples 1-3, the following optical characteristic and surface shape were evaluated. Moreover, when the decorative molded product was manufactured using the decorative sheet produced in Examples 4-6, it was excellent in moldability and transferability.
(Evaluation of optical properties)
The decorative sheet's transfer layer (adhesive layer) side is overlaid with a transparent acrylic sheet (Kuraray Co., Ltd., Comoglas DK3, thickness 2 mm), heated and transferred from the antistatic layer (opposite to the transfer layer) side of the decorative sheet. A decorative molded product was produced. The decorative molded product was measured for total light transmittance (%), haze value (%), and image definition (%). Similarly, the decorative sheet is overlapped with a black acrylic sheet (manufactured by Mitsubishi Rayon Co., Ltd.), heat-transferred from the antistatic layer (opposite to the transfer layer) side of the decorative sheet to produce a decorative molded product, The reflectance (%) was measured by the above method, and the measurement results are shown in Table 1.

(Evaluation of surface shape)
The transfer layer (adhesive layer) side of the decorative decorative sheet is overlapped with a transparent acrylic sheet (Kuraray Co., Ltd., COMOGLASS DK3, thickness 2 mm), and transferred from the antistatic layer (opposite to the transfer layer) side of the decorative sheet. Thus, a decorative molded product was produced. For the surface of the transfer layer, arithmetic average roughness Ra (μm), ten-point average roughness Rz (μm), average interval Sm (mm), root mean square roughness Rq (μm), maximum peak height Rp of the roughness curve (Μm), maximum valley depth Rv (μm) of roughness curve, average length RSm (mm) of roughness curve elements, skewness Rsk of roughness curve, kurtosis Rku of roughness curve, average inclination angle θa (degrees) ) Was measured by the above method, and the measurement results are shown in Tables 2-7. In addition, each measurement was performed 3 times and the average value was computed.

  It was found that the decorative sheet satisfying the configuration of the present invention can impart surface characteristics such as high designability by forming a desired surface shape on the surface of the transfer layer.

10, 20, 30, 40, 50 Decorative sheet 11, 21, 31, 41, 51 Base material layer 12, 22, 32, 42, 52 Concavity and convexity layer 13, 23, 34, 43, 53 Peeling layer 14, 24, 35, 44, 55 Protective layer 15, 25, 36, 45, 56 Anchor layer 16, 26, 37, 47, 57 Adhesive layer 17, 28, 38, 48, 58 Release sheet 18, 29, 39, 49, 59 Transfer layer 27 Antistatic layer 33 Release layer 46 Picture layer 54 Low refractive index layer 61 Decorative molded product 62 Transfer object

Claims (10)

A decorative sheet having at least a release sheet and a transfer layer ,
The release sheet has a base material layer and an uneven layer,
The transfer layer has, in order from the release sheet side, a release layer, a protective layer, and an adhesive layer.
JIS B0601: based on 2001, a 0.8mm cutoff values, the mean interval Sm of irregularities of when the decorative sheet was measured surface of the transfer layer when it is transferred to the transfer receiving material is, the transfer The decorative sheet which is 0.05 mm or more and 0.20 mm or less in the at least one part area | region of the surface of a layer. JIS B0601: Based on 2001, as 0.25mm cut off value, wherein the decorative sheet is the ten-point average roughness Rz when measuring the surface of the transfer layer when it is transferred to the transfer receiving material is, the The decorative sheet according to claim 1, wherein the decorative sheet has a thickness of 0.20 μm or more and 3.50 μm or less in at least a part of the surface of the transfer layer. The said transfer layer is a decorating sheet of Claim 1 or 2 which has the said peeling layer which contacts the said release sheet. The said release sheet is a decorating sheet as described in any one of Claims 1-3 which has the said release layer in the surface at the side of the said transfer layer .   The decorative sheet according to any one of claims 1 to 4, further comprising a low refractive index layer between the release layer and the protective layer. The decorating sheet according to any one of claims 1 to 5 , further comprising an anchor layer between the protective layer and the adhesive layer .   The decorative sheet according to claim 6, further comprising a pattern layer between the anchor layer and the adhesive layer.   The decorative sheet according to any one of claims 1 to 7, further comprising an antistatic layer on a surface of the base material layer opposite to the uneven layer. A decorative molded product comprising a transfer layer on a transfer material,
The transfer layer has at least a release layer, a protective layer, and an adhesive layer located on the transferred object side in this order ,
Based on JIS B0601: 2001, when the cut-off value is 0.8 mm and the surface of the transfer layer is measured, the average spacing Sm of the unevenness is 0.05 mm in at least a part of the surface of the transfer layer. A decorative molded product having a size of 0.20 mm or less. A method for producing a decorative molded product, wherein the decorative sheet according to any one of claims 1 to 8 is used to form a transfer layer on a transfer target,
The transfer layer has at least a release layer, a protective layer, and an adhesive layer located on the transferred body side in this order ,
Based on JIS B0601: 2001, when the cut-off value is 0.8 mm and the surface of the transfer layer is measured, the average spacing Sm of the unevenness is 0.05 mm in at least a part of the surface of the transfer layer. The manufacturing method of the decorative molded product which is 0.20 mm or less.

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