JP2017047597A - Decorative sheet, decorative molded product and method for producing decorative molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of imparting desired surface characteristics such as high designability to a surface of a decorative molded product.SOLUTION: There is provided a decorative sheet formed by sequentially laminating at least a first substrate layer, a peeling layer, a protective layer and a second substrate layer, wherein when a cut-off value is set to 0.8 mm based on JIS B0601:2001 and an average spacing Sm of irregularities when the surface of a transfer layer is measured in the case where the decorative sheet is transferred to a transferred body is 0.05 mm or more and 0.20 mm or less in at least a part of a region on the surface of the transfer layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet, and more particularly, to a decorative sheet in which at least a first base material layer, a release layer, a protective layer, and a second base material 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.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. The inventors have found that the above problem can be solved by controlling the surface shape of the transfer layer when the decorative sheet is transferred to the transfer target, and have completed the present invention.

That is, according to one aspect of the present invention,
At least a decorative sheet in which a first base layer, a release layer, a protective layer, and a second base 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 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 second base material 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 release 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,
There is provided a decorative molded product in which an average interval Sm of unevenness when the surface of the transfer layer is measured is 0.05 mm or more and 0.20 mm or less in at least a partial region of the surface of the transfer layer.

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,
Provided is a method for producing a decorative molded product, wherein an average interval Sm of unevenness when the surface of the transfer layer is measured is 0.05 mm or more and 0.20 mm or less in at least a partial region of the surface of the transfer layer. Is done.

  In the present invention, at least in the decorative sheet in which the first base material layer, the release layer, the protective layer, and the second base material layer are sequentially laminated, the decorative sheet is transferred to the transfer object. By controlling the surface shape of the transfer layer, desired surface characteristics such as high designability can be imparted to the surface of the 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 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>
In the decorative sheet according to the present invention, at least a first base material layer, a release layer, a protective layer, and a second base material layer are sequentially laminated. 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 off at the interface between the release layer and the protective layer. At the time of molding, the transfer layer having at least the protective layer and the second base material layer is at least released from the first base material layer and the release layer. It is peeled from the release sheet having the layer and transferred to a transfer target (for example, a resin molded product or a display panel).

  The decorative sheet may further include a low refractive index layer between the release layer and the protective layer. An anchor layer may be further laminated on the second base material layer, an adhesive layer may be further laminated on the anchor layer, and a pattern layer may be further provided between the anchor layer and the adhesive layer. Good. Furthermore, you may further provide an antistatic layer in the surface on the opposite side to the mold release layer of a 1st base material layer.

  1 to 4 are schematic cross-sectional views showing an embodiment of a decorative sheet according to the present invention. In the decorative sheet 10 illustrated in FIG. 1, a release layer 12, a protective layer 13, a second substrate layer 14, an anchor layer 15, and an adhesive layer 16 are sequentially laminated on a first substrate layer 11. It is a thing. That is, the decorative sheet 10 includes a release sheet 17 including a base material layer 11 and a release layer 12, and a transfer layer 18 including a protective layer 13, a second base material layer 14, an anchor layer 15, and an adhesive layer 16. It consists of.

  The decorative sheet 20 shown in FIG. 2 has a release layer 22, a protective layer 23, a second base material layer 24, an anchor layer 25, and an adhesive layer 26 on one surface of the first base material layer 21. Are sequentially stacked. 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 first base layer 21, and a release layer 22, a protective layer 23, a second base layer 24, an anchor layer 25, And a transfer layer 29 having an adhesive layer 26.

  3 has a release layer 32, a protective layer 33, a second base material layer 34, an anchor layer 35, a picture layer 36, and an adhesive layer 37 on the first base material layer 31. Are sequentially stacked. That is, the decorative sheet 30 includes a release sheet 38 including a first base layer 31 and a release layer 32, a protective layer 33, a second base layer 34, an anchor layer 35, a picture layer 36, and an adhesive. A transfer layer 39 including a layer 37.

4 has a release layer 42, a low refractive index layer 43, a protective layer 44, a second base material layer 45, an anchor layer 46, and an adhesive layer on a first base material layer 41. The layer 47 is laminated in order. That is, the decorative sheet 40 includes a release sheet 48 including a first base layer 41 and a release layer 42, a low refractive index layer 43, a protective layer 44, a second base layer 45, an anchor layer 46, And a transfer layer 49 having an adhesive layer 47.
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 slope 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 in accordance with 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 irregularities is 0.05 mm or more and 0.20 mm or less, preferably 0.06 mm or more and 0.18 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 mm or more and 0.50 mm 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.

(First and second base material layers)
The first and second base material layers of the decorative sheet according to the present invention include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol. Vinyl resins such as copolymers, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene such as polystyrene Resin based on acrylonitrile resin, acrylonitrile / butadiene / styrene copolymer, cellulose triacetate, cellophane, polycarbonate, polyurethane resin and the like 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. The first and second base material layers may be the same or different.

(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.

  For the release layer, melamine resins, silicone resins, fluorine resins, cellulose resins, urea resins, polyolefin resins, paraffin resins, acrylic resins, and composite resins thereof are preferably used. Among these, from the viewpoint of reliably peeling the release layer and the protective layer, a composite of melamine resin, acrylic resin, acrylic-melamine, or the like is preferable. When using a melamine-based resin, it is preferable to use an acid catalyst in order to accelerate curing. The acid catalyst is not particularly limited, and preferable examples include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalenedisulfonic acid. The amount of the acid catalyst used is preferably about 0.05 to 3%, more preferably 0.05 to 1%, based on the solid content of the melamine resin. Moreover, in order to accelerate | stimulate hardening, it is preferable to perform 130-170 degreeC heat processing for about 30 second-2 minutes.

  In particular, the release layer is preferably formed using an ester group-containing curable resin, and may contain 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 protective layer can be increased by the interaction between the ester group-containing curable resin of the release layer and the acrylic resin of the protective layer described later. By such a combination of a release layer and a protective 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 release 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, polyvinyl carbazole, 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 release layer, and may include an antistatic layer on the opposite side of the base material layer from the release layer.

(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, and when a heating means is used for the curing treatment, for example, radicals are generated by heating to cause polymerization. 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 the molded product or the picture layer from abrasion, light, chemicals, etc. after the transfer layer is transferred from the decorative sheet to the transfer target. Moreover, the protective layer of the decorative sheet according to the present invention has an uneven shape on the surface (the surface on the release layer side of the protective layer), and on the surface of the transfer layer when the decorative sheet is transferred to the transfer object. It is a layer provided in order to form a desired uneven shape. The protective layer can be formed using a binder resin and may contain fine particles. Alternatively, the protective layer may be formed by applying a binder resin to the second base material layer and then shaping a release film having irregularities on the surface. The protective layer preferably has discrete irregular shapes. By adjusting the surface shape of the protective layer (especially the parameters representing the surface shape (Sm, θa, Rz, Ra, etc.)), the desired irregularities on the surface of the transfer layer when the decorative sheet is transferred to the transfer target The protective layer may contain a release agent such as silicone, etc. The protective layer contains the release agent, so that the transfer layer can be reliably and easily transferred from the decorative sheet. The release sheet can be reliably peeled off.

  In the present invention, since the surface of the protective layer has an uneven shape, it has desired optical characteristics with respect to optical parameters such as haze value, total light transmittance, 60 degree gloss, and image sharpness. When the decorative sheet is transferred to the transfer target, the surface shape of the transfer layer on the transfer target has the same optical characteristics with respect to the optical parameters.

  In the present invention, the haze value can be measured according to JIS K-7136 (how to determine the internal haze is as follows). 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 4 types of optical combs (0.125 mm, 0.5 mm, 1 mm, according to JISK7105) using a image clarity measuring instrument (Suga Test Instruments Co., Ltd., product number: “ICM-1DP”). And 2 mm).

(Internal haze)
The “internal haze” is obtained as follows. A resin such as pentaerythritol triacrylate (including a resin component such as a monomer or an oligomer) is diluted with toluene or the like on the unevenness of the protective layer to obtain a solid content of 60%, and the dry film thickness becomes 8 μm with a wire bar. Apply as follows. As a result, the surface irregularities of the protective layer are crushed and a flat layer is formed. However, if the leveling agent is contained in the composition forming the protective layer, and the recoat agent is easy to repel and is difficult to wet, the sample is saponified in advance (2 mol / l NaOH (or KOH)). The solution is immersed in 55 ° C for 3 minutes, washed with water, completely removed with a Kimwipe, and then dried in a 50 ° C oven for 1 minute). The sample whose surface is flat has no internal haze and no haze due to surface irregularities. This haze can be determined as an internal haze. And the value which deducted the internal haze from the haze (whole haze) of the original sample is calculated | required as a haze (external haze) resulting only from surface unevenness | corrugation.

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 (total value of internal haze and external haze) 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 release sheet has a haze value, total light transmittance, 60-degree gloss, and image definition within the above numerical ranges, the transfer layer when the decorative sheet is transferred to the transfer medium has color reproducibility and visual recognition. And surface properties such as 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.

  As the binder resin, a translucent ionizing radiation curable resin or a thermosetting resin can be used. In order to form a protective layer, a resin composition containing an ionizing radiation curable resin or a thermosetting resin is applied to a second substrate layer that is a transparent substrate, and a monomer contained in the resin composition, It can be formed by crosslinking and / or polymerizing oligomers and prepolymers. 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, it is possible to adjust the diffuse transmission intensity distribution due to the internal diffusion and / or external diffusion and / or the interaction between the internal diffusion element and the surface irregularities. For example, it is preferable to use fine particles for imparting external diffusibility having a larger average particle diameter than fine particles for imparting internal diffusibility. 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 protective layer is obtained as an average value of the maximum diameters of 10 particles in the transmission optical microscope observation of the protective 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-based 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 protective layer is preferably about 3 to 10 μm in order to form a sufficient uneven shape. The average particle diameter R of the diffusion particles and the protective layer thickness T preferably satisfy 0.35 <R / T <0.65. When the average particle diameter R of the diffusing particles and the protective layer thickness T are within this numerical range, an appropriate uneven shape can be formed on the surface.

(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 cured acrylic polyol with isocyanate, resin cured 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 property 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, 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 properties such as a target viscosity. For example, as solvents, 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.

<Method for producing decorative sheet>
The method for producing a decorative sheet according to the present invention comprises:
At least a method for producing a decorative sheet in which a first base material layer, a release layer, a protective layer, and a second base material layer are sequentially laminated,
The method includes a step of bonding a first member having at least a first base material layer and at least a second member in which a second base material layer, a protective layer, and a release layer are sequentially laminated. Alternatively, the method includes a step of bonding a third member having at least a first base material layer and a release layer, and a fourth member in which at least a second base material layer and a protective layer are sequentially laminated. . Each layer and member are as described above.

<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. 5 is a schematic cross-sectional view showing an embodiment of a decorative molded product according to the present invention. The decorative molded product 51 includes a transfer layer including the adhesive layer 16, the anchor layer 15, the second base material layer 14, and the protective layer 13 on one surface of the transfer target 52.

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. 6 is a schematic view showing an embodiment of a process for producing a decorative molded product using the decorative sheet according to the present invention. As shown in FIG. 6, 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 (A4300, thickness 50 μm) as a second substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. Then, the following binder resin was cured to form a 2 μm-thick concavo-convex layer to obtain a laminate 1 of a second substrate and a protective layer. Next, the surface of the laminate 1 opposite to the protective layer (uneven surface) is coated with an anchor layer ink having the following composition by a gravure printing method, and is 3 g / m ² after drying. An anchor layer was formed. Subsequently, the adhesive layer was formed on the anchor layer by gravure printing using an adhesive layer ink having the following composition, and dried to 2 g / m ² . On the other hand, a PET film substrate (A4300, thickness 50 μm, manufactured by Toray Industries, Inc.) is prepared as a first substrate layer, and an antistatic layer having the following composition is formed on one surface of the first substrate layer by a gravure printing method. A first member was obtained by coating with an ink and forming an antistatic layer so that the coating amount after drying was 3 g / m ² . Next, the surface of the first substrate that is not coated with the antistatic layer is coated with a release layer ink having the following composition by a gravure printing method, and dried to 0.5 g / m ^2. After forming the release layer, the protective layer surface of the second member and the first release layer surface (the surface opposite to the antistatic layer) of the first member are bonded together, and the decorative sheet 1 Was made. As described above, the decorative sheet 1 in which the antistatic layer, the first base material layer, the release layer, the protective layer, the second base material layer, the anchor layer, and the adhesive layer were laminated in this order 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 1 for protective 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 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 (composition of release layer ink)
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 / diluent: methyl ethyl ketone, toluene (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 (A4300, thickness 50 μm) as a second substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. Then, the following binder resin was cured to form a 3 μm-thick concavo-convex layer to obtain a laminate 2 in which the second base material layer and the protective layer were laminated. Next, a decorative sheet 2 (order of layer configuration: antistatic layer, first base material layer, release layer) is the same as in Example 1 except that the laminate 2 is used instead of the laminate 1. , Protective layer, second substrate layer, anchor layer, adhesive layer).

(Composition of ink 2 for protective 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 (manufactured by 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 is applied to one side of a PET film substrate (A4300, thickness 50 μm) as a second substrate layer, dried, and then irradiated with ultraviolet rays in a nitrogen atmosphere. Then, the following binder resin was cured to form a protective layer having a thickness of 5.5 μm to obtain a laminate 3 of the second base material layer and the protective layer. Next, the decorative sheet 3 (order of layer configuration: antistatic layer, first base material layer, release layer) is the same as in Example 1 except that the laminate 3 is used instead of the laminate 1. , Protective layer, second substrate layer, anchor layer, adhesive layer).

(Composition of ink 3 for protective 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 (manufactured 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 Non-mixed solvent (mass ratio 7: 2: 1) 190 parts by mass

<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 1-3, 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 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. 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 Decorative sheet 11, 21, 31, 41 First base layer 12, 22, 32, 42 Release layer 13, 23, 33, 44 Protective layer 14, 24, 34, 45 First 2 base material layers
15, 25, 35, 46 Anchor layer 16, 26, 37, 47 Adhesive layer 17, 28, 38, 48 Release sheet 18, 29, 39, 49 Transfer layer 27 Antistatic layer 36 Picture layer 43 Low refractive index layer 51 Decorative molded product 52 Transfer object

Claims (9)

At least a decorative sheet in which a first base layer, a release layer, a protective layer, and a second base 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. The decoration 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.   Based on JIS B0601: 2001, the cut-off value is set to 0.25 mm, and the ten-point average roughness Rz when the surface of the transfer layer is measured when the decorative sheet is transferred to the transfer target is the transfer 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 partial region of the surface of the layer.   The decorative sheet according to claim 1, 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 3, wherein an anchor layer is further laminated on the second base material layer.   The decorative sheet according to claim 4, wherein an adhesive layer is further laminated on the anchor layer.   The decorative sheet according to claim 5, further comprising a picture layer between the anchor layer and the adhesive layer.   The decorative sheet according to any one of claims 1 to 6, further comprising an antistatic layer on a surface of the base material layer opposite to the release layer. A decorative molded product comprising a transfer layer on a transfer material,
The transfer layer has at least a protective layer,
The decorative molded product, wherein an average interval Sm of unevenness when the surface of the transfer layer is measured is 0.05 mm or more and 0.20 mm or less in at least a partial region of the surface of the transfer layer. A method for producing a decorative molded product, wherein a transfer layer is formed on a transfer object using the decorative sheet according to claim 1,
The transfer layer has at least a protective layer,
The method for producing a decorative molded product, wherein an average interval Sm of unevenness when the surface of the transfer layer is measured is 0.05 mm or more and 0.20 mm or less in at least a partial region of the surface of the transfer layer.

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