JP2018058220A - Decorative sheet, decorative resin molding, and method for producing decorative resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having an excellent texture.SOLUTION: A decorative sheet at least has a laminate having a metal thin film layer 4, a pattern layer 3, a first protective layer 1, and a second protective layer 2 in the stated order. The pattern layer 3 is provided on part of the metal thin film layer 4, and the second protective layer 2 is provided on the pattern layer 3 and also on part of the first protective layer 1. There can be also provided a decorative resin molding using the decorative sheet.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet, a decorative resin molded product, and a method for manufacturing a decorative resin molded product.

  Conventionally, a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for an interior / exterior part of a vehicle, a building material interior material, a home appliance housing, and the like. In the production of such a decorated resin molded product, a molding method or the like is used in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding. As a typical example of a method for producing such a decorative resin molded product, for example, an insert molding method is known. In the insert molding method, a decorative sheet is molded into a three-dimensional shape in advance using a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a flow state is injected into the injection mold. And a decorative sheet.

  In recent years, decorative resin molded products, such as automobile interiors, have been increasingly designed, and decorative sheets can be recognized with a three-dimensional appearance when the appearance is visually observed, thereby displaying a high texture. Is required. Conventionally, as a method of imparting a high texture to a decorative resin molded product, in a decorative sheet, a design expression by combining a low gloss layer partially provided and a surface protective layer formed on the entire surface of the sheet is used. Techniques that are suitable for use in injection molding have been proposed (for example, Patent Documents 1 and 2). In addition, as a technique for expressing a higher texture, a technique for expressing a design by combining a surface protective layer (low gloss) and a partially formed pattern forming resin layer (high gloss) has been developed (for example, Patent Documents 3 and 4). However, with the recent diversification and upgrading of designs, there are cases where conventional decorative sheets cannot meet the demands of consumers.

JP 2009-132145 A JP 2010-30277 A JP 2001-138469 A International Publication No. 2015/046568

  The main object of the present invention is to provide a decorative sheet having a high texture.

  The present inventor has intensively studied to solve the above problems. As a result, it comprises a laminate having at least a metal thin film layer, a picture layer, a first protective layer, and a second protective layer in this order, and the picture layer is provided on a part of the metal thin film layer. The decorative sheet provided on the pattern layer and on the part of the first protective layer can express a high texture. I found it. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. It consists of a laminate having at least a metal thin film layer, a pattern layer, a first protective layer, and a second protective layer in this order,
The pattern layer is provided on a part of the metal thin film layer,
The second protective layer is a decorative sheet provided on the pattern layer and provided on a part of the first protective layer.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the metal thin film layer is a metal vapor deposition layer, a metal sputtering layer, a metal ion plating layer, a high-brightness ink layer, or a metal plating layer.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the first protective layer is provided on the entire surface of one side of the decorative sheet.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, comprising a transparent resin layer between the metal thin film layer and the pattern layer.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the first protective layer contains at least one of inorganic particles and resin particles.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the second protective layer contains at least one of inorganic particles and resin particles.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the metal thin film layer can be visually recognized when the decorative sheet is viewed in plan from the second protective layer side at an observation distance of 1 m.
Item 8. Any one of Items 1-7, wherein the cross section in the thickness direction of the decorative sheet has a portion in which the width x of the region A where the second protective layer and the pattern layer are not provided is 1 mm or more. The decorative sheet described in 1.
Item 9. Items 1-8, wherein the concave shape formed by the portion where the second protective layer is provided and the portion where the second protective layer is not provided on the first protective layer is synchronized with the pattern of the picture layer. The decoration sheet in any one of.
Item 10. At least comprising a laminate having in this order a molded resin layer, a metal thin film layer, a pattern layer, a first protective layer, and a second protective layer,
The pattern layer is provided on a part of the metal thin film layer,
The second protective layer is a decorative resin molded product provided on the picture layer and provided on a part of the first protective layer.
Item 11. The decorative sheet according to any one of Items 1 to 9 is inserted into an injection mold, the injection mold is closed, a resin in a fluid state is injected into the injection mold, and the resin and the decorative sheet Integration process to integrate,
A method for producing a decorated resin molded product.
Item 12. Item 12. The method for producing a decorated resin molded article according to Item 11, wherein a vacuum forming step of forming the decorative sheet into a three-dimensional shape in advance by a vacuum forming die is provided before the integration step.

  According to the present invention, a decorative sheet having a high texture can be provided. Furthermore, according to this invention, the manufacturing method of the decorating resin molded product using the said decorating sheet and the said decorating resin molded product can also be provided.

It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating resin molded product of this invention. It is a schematic diagram of an example at the time of planarly viewing the decorating sheet of this invention.

1. Decorative sheet The decorative sheet of the present invention comprises a laminate having at least a metal thin film layer, a pattern layer, a first protective layer, and a second protective layer in this order. The second protective layer is provided on a part of the thin film layer, and the second protective layer is provided on the pattern layer and on a part of the first protective layer. By providing such a specific configuration, the decorative sheet of the present invention can exhibit an excellent texture that cannot be expressed by a conventional decorative sheet. In particular, when the decorative sheet of the present invention is viewed in plan from the second protective layer side (the observation distance is, for example, about 1 m), the metal thin film layer is designed to be visually recognized. In this case, for example, as shown in the schematic diagram of FIG. 5, an excellent design expressed by the gloss region P of the metal thin film layer that can be visually recognized, and the second protective layer and the picture layer provided partially ( An excellent texture can be exhibited by a combination with a pattern area Q (for example, a wood grain pattern) having an excellent stereoscopic effect.

  Hereinafter, the decorative sheet of the present invention will be described in detail. In the present specification, the numerical range indicated by “to” means “above” or “below”, except for the portions specified as “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a metal thin film layer, a picture layer, a first protective layer, and a second protective layer are laminated in this order. For example, as shown in FIG. 1, the pattern layer 3 is provided on a part of the metal thin film layer 4. The second protective layer 2 is provided on the pattern layer 3 and on a part 1 a of the first protective layer 1. On the surface of the first protective layer 1, an uneven shape is formed by a portion 1 a provided with the second protective layer 2 and a portion 1 b provided with no second protective layer 2. .

  For example, as shown in FIG. 2, in the decorative sheet of the present invention, the metal thin film layer 4 and the pattern layer are used for the purpose of improving the scratch resistance and weather resistance of the decorative sheet, and improving shape retention. 3 may have a transparent resin layer 5 as required. In addition, for the purpose of improving the shape retention of the decorative sheet, the base layer 6 may be provided on the opposite side of the metal thin film layer 4 from the first protective layer, if necessary. . Moreover, you may provide the primer layer 7 as needed from a viewpoint of improving the adhesiveness of the metal thin film layer 4 and the layer adjacent to this. In addition, as shown in FIG. 3, an adhesive layer 8 may be provided as necessary for the purpose of improving the adhesion between the base material layer 6 and the transparent resin layer 5 and the layers adjacent thereto. . In addition, in order to suppress the color change and variation of the base material layer 6, between the base material layer 6 and the first protective layer 1, between the base material layer 6 and the pattern layer 3, and the like as necessary. A concealing layer (not shown) may be provided.

  1 to 4 are schematic views for showing a laminated structure of a decorative sheet and a decorative resin molded product, and a layer is formed between partially formed pattern layers 3 for convenience of drawing. Although it is depicted as if there is a non-existing space, in an actual decorative sheet, such a portion does not substantially exist and is filled with layers that are sequentially laminated.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a metal thin film layer / picture layer / first protective layer / second protective layer are laminated in this order; base material layer / primer layer / metal thin film layer / transparent Laminated structure in which resin layer / picture layer / first protective layer / second protective layer are laminated in this order; substrate layer / adhesive layer / metal thin film layer / primer layer / adhesive layer / transparent resin layer / design layer / A laminated structure in which the first protective layer / the second protective layer are laminated in this order is exemplified. FIG. 1 is a schematic view of an example of a decorative sheet in which a metal thin film layer / a pattern layer / a first protective layer / a second protective layer are stacked in this order as an aspect of the laminated structure of the decorative sheet of the present invention. A cross-sectional view is shown. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the present invention, a base layer / primer layer / metal thin film layer / transparent resin layer / picture layer / first protective layer / second protective layer are arranged in this order. The schematic sectional drawing of an example of the laminated | stacked decorating sheet is shown. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present invention, a base layer / adhesive layer / metal thin film layer / primer layer / adhesive layer / transparent resin layer / picture layer / first protective layer / second The schematic-drawing sectional drawing of an example of the decorating sheet | seat on which this protective layer was laminated | stacked in this order is shown.

  In the decorative sheet of the present invention, when the decorative sheet is viewed in plan, it is expressed by the metallic luster that is partially visually recognized, and the second protective layer 2 and the pattern layer 3 that are partially provided. By combining with a design with excellent three-dimensional effect, high texture can be demonstrated. Specifically, for example, as shown in the cross-sectional view of FIG. 1, the decorative sheet of the present invention includes a metal thin film layer 4, a pattern layer 3 provided on a part of the metal thin film layer 4, and a first The protective layer 1 and the second protective layer 2 on the pattern layer 3 and provided on a part of the first protective layer 1 are provided in this order. Since the pattern layer 3 is provided on a part of the metal thin film layer 4, when the decorative sheet is viewed in plan, the metal thin film layer 4 is visually recognized through a portion where the pattern layer 3 is not provided. can do.

  In the decorative sheet of the present invention, high texture is achieved by a combination of such a partially visible metallic luster and a design expressed by the second protective layer 2 and the pattern layer 3 provided partially. In the cross section in the thickness direction of the decorative sheet, the width x of the region A in which the second protective layer 2 and the pattern layer 3 are not provided is 1 mm or more. Preferably it is. The range of the width x varies depending on the design to be applied to the decorative sheet, but is preferably about 1 to 100 mm, more preferably about 10 to 30 mm. For example, as shown in FIG. 5, the cross section at this time is a cross section in the region A along the direction of the short width x when the decorative sheet is viewed in plan.

  Moreover, as shown in FIG. 1, in the decorative sheet of the present invention, in the portion where the pattern layer 3 adjacent to the region A is present, the region B (one of the convex portions of the second protective layer 2) An independent convex portion, width y) and a region C (one independent concave portion, width z) of a concave portion (a portion where the second protective layer is not present) of the second protective layer 2 exist. . From the viewpoint that the decorative sheet of the present invention suitably exhibits a high texture, the width x preferably has a value that is one or more times larger than the sum of the width y and the width z, more preferably 5 times. It has a larger value. For convenience of drawing, the widths y and z are drawn large in FIG.

  In the present invention, the width y is usually about 0.1 to 10 mm, although it varies depending on the design applied to the decorative sheet. Similarly, the width z is usually about 0.1 to 3 mm.

  For example, from the viewpoint of exhibiting excellent texture when used for vehicle interior / exterior parts, building material interior materials, home appliance housings, etc., the decorative sheet of the present invention is the observation distance of the decorative sheet from the second protective layer 2 side. It is preferable that the metal thin film layer 4 can be visually recognized when viewed in plan at 1 m.

Each layer forming the decorative sheet [metal thin film layer 4]
The metal thin film layer 4 is a layer that imparts a partial metallic luster to the decorative sheet. In the decorative sheet of the present invention, the metal thin film layer 4, the pattern layer 3 provided on a part of the metal thin film layer 4, the first protective layer 1, and the pattern layer 3, and Since it consists of a laminated body which has the 2nd protective layer 2 provided on a part of 1st protective layer 1 in this order, when the decoration sheet of this invention is planarly viewed, the metal thin film layer 4 The metallic luster based on is partially visible. As described above, in the decorative sheet of the present invention, such an excellent solid expressed by the partially visible metallic luster and the partially provided second protective layer 2 and pattern layer 3. High texture can be achieved by combining with the design of feeling.

  From the viewpoint of imparting a high texture to the decorative sheet, the metal thin film layer 4 is preferably provided on the entire surface of one side of the decorative sheet.

  The metal forming the metal thin film layer 4 is not particularly limited as long as it is a metal that can impart a metallic design to the decorative sheet. For example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum , Zinc, and alloys containing at least one of them. Among these, tin, indium, and chromium are preferable from the viewpoint of excellent extensibility. In addition, since the metal thin film layer 4 is formed of a metal having excellent extensibility, there is an advantage that cracks are hardly generated when the decorative sheet is three-dimensionally formed. The metal thin film layer 4 may be formed of one kind of metal or may be formed of two or more kinds of metals.

  The metal thin film layer 4 includes, for example, a metal vapor deposition layer that can be formed by metal vapor deposition (for example, vacuum vapor deposition), a metal sputtering layer that can be formed by metal sputtering, and a metal ion plating layer that can be formed by metal ion plating. In addition, a high-brightness ink layer (metal-containing high-brightness ink layer) that can be formed with a metal-containing ink, a metal plating layer, or the like can be used. In particular, the vacuum deposition method is preferably a metal deposition layer because of low cost and little damage to the deposition target. The conditions for the vapor deposition may be appropriately set according to the melting temperature or the evaporation temperature of the metal to be used.

  Although it does not specifically limit as thickness of the metal thin film layer 4, From a viewpoint of improving the texture of a decorating sheet, Preferably it is 200 nm or less, More preferably, it is about 10-100 nm, More preferably, about 20-60 nm is mentioned.

[First protective layer 1]
The 1st protective layer 1 is a layer provided in order to improve the scratch resistance of a decorating sheet, a weather resistance, etc., and also to give a high texture to a decorating sheet with the 2nd protective layer 2 mentioned later. The first protective layer 1 is provided on one side of the decorative sheet from the viewpoint of imparting a high texture to the decorative sheet together with the second protective layer 2 described later while enhancing the scratch resistance and weather resistance of the decorative sheet. It is preferable to be provided on the entire surface.

  The resin contained in the resin composition forming the first protective layer 1 is not particularly limited, and examples thereof include an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin. Among these, it is preferable that the 1st protective layer 1 is comprised by the hardened | cured material of the ionizing radiation curable resin composition.

  The thermosetting resin in the first protective layer 1 is not particularly limited, and examples thereof include epoxy resins, phenol resins, urea resins, unsaturated polyester resins, melamine resins, alkyd resins, polyimide resins, silicone resins, and hydroxyl functionalities. An acrylic resin, a carboxyl functional acrylic resin, an amide functional copolymer, a urethane resin, etc. are mentioned. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  The mode of curing of these thermosetting resins is not particularly limited, and examples include the following modes. For example, in the case of an epoxy resin, reaction with an amine, an acid catalyst, a carboxylic acid, an acid anhydride, a hydroxyl group, dicyandiamide, or ketimine can be used. If it is a phenol resin, the reaction of a base catalyst and excess aldehyde etc. are mentioned. If it is a urea resin, a polycondensation reaction under alkaline or acidic conditions may be used. Examples of unsaturated polyester resins include co-condensation reaction of maleic anhydride and diol. If it is a melamine resin, the heat polycondensation reaction of methylol melamine etc. are mentioned. If it is an alkyd resin, the reaction by the air oxidation of the unsaturated groups introduced into the side chain etc. are mentioned. In the case of a polyimide resin, a reaction in the presence of an acid or a weak alkali catalyst, a reaction with an isocyanate compound (in the case of a two-component type), or the like can be given. In the case of a silicone resin, a condensation reaction in the presence of a silanol group acid catalyst may be used. If it is a hydroxyl functional acrylic resin, the reaction (in the case of 1 liquid type) with a hydroxyl resin and the amino resin which it has is mentioned. If it is a carboxyl functional acrylic resin, the reaction by carboxylic acid, such as acrylic acid or methacrylic acid, and an epoxy compound etc. are mentioned. If it is an amide functional copolymer, a reaction with a hydroxyl group or a self-condensation reaction may be mentioned. In the case of a urethane resin, a reaction between a hydroxyl group-containing polyester resin, a polyether resin, an acrylic resin or the like and an isocyanate compound or a modified product thereof may be used.

  Specific examples of the thermoplastic resin in the first protective layer 1 include acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; Polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin; and the like. A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. When a thermoplastic resin is used to form the first protective layer 2, the first protective layer 1 is formed by forming a resin composition containing a thermoplastic resin softened by heating into layers and then cooling. It can be set as a cured product.

(Ionizing radiation curable resin)
The ionizing radiation curable resin contained in the ionizing radiation curable resin composition used for forming the first protective layer 1 is a resin that crosslinks and cures when irradiated with ionizing radiation. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Also included are electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require an initiator for photopolymerization, and provides stable curing characteristics. Therefore, the first protective layer 1 is formed. Are preferably used.

  From the viewpoint of enhancing the scratch resistance, weather resistance, etc. of the decorative sheet and further imparting a high texture to the decorative sheet together with the second protective layer 2 described later, the first protective layer is a polyfunctional polycarbonate (meth) acrylate. It is preferable that it is comprised by the hardened | cured material of the ionizing radiation curable resin composition containing this.

<Multifunctional polycarbonate (meth) acrylate>
The polyfunctional polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and two or more (meth) acrylates in the terminal or side chain. For example, it has a polycarbonate skeleton. Urethane (meth) acrylate may be used. The (meth) acrylate is preferably 2 to 6 functional groups per molecule from the viewpoint of improving crosslinking and curing. A polyfunctional polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.

  The polyfunctional polycarbonate (meth) acrylate is obtained, for example, by converting a part or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

  The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction of a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R ¹ —OH. Here, R < ¹ > is a C2-C20 bivalent hydrocarbon group, Comprising: The group may contain the ether bond. R ¹ is, for example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2 -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide is added to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compound (C) used as a raw material of the polycarbonate polyol, which is a carbonyl component, is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Examples include esters. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. What is necessary is just to set the preparation molar ratio of a diol compound (A) and a polyhydric alcohol (B) in the range of 50: 50-99: 1, for example. Further, the charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl group of the diol compound and the polyhydric alcohol. What is necessary is just to set to the range of an equivalent.

  The number of equivalents of hydroxyl groups (eq./mol) present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charge ratio is, for example, 3 or more on average in one molecule, preferably 3 to 50, more preferably 3-20 are mentioned. When such an equivalent number is satisfied, a necessary amount of (meth) acrylate groups is formed by an esterification reaction described later, and appropriate flexibility is imparted to the polyfunctional polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

  The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

  Although there is no restriction | limiting in particular about the molecular weight of polyfunctional polycarbonate (meth) acrylate, For example, a weight average molecular weight is 5000 or more, Preferably 10,000 or more is mentioned. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth) acrylate is not particularly limited, but is, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. The weight average molecular weight of the polyfunctional polycarbonate (meth) acrylate is preferably 10,000 to 50,000, and more preferably 10,000, from the viewpoint of further improving the expression effect of the rich and low gloss feeling with a texture and the moldability. -20,000.

  In addition, the weight average molecular weight of the polyfunctional polycarbonate (meth) acrylate in this specification is a value measured with polystyrene as a standard substance by gel permeation chromatography.

  The content of the polyfunctional polycarbonate (meth) acrylate in the ionizing radiation curable resin composition is not particularly limited as long as the effect of the present invention is achieved, but it enhances the scratch resistance, weather resistance, etc. of the decorative sheet. Furthermore, from the viewpoint of imparting a high texture to the decorative sheet together with the second protective layer 2 described later, the content is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

  In addition to the polyfunctional polycarbonate (meth) acrylate, the ionizing radiation curable resin composition used for forming the first protective layer 1 further includes a polyfunctional urethane (meth) acrylate as an ionizing radiation curable resin. May be included. The polyfunctional urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and two or more (meth) acrylates in the terminal or side chain. Such a polyfunctional urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. In addition, the polyfunctional urethane (meth) acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving crosslinking and curing. Polyfunctional urethane (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although there is no restriction | limiting in particular about the molecular weight of polyfunctional urethane (meth) acrylate, For example, a weight average molecular weight is 2000 or more, Preferably 5000 or more is mentioned. The upper limit of the weight average molecular weight of the polyfunctional urethane (meth) acrylate is not particularly limited, but may be, for example, 30,000 or less, preferably 10,000 or less, from the viewpoint of controlling the viscosity not to be too high.

  In addition, the weight average molecular weight of the polyfunctional urethane (meth) acrylate in this specification is the value which measured polystyrene as the standard substance by the gel permeation chromatography method.

  The content of the polyfunctional urethane (meth) acrylate in the ionizing radiation curable resin composition used for the formation of the first protective layer 1 is not particularly limited as long as the effect of the present invention is achieved, From the viewpoint of enhancing the scratch resistance, weather resistance and the like of the decorative sheet and further imparting a high texture to the decorative sheet together with the second protective layer 2 described later, it is preferably 50% by mass or less, more preferably 20% by mass. Hereinafter, more preferably 15 mass% or less is mentioned.

  When the polyfunctional polycarbonate (meth) acrylate and the polyfunctional urethane (meth) acrylate are used in combination in the ionizing radiation curable resin composition used for forming the first protective layer 1, the mass ratio of these (polyfunctional polycarbonate) (Meth) acrylate: polyfunctional urethane (meth) acrylate) is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and still more preferably about 85:15 to 99: 1. Is mentioned.

  Further, the other ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with the ionizing radiation described above, and specifically, a prepolymer having a polymerizable unsaturated bond or an epoxy group in the molecule. What mixed suitably at least 1 sort (s) among a polymer, an oligomer, a monomer, etc. is mentioned.

  As the monomer used as the other ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as said oligomer used as other ionizing radiation curable resin, the (meth) acrylate oligomer which has a radically polymerizable unsaturated group in a molecule | numerator is suitable, Especially, a polymerizable unsaturated bond is 2 in a molecule | numerator. A polyfunctional (meth) acrylate oligomer having at least one (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include acrylic silicone (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, and silicone (meth) acrylate. And oligomers having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Here, acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  These other ionizing radiation curable resins may be used alone or in combination of two or more. Among these other ionizing radiation curable resins, acrylic silicone (meth) acrylate and the like are preferably used from the viewpoint of further improving the three-dimensional formability and scratch resistance of the decorative sheet.

  The first protective layer 1 may contain at least one of inorganic particles and resin particles. In the first protective layer 1, the inorganic particles and the resin particles mainly have a function of reducing the gloss of the first protective layer 1, and the function of reducing the gloss is generally higher for inorganic particles. It tends to be larger than resin particles. When inorganic particles or resin particles are included in the first protective layer 1, these particles are dispersed in the first protective layer 1.

  The inorganic particles are not particularly limited as long as they are particles formed of an inorganic compound, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. Among these, silica is preferable. Particles. An inorganic particle may be used individually by 1 type, and may be used in combination of 2 or more types. As a particle diameter of an inorganic particle, about 0.5-20 micrometers, for example, Preferably about 1-10 micrometers is mentioned. In the present invention, the particle size of the inorganic particles is dispersed in the air by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100, injecting the powder to be measured from the nozzle using compressed air. It is a value measured by an injection-type dry measurement method.

  When the first protective layer 1 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably 1 to 60 masses with respect to 100 parts by mass of the resin contained in the first protective layer 1. About 10 parts by weight, more preferably about 10 to 40 parts by weight. An inorganic particle may be used individually by 1 type, and may be used in combination of 2 or more types.

  Further, the resin particles are not particularly limited as long as they are particles formed of a resin. For example, urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene Examples include beads. Among these resin particles, urethane beads are preferably used from the viewpoint of further improving the scratch resistance of the decorative sheet. The resin particles may be used alone or in combination of two or more. The particle diameter of the resin particles is, for example, about 0.5 to 30 μm, preferably about 1 to 20 μm. The particle diameter of the resin particles is a value measured by the same method as that for the inorganic particles.

  When the first protective layer 1 contains resin particles, the content of the resin particles is not particularly limited, but is preferably 1 to 200 masses with respect to 100 parts by mass of the resin contained in the first protective layer 1. About 10 parts by weight, more preferably about 10 to 150 parts by weight.

  When the first protective layer 1 contains at least one of inorganic particles and resin particles, a part of these particles may protrude from the surface of the first protective layer 1, or the first protection layer 1 Particles may be buried inside the layer 1.

  Various additives can be blended in the first protective layer 1 in accordance with desired physical properties to be provided in the first protective layer 1. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

  Although there is no restriction | limiting in particular about the thickness after hardening of the 1st protective layer 1, For example, about 0.1-20 micrometers, Preferably it is about 0.5-10 micrometers, More preferably, about 1-5 micrometers is mentioned. When the thickness within such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance can be obtained. Further, when the first protective layer 1 is constituted by a cured product of the ionizing radiation curable resin composition, it is possible to uniformly irradiate the ionizing radiation curable resin composition with ionizing radiation. It is possible to cure uniformly, which is economically advantageous. On the other hand, from the viewpoint of particularly improving the wear resistance of the decorative sheet, the thickness of the first protective layer 1 after curing is preferably 4 μm or more, more preferably about 5 to 10 μm. In addition, when the 1st protective layer 1 contains at least one of the above-mentioned inorganic particle and resin particle, the thickness of the 1st protective layer 1 means that the inorganic particle or the resin particle is located on the surface of the first protective layer 1. The thickness of the part that is not.

  The formation of the first protective layer 1 is performed, for example, by preparing an ionizing radiation curable resin composition, applying it, and crosslinking and curing it. In addition, the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form an uncured resin layer on the layer adjacent to the 1st protective layer 1 with the below-mentioned application system. In the present invention, the prepared coating solution is well-known such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat on the layer adjacent to the first protective layer 1 so as to have the thickness described above. This method is preferably applied by gravure coating to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the first protective layer 1. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In the electron beam irradiation, the transmission capability increases as the acceleration voltage is higher. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the first protective layer 1, the transmission depth of the electron beam The acceleration voltage is selected so that the thicknesses of the first protective layer 1 are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the 1st protective layer 1 can be suppressed, and deterioration of each layer by an excess electron beam can be minimized. The irradiation dose is preferably such that the crosslinking density of the protective layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Can be used. When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[Second protective layer 2]
The second protective layer 2 is provided on the pattern layer 3. The second protective layer 2 is provided on a part of the first protective layer 1. In the decorative sheet of the present invention, a high three-dimensional effect is imparted to the decorative sheet by the uneven shape formed by such a configuration. Moreover, by providing a gloss difference between the second protective layer 2 and the first protective layer 1, a high three-dimensional effect can be imparted to the decorative sheet. For example, the second protective layer 2 is in a highly glossy state (gross), the first protective layer 1 is in a low glossy state (matte), and both layers, and thus the formed and non-formed portions of the second protective layer 2 A high texture can be imparted to the decorative sheet by developing a gloss difference between the two. Note that the first protective layer 1 and the second protective layer 2 are preferably in contact with each other.

  Moreover, the shape formed by the recessed part shape formed by the part 1a in which the 2nd protective layer 2 on the surface of the 1st protective layer 1 was provided, and the part 1b in which it is not provided, and the pattern layer 3 mentioned later By synchronizing with, it is possible to give the decorative sheet a high three-dimensional feeling and a genuine design feeling. For example, when the pattern formed on the pattern layer 3 described later is a wood grain pattern, the wood grain pattern is made to have a real feeling by synchronizing the conduit portion expressed by the pattern with the concave and convex portions of the above-described uneven shape. Can do. Furthermore, in this invention, since the 2nd protective layer 2 and the pattern layer 3 are partially provided, and the metal thin film layer 4 can be visually observed from the surface of a decorating sheet, the 2nd protective layer 2 and the design layer formed by the pattern layer 3 are combined with the metallic luster expressed by the metal thin film layer 4 to obtain a decorative sheet having a high texture that has not been obtained conventionally.

  In addition, the 2nd protective layer 2 should just be provided on the pattern layer 3 and a part of 1st protective layer 1, for example, the part in which the pattern layer 3 is not provided The second protective layer 2 may also be provided on the top.

  The second protective layer 2 is formed of a resin composition. Specifically, the 2nd protective layer 2 is comprised by the hardened | cured material of the said resin composition. The resin contained in the resin composition forming the second protective layer 2 is not particularly limited, and for example, the same ionizing radiation curable resin, thermosetting resin as those exemplified in the first protective layer 1, A thermoplastic resin etc. are mentioned. The 2nd protective layer 2 is comprised with the hardened | cured material of the ionizing radiation-curable resin composition similarly to the 1st protective layer 1 from viewpoints, such as the three-dimensional moldability of a decorating sheet, and scratch resistance. Although it is preferable, it can select suitably as resin which forms the 2nd protective layer 2 according to the use of a decorating sheet.

  The second protective layer 2 may include at least one of inorganic particles and resin particles. Examples of the inorganic particles and the resin particles are the same as the inorganic particles and the resin particles exemplified in the first protective layer 1, respectively. In the second protective layer 2, the inorganic particles and the resin particles mainly exhibit a function of reducing the gloss of the second protective layer 2. As above-mentioned, by providing a gloss difference in the 1st protective layer 1 and the 2nd protective layer 2, a high three-dimensional effect can be provided to a decorating sheet. When inorganic particles and resin particles are included in the second protective layer 2, these particles are dispersed in the second protective layer 2.

  Although it does not restrict | limit especially as a particle diameter of the inorganic particle contained in the 2nd protective layer 2, Preferably it is about 0.5-15 micrometers, More preferably, about 1-10 micrometers is mentioned. The particle size of the resin particles is not particularly limited, but is preferably about 0.1 to 20 μm, more preferably about 0.5 to 15 μm.

  When the second protective layer 2 contains inorganic particles, the content of the inorganic particles contained in the second protective layer 2 is not particularly limited, and the amount of the resin contained in the second protective layer 2 is 100 parts by mass. On the other hand, Preferably about 1-50 mass parts, More preferably, about 5-30 mass parts is mentioned. Further, the content of the resin particles is not particularly limited, and is preferably about 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the resin contained in the second protective layer 2. Part grade.

  When the second protective layer 2 contains at least one of inorganic particles and resin particles, a part of these particles may protrude from the surface of the second protective layer 2, or the second protective layer 2 Particles may be buried inside the layer 2.

  Although the thickness of the 2nd protective layer 2 is not restrict | limited in particular, While giving a three-dimensional feeling to a decorating sheet, the uneven | corrugated shape formed by the 2nd protective layer 2 is hold | maintained also after shaping | molding, From the viewpoint of effectively suppressing the deterioration of the high stereoscopic effect that has been expressed, it is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm, and still more preferably about 1 to 5 μm. In addition, when the 2nd protective layer 2 contains at least one of the above-mentioned inorganic particle and resin particle, the thickness of the 2nd protective layer 2 is a position where the inorganic particle or the resin particle is located on the surface of the 2nd protective layer 2 The thickness of the part that is not.

  The second protective layer 2 can be formed by the same method as the first protective layer 1 described above. Specifically, a resin composition for forming the second protective layer 2 is prepared, and a known printing method such as gravure printing, offset printing, silk screen printing, ink jet printing, etc., so as to have the above-mentioned thickness, preferably It can be formed by applying a resin composition on a part of the first protective layer 1 by gravure printing and curing the resin composition by heating or irradiation with ionizing radiation as necessary. Further, the second protective layer 2 is formed on the first protective layer 1 by a transfer method using a transfer sheet obtained by forming a resin layer in a pattern on a separately prepared substrate. You can also.

  When the second protective layer 2 is formed of an ionizing radiation curable resin composition, the second protective layer 2 is in an uncured or semi-cured state of the ionizing radiation curable resin composition forming the first protective layer 1. The ionizing radiation curable resin composition for forming the ionizing radiation is partially formed, and then the ionizing radiation curable resin composition of both the first protective layer 1 and the second protective layer 2 is ionized according to conditions capable of crosslinking and curing. By irradiating with radiation, both layers can be formed by a single ionizing radiation irradiation step. Further, the ionizing radiation may be irradiated twice at the time of forming the first protective layer 1 and at the time of forming the second protective layer 2.

[Picture layer 3]
The pattern layer 3 is a layer that gives decorativeness to the resin molded product, and is formed by printing various patterns using ink and a printing machine. As described above, in the decorative sheet of the present invention, the pattern layer is partially provided so that the metallic luster due to the metal thin film layer 4 can be visually recognized when the decorative sheet is viewed in plan. Note that the width x described above corresponds to the width of the portion where the pattern layer is not provided (see FIG. 1).

  The pattern formed by the pattern layer 3 is not particularly limited. For example, a grain pattern simulating the surface of a rock such as a grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth simulating a texture or a cloth pattern Patterns, tiled patterns, brickwork patterns, etc., and patterns such as marquetry and patchwork that combine these are also included. These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed.

  As the pattern ink used for the pattern layer 3, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, Examples thereof include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. These resins may be used alone or in combination of two or more.

  The colorant is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Pigments.

  Although the thickness in particular of the pattern layer 3 is not restrict | limited, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

[Transparent resin layer 5]
The transparent resin layer 5 plays a role as a support that enhances the scratch resistance and weather resistance of the decorative sheet of the present invention and also enhances moldability. If necessary, the transparent resin layer 5 includes the metal thin film layer 4 and the pattern layer 3. Between. The transparent resin layer 5 can also be provided for the purpose of protecting the metal thin film layer 4. The transparent resin layer 5 is not particularly limited as long as it does not conceal the design of the metal thin film layer 4, and examples thereof include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic resins. .

  The thickness of the transparent resin layer 5 is not particularly limited, but is usually about 15 to 200 μm, preferably about 30 to 150 μm, from the viewpoint of serving as a support. From the viewpoint of protecting the metal thin film layer 4, the thickness is usually about 0.3 to 5 μm, preferably about 0.5 to 3 μm. The method for forming the transparent resin layer 5 is not particularly limited. For example, a method of laminating a film constituting the transparent resin layer 5 by heat lamination, dry lamination, or the like, or a method of applying a resin constituting the transparent resin layer 5 Etc.

[Base material layer 6]
The base material layer 6 is provided as necessary in order to serve as a support in the decorative sheet of the present invention. The resin component used for the base material layer 6 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the injection resin layer, and the like, and preferably a thermoplastic resin. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylic ester resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET). Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As a resin component which forms the base material layer 6, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 6 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind of resin.

  The base material layer 6 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion with an adjacent layer. . Examples of the oxidation method performed as the surface treatment of the base material layer 6 include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method and the like. Moreover, as the uneven | corrugated method performed as surface treatment of the base material layer 6, a sandblast method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 6, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  In addition, the base material layer 6 may be colored with a colorant or the like, painted for adjusting the color, formation of a pattern for imparting design properties, or the like.

  The thickness of the base material layer 6 is not particularly limited and is appropriately set depending on the use of the decorative sheet, etc., but is usually about 50 to 800 μm, preferably about 100 to 600 μm, more preferably about 200 to 500 μm. It is done. When the thickness of the base material layer 6 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.

[Hidden layer]
The concealing layer is necessary between the base material layer 6 and the first protective layer 1, between the base material layer 6 and the picture layer 3, etc., for the purpose of suppressing the color change and variation of the base material layer 6. It is a layer provided according to.

  Since the concealing layer is provided in order to prevent the base material layer 6 from adversely affecting the color tone and pattern of the decorative sheet, it is generally formed as an opaque layer.

  The concealing layer is formed using an ink composition in which a binder, a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The ink composition for forming the concealing layer is appropriately selected from those used for the picture layer 3 described above.

  The concealing layer is usually set to a thickness of about 1 to 20 μm and is desirably formed as a so-called solid printing layer.

[Primer layer 7]
The primer layer 7 is a layer included as necessary between these layers for the purpose of improving the adhesion between the metal thin film layer 4 and a layer adjacent thereto. The primer layer 7 can be formed of a resin.

  Although it does not restrict | limit especially as resin which forms the primer layer 7, For example, a urethane resin, an acrylic resin, (meth) acryl-urethane copolymer resin, a polyester resin, a butyral resin etc. are mentioned. Among these resins, a urethane resin, an acrylic resin, and a (meth) acryl-urethane copolymer resin are preferable. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be any compound having two or more hydroxyl groups in the molecule, and specific examples include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule; aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, Examples include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

  Among the urethane resins, from the viewpoint of improving the adhesion after crosslinking, preferably a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a crosslinking material; Includes a combination of acrylic polyol and hexamethylene diisocyanate.

  Although it does not restrict | limit especially as said acrylic resin, For example, the homopolymer of (meth) acrylic acid ester, the copolymer of 2 or more types of different (meth) acrylic acid ester monomers, or (meth) acrylic acid ester and others And a copolymer with the above monomer. More specifically, as a (meth) acrylic resin, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylic acid Methyl- (meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl (meth) acrylate copolymer Examples include (meth) acrylic acid esters such as polymers. These acrylic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although it does not restrict | limit especially as (meth) acryl-urethane copolymer resin, For example, acrylic-urethane (polyester urethane) block copolymer resin is mentioned. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

  Although it does not restrict | limit especially about the thickness of the primer layer 7, For example, about 0.1-10 micrometers, Preferably about 1-10 micrometers is mentioned. When the primer layer 7 satisfies such a thickness, cracking, breakage, whitening, etc. of the first protective layer 1 can be effectively suppressed.

  The primer layer 7 is a resin that forms the primer layer 7, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, It is formed by a normal coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or the like, or transfer coating. Here, the transfer coating method is a method in which a primer layer or an adhesive layer is formed on a thin sheet (film substrate) and then the surface of the target layer in the decorative sheet is coated.

[Adhesive layer 8]
The adhesive layer 8 is a layer provided as necessary for the purpose of improving the adhesion between the transparent resin layer 5 and the base material layer 6 and the adjacent layers. Further, the adhesive layer 8 may be provided on the back surface of the base material layer 6.

  The resin forming the adhesive layer 8 is not particularly limited as long as it can improve the adhesion between the decorative sheet and the injection resin, and for example, a thermoplastic resin or a thermosetting resin is used. Examples of the thermoplastic resin include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Further, the adhesive layer 8 may be a heat seal layer that develops adhesiveness by heating and pressurizing as necessary.

  The adhesive layer 8 can be formed by applying a resin used for forming the adhesive layer 8. The thickness of the adhesive layer 8 is not particularly limited, but preferably about 1 to 20 μm.

2. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention is a laminate having a molded resin layer 10, a metal thin film layer 4, a picture layer 3, a first protective layer 1, and a second protective layer 2 in this order. The pattern layer 3 is provided on a part of the metal thin film layer 4, the second protective layer 2 is on the pattern layer 3, and a part of the first protective layer 1 is formed. It is provided on the top. In the decorative resin molded product of the present invention, if necessary, the decorative sheet is further provided with at least one layer such as the above-described transparent resin layer 5, base material layer 6, primer layer 7, adhesive layer 8, and concealing layer. It may be.

  The decorative resin molded product of the present invention is produced, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. The In the present invention, the decorative sheet of the present invention is subjected to various injection molding methods to produce a decorated resin molded product, thereby exhibiting the above-described effect of suppressing the loss of stereoscopic effect during injection molding. can do. Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable.

  In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum forming die,
Trimming process to trim the excess part of the vacuum-decorated decorative sheet to obtain the molded sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the fluid resin into the injection mold Integration process to integrate the resin and the molded sheet.

  In the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, when an ABS resin film is used as the base material layer If it exists, it can be normally about 120-200 degreeC. In the integration step, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After performing, the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding simultaneously with the injection molding Thus, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the metal thin film layer side surface of the decorative sheet faces the molding surface of the movable mold having a predetermined-shaped molding surface, the decorative sheet is heated. The pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold,
After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.

  In the preforming step of the simultaneous injection molding method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. For example, if a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. Moreover, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

  In addition, the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made. In the vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The vacuum chamber side is placed in a vacuum pressure bonding machine so that the resin molded body is on the second vacuum chamber side, and the base material layer 6 side of the decorative sheet faces the resin molded body side. To do. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the formability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. Although the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, it can be about 60-200 degreeC.

  In the decorative resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the application. The molding resin that forms the molding resin layer may be a thermoplastic resin or a thermosetting resin.

  Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Since the decorative resin molded product of the present invention has a high texture, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings. A housing for home appliances such as a television receiver and an air conditioner; it can be used as a container.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Example 1>
(Preparation of decorative sheet)
An ABS film (thickness: 475 μm) was used as the base material layer 6, and a primer layer 7 made of acrylic resin for vapor deposition adhesion was printed on the surface of the base material layer 6 by gravure coating so as to have a thickness of 1 μm. Then, tin (Sn) was laminated | stacked by the thickness of about 50 nm using the vacuum evaporation machine, and it was set as the metal thin film layer 4. FIG. Subsequently, the transparent resin layer 5 made of an acrylic resin was printed by gravure coating so as to have a thickness of 1 μm. Next, the pattern layer 3 (thickness 1 μm) having a grain pattern was formed in a pattern (partial) by gravure coating using a pattern layer forming ink containing an acrylic-vinyl chloride-vinyl acetate copolymer. Next, an electron beam curable resin (polyfunctional polycarbonate (meth) acrylate) for forming the first protective layer 1 is applied to the surface of the pattern layer 3 by gravure coating in a thickness range of 1 to 6 μm. did. Subsequently, an electron beam curable resin (polyfunctional polycarbonate (meth) acrylate) for forming the second protective layer 2 so as to synchronize with the non-conduit portion of the grain formed by the pattern layer 3 described above, It was formed in a pattern (partial) by gravure coating in a thickness range of 2 to 3 μm. Finally, the electron beam curable resin for forming the first protective layer 1 and the second protective layer 2 is irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad), to thereby form an electron beam curable resin. Was cured to form a first protective layer 1 and a second protective layer 2 to obtain a decorative sheet having a laminated structure as shown in FIG. In addition, the decorative sheet obtained in Example 1 is provided with a plurality of portions having a width x of 2 to 10 mm in the region A where the second protective layer and the pattern layer are not provided in the cross section in the thickness direction. For example, as shown in the schematic diagram of FIG. 5, the metal thin film layer has a design that can be recognized as a pattern when viewed in plan from an observation distance of 1 m.

<Example 2>
(Preparation of decorative sheet)
A biaxially stretched polyethylene terephthalate film (thickness 38 μm) was used as the transfer substrate sheet. On the surface of the transfer substrate sheet, a primer layer 7 made of an acrylic resin for vapor deposition adhesion was printed by gravure coating so as to have a thickness of 1 μm. Then, tin (Sn) was laminated | stacked by the thickness of about 50 nm using the vacuum evaporation machine, and it was set as the metal thin film layer 4. FIG. Subsequently, an adhesive layer 8 (heat seal layer) made of polyester was printed by gravure coating, and then transferred to an ABS film (thickness 400 μm) as the base material layer 6 by heat lamination.
On the other hand, on the one side of an acrylic film (transparent resin layer 5) having a thickness of 75 μm, a pattern layer-forming ink containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer is used, and by gravure coating, the pattern layer 3 of wood grain pattern ( 1 μm thick) was formed in a pattern (partial). Next, an electron beam curable resin (polyfunctional polycarbonate (meth) acrylate) for forming the first protective layer 1 is applied to the surface of the pattern layer 3 by gravure coating in a thickness range of 1 to 6 μm. did. Subsequently, an electron beam curable resin (polyfunctional polycarbonate (meth) acrylate) for forming the second protective layer 2 is formed in a thickness so as to synchronize with the non-conduit portion of the grain formed by the pattern layer 3. In the range of 2 to 3 μm, a pattern (partial) was formed by gravure coating. Finally, the electron beam curable resin for forming the first protective layer 1 and the second protective layer 2 is irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad), to thereby form an electron beam curable resin. Was cured to form a first protective layer 1 and a second protective layer 2.
Next, the primer layer 7 side of the laminate in which the adhesive layer 8 made of polyester polyol is printed by gravure coating on the other side of the acrylic film of the obtained laminate and the metal thin film layer 4 is provided by dry lamination. And a decorative sheet having a laminated structure as shown in FIG. 3 was obtained. In addition, the decorative sheet obtained in Example 2 is provided with a plurality of portions having a width x of 2 to 10 mm in the region A where the second protective layer and the pattern layer are not provided in the cross section in the thickness direction. For example, as shown in the schematic diagram of FIG. 5, the metal thin film layer has a design that can be recognized as a pattern when viewed in plan from an observation distance of 1 m.

<Comparative Example 1>
(Preparation of decorative sheet)
An ABS film (thickness: 475 μm) was used as the base material layer. On the surface of the base material layer, a pattern layer (thickness 1 μm) having a grain pattern was formed by gravure coating using a pattern layer forming ink containing an acrylic-vinyl chloride-vinyl acetate copolymer. Next, an electron beam curable resin (polyfunctional polycarbonate (meth) acrylate) for forming a first protective layer was applied to the surface of the pattern layer by gravure coating in a thickness range of 1 to 6 μm. Subsequently, on the surface of the first protective layer, an electron beam curable resin (polyfunctional polycarbonate (Metal) for forming the second protective layer so as to synchronize with the non-conduit portion of the grain formed by the pattern layer. ) Acrylate) was formed in a pattern (partial) by gravure coating in a thickness range of 2-3 μm. Finally, the electron beam curable resin for forming the first protective layer and the second protective layer is irradiated with an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin. Then, the first protective layer and the second protective layer were formed to obtain a decorative sheet. In addition, in the decorative sheet obtained in Comparative Example 1, the pattern layer is provided on substantially the entire surface, and when viewed in plan from an observation distance of 1 m, it has an excellent three-dimensional wood grain design as a whole. However, since it does not have a metal thin film layer, it does not have a metallic design feeling.

<Comparative example 2>
(Preparation of decorative sheet)
As a transfer base sheet, a biaxially stretched matted polyethylene terephthalate film (thickness 38 μm) is used, and as the surface protective layer forming resin, the thickness after curing is 10 μm. Polyfunctional polycarbonate (meth) acrylate) was printed on the surface of the transfer substrate sheet by gravure coating. A primer layer made of an acrylic resin was printed on the uncured resin layer by gravure coating so as to have a thickness of 1 μm. Next, a pattern layer (thickness 1 μm) with a grain pattern was formed into a pattern (partial) by gravure coating using a pattern layer forming ink containing an acrylic-vinyl chloride-vinyl acetate copolymer. A primer layer made of an acrylic resin for vapor deposition adhesion was printed by gravure coating to a thickness of 1 μm. Next, tin (Sn) was laminated | stacked by the thickness of about 50 nm using the vacuum evaporation machine, and it was set as the metal thin film layer. Subsequently, an adhesive layer (heat seal layer) made of polyester was printed by gravure coating, and then transferred to an ABS film (thickness: 475 μm) as a base material layer by heat lamination to obtain a decorative sheet. In addition, the decorative sheet obtained in Comparative Example 2 has a plurality of portions where the width x of the region A in which the second protective layer and the pattern layer are not provided is 2 to 10 mm in the cross section in the thickness direction. For example, as shown in the schematic diagram of FIG. 5, the metal thin film layer has a design that can be recognized as a pattern when viewed from an observation distance of 1 m, but there is no three-dimensional effect of the wood grain pattern portion. It is a design.

(Evaluation of texture of decorative sheet)
Using 20 industrial designers as monitors, sensory evaluation was performed to determine whether the texture of each decorative sheet obtained above had a sufficient texture. A decorative sheet with a texture of 15 or more and 20 or less is rated as “good”, and a decorative sheet with a texture of 5 or more but less than 15 is normally “△”. The decorative sheet of less than 5 people was evaluated as “x” with poor texture. The results are shown in Table 1.

As shown in Table 1, a metal thin film layer, a picture layer provided on a part of the metal thin film layer, a first protective layer, and a part of the first protective layer are provided. The decorative sheet of Examples 1 and 2 consisting of a laminated body having the second protective layer in this order, the metallic luster partially visible when the decorative sheet is viewed in plan, and partially It was evaluated that it had an excellent texture due to the combination with the design (wood grain pattern) of excellent three-dimensional effect expressed by the provided second protective layer and the pattern layer.
On the other hand, the decorative sheet of Comparative Example 1 had an excellent three-dimensional wood grain pattern, but the texture was inferior to the decorative sheets of Examples 1 and 2. In addition, the decorative sheet of Comparative Example 2 has a good texture due to the presence of partially visible metallic luster, but lacks the three-dimensional effect of the wood grain pattern, and the decorative sheet of Examples 1 and 2 as a whole. The evaluation was inferior to the decorative sheet.

DESCRIPTION OF SYMBOLS 1 ... 1st protective layer 2 ... 2nd protective layer 3 ... Pattern layer 4 ... Metal thin film layer 5 ... Transparent resin layer 6 ... Base material layer 7 ... Primer layer 8 ... Adhesive layer 10 ... Molding resin layer

Claims (12)

It consists of a laminate having at least a metal thin film layer, a pattern layer, a first protective layer, and a second protective layer in this order,
The pattern layer is provided on a part of the metal thin film layer,
The second protective layer is a decorative sheet provided on the pattern layer and provided on a part of the first protective layer.   The decorative sheet according to claim 1, wherein the metal thin film layer is a metal vapor deposition layer, a metal sputtering layer, a metal ion plating layer, a high-brightness ink layer, or a metal plating layer.   The decorative sheet according to claim 1 or 2, wherein the first protective layer is provided on the entire surface of one side of the decorative sheet.   The decoration sheet in any one of Claims 1-3 which has a transparent resin layer between the said metal thin film layer and the said pattern layer.   The decorative sheet according to any one of claims 1 to 4, wherein the first protective layer contains at least one of inorganic particles and resin particles.   The decorative sheet according to any one of claims 1 to 5, wherein the second protective layer includes at least one of inorganic particles and resin particles.   The decoration sheet according to any one of claims 1 to 6, wherein the metal thin film layer can be visually recognized when the decoration sheet is viewed in plan from the second protective layer side at an observation distance of 1 m. .   The cross section of the thickness direction of the said decoration sheet WHEREIN: The width x of the area | region A where both the said 2nd protective layer and the said pattern layer are not provided has a part which is 1 mm or more. Decorative sheet according to crab.   On the first protective layer, a concave shape formed by a portion where the second protective layer is provided and a portion where the second protective layer is not provided is synchronized with the pattern of the picture layer. The decorative sheet according to any one of 8. At least comprising a laminate having in this order a molded resin layer, a metal thin film layer, a pattern layer, a first protective layer, and a second protective layer,
The pattern layer is provided on a part of the metal thin film layer,
The second protective layer is a decorative resin molded product provided on the picture layer and provided on a part of the first protective layer. The decorative sheet according to any one of claims 1 to 9 is inserted into an injection mold, the injection mold is closed, and a resin in a fluid state is injected into the injection mold, thereby the resin and the decorative sheet. Integration process to integrate
A method for producing a decorated resin molded product.   The manufacturing method of the decorative resin molded product of Claim 11 which provides the vacuum forming process which shape | molds the said decoration sheet | seat into a solid | 3D shape previously with a vacuum forming die before the said integration process.