JP6232884B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet capable of imparting an excellent design feeling and touch feeling due to an uneven shape. More specifically, the present invention relates to a decorative sheet that can give an excellent design feeling and touch feeling without damaging the uneven shape even when subjected to injection molding. Furthermore, this invention relates to the manufacturing method of the decorative resin molded product using the said decorating sheet.

  A decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for a vehicle interior part, a building material interior material, a home appliance housing, and the like. In recent years, with the diversification of consumer needs, decorative resin molded products having various design properties have been demanded. In order to follow the diversifying consumer needs, it is desired to develop a decorative resin molded product having a concavo-convex shape on the surface and having a good touch as well as a design feeling.

  Conventionally, in the production of a decorative resin molded product, a molding method in which a decorative sheet that has been given designability in advance is integrated with a resin by injection molding is used, and a decorative resin molded product in which an uneven shape is formed In the manufacture of the above, a decorative sheet having an uneven shape on the surface is used.

  However, when manufacturing a decorative resin molded product using a decorative sheet having a concavo-convex shape, the concavo-convex shape may be deformed by heat or pressure when the decorative sheet is subjected to injection molding or pre-formation (vacuum molding) prior to that. In other words, the decorative sheet after injection molding cannot maintain the initial concavo-convex shape, and the design feeling and touch feeling due to the concavo-convex shape cannot be sufficiently imparted. In order to overcome such drawbacks, vacuum molding and injection molding are performed by laminating a cushion layer made of thermoplastic resin by extrusion molding or hot melt coating method on the surface of the decorative sheet on which irregularities are formed by embossing. There has been reported a method of suppressing deformation and disappearance of the uneven shape that sometimes occurs and removing the cushion layer after injection molding (see, for example, Patent Document 1). However, in the method described in Patent Document 1, since the softening point of the resin of the cushion layer provided on the surface of the decorative sheet is low, the dimensional stability is poor, and the cushion layer contracts or peels over time. There is a drawback.

JP 2008-137216 A

  An object of the present invention is to provide a decorative sheet that is dimensionally stable and that can maintain an excellent design feeling and touch feeling due to an uneven shape even when subjected to injection molding, and a decorative resin molded article using the decorative sheet. Is to provide a method.

  The inventors of the present invention have made extensive studies to solve the above problems, and in the decorative sheet in which the base material layer, the surface layer having an uneven shape, and the peelable uneven protective layer are laminated in this order, By forming the surface layer and the protective layer with a cured product of a resin composition containing an ionizing radiation curable resin, it is possible to suppress deformation and disappearance of the uneven shape that occurs during vacuum molding and injection molding, and molded as a decorative resin molded product It has been found that even if it is integrally molded with a resin, it is possible to maintain an excellent design feeling and touch feeling due to unevenness. In the decorative sheet, since the protective layer is formed of a cured product of a resin composition containing an ionizing radiation curable resin, the protective layer is excellent in dimensional stability, and the protective layer shrinks with time. It has also been found that peeling and the like can be suppressed. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The decorative sheet, wherein the surface layer and the protective layer are formed of a cured product of a resin composition containing an ionizing radiation curable resin.
Item 2. Item 2. The decorative sheet according to Item 1, comprising polycarbonate (meth) acrylate as the ionizing radiation curable resin.
Item 3. Furthermore, the decorating sheet | seat of claim | item 2 containing polyfunctional urethane (meth) acrylate as said ionizing radiation curable resin.
Item 4. Item 4. The decorative sheet according to Item 3, wherein the mass ratio of the polycarbonate (meth) acrylate and the multifunctional urethane (meth) acrylate is 50:50 to 99: 1.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the uneven protective layer has a thickness of 10 to 100 µm.
Item 6. A first step of forming a laminate in which a surface layer made of a cured product of a resin composition having an uneven shape and containing an ionizing radiation curable resin is laminated on a base material layer, and obtained in the first step The manufacturing method of a decorating sheet | seat including the 2nd process of forming an uneven | corrugated protective layer by apply | coating and hardening the resin composition containing ionizing radiation curable resin on the surface layer of the laminated body.
Item 7. A molded resin layer, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The decorative resin molded article with an uneven protective layer, wherein the surface layer and the protective layer are formed of a cured product of a resin composition containing an ionizing radiation curable resin.
Item 8. The manufacturing method of the decorative resin molded product with an uneven | corrugated protective layer including the process of forming a molded resin layer by injecting resin to the base material layer side of the decorating sheet in any one of claim | item 1 -5.
Item 9. The manufacturing method of a decorative resin molded product including the process of peeling an uneven | corrugated protective layer from the decorative resin molded product with an uneven | corrugated protective layer of claim | item 7.

  Even if the decorative sheet of the present invention is subjected to vacuum molding or injection molding, the uneven shape can be stably maintained, so that the decorative resin molded product maintains an excellent design feeling and touch feeling due to the uneven shape. Can do. In addition, the decorative sheet of the present invention has a good dimensional stability because the protective layer peeled off after being subjected to injection molding is formed of a cured product of a resin composition containing an ionizing radiation curable resin. In addition, the protective layer can be prevented from shrinking or peeling off over time.

  Furthermore, since the decorative sheet of the present invention can also have excellent three-dimensional formability, it can be used for the production of a decorative resin molded product having a complicated surface shape such as a three-dimensional curved surface.

It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorative resin molded product with an uneven | corrugated protective layer of this invention. It is a figure which shows the cross-sectional structure of one form of the decorative resin molded product manufactured by peeling the uneven | corrugated protective layer from the decorative resin molded product with an uneven | corrugated protective layer of this invention.

1. The decorative sheet of the present invention comprises at least a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer in this order, and the surface layer and the uneven protective layer are ionizing radiation. It is formed with the hardened | cured material of the resin composition containing curable resin, It is characterized by the above-mentioned. Hereinafter, the decorative sheet of the present invention will be described in detail. In the present specification, unless otherwise specified, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations 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 base material layer 1, a surface layer 2 having an uneven shape, and a peelable uneven protective layer 3 are laminated in this order.

  In the decorative sheet of the present invention, a primer layer 4 may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of improving the adhesion between the layers.

  Moreover, you may provide the pattern layer 5 between the base material layer 1 and the surface layer 2 as needed in order to provide decorating property. When the primer layer 4 is provided, a pattern layer may be provided between the base material layer 1 and the primer layer 4.

  Moreover, between the base material layer 1 and the surface layer 2, the concealing layer 6 may be provided as needed for the purpose of suppressing the color change and variation of the base material layer 1. If the primer layer 4 is provided, the concealing layer 6 may be provided between the base material layer 1 and the primer layer 4, and if the pattern layer 5 is provided, the concealing layer 6 is a base layer. What is necessary is just to provide between the material layer 1 and the pattern layer 5. FIG.

  Further, a transparent resin layer 7 may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of improving scratch resistance. If the primer layer 4 is provided, the transparent resin layer 7 may be provided between the pattern layer 5 and the primer layer 4.

Furthermore, in the decorative sheet of the present invention, the back surface of the base material layer 1 (the surface on the side opposite to the surface layer 2) for the purpose of enhancing the adhesion with the molding resin during the molding of the decorative resin molded product. For example, the adhesive layer 8 may be provided as necessary. As an example of the laminated structure of the decorative sheet of the present invention, the base material layer 1 / the pattern layer 5 / the surface layer 2 / the uneven protective layer 3 are laminated in order. Laminated structure; substrate layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / unevenness protection layer 3 laminated in order; substrate layer 1 / pattern layer 5 / transparent resin layer 7 / primer layer 4 / surface layer 2 / concave / convex protective layer 3 are laminated in order. FIG. 1 shows a cross-sectional view of a decorative sheet in which a base layer 1 / a pattern layer 5 / a surface layer 2 / an uneven protective layer 3 are sequentially stacked as an aspect of the laminated structure of the decorative sheet of the present invention. In FIG. 2, as an aspect of the laminated structure of the decorative sheet of the present invention, the base layer 1 / the pattern layer 5 / the transparent resin layer 7 / the primer layer 4 / the surface layer 2 / the uneven protective layer 3 are sequentially laminated. Sectional drawing of a decoration sheet is shown.
Composition of each layer of the decorative sheet [base material layer 1]
The base material layer 1 is a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molding resin, and the like. Preferably, a resin film made of a thermoplastic resin is used. Can be mentioned. Specific examples of the thermoplastic resin include acrylonitrile / butadiene / styrene resin (hereinafter sometimes referred to as “ABS resin”), acrylonitrile / styrene / acrylic ester resin (hereinafter referred to as “ASA resin”). A), polyolefin resins such as acrylic resin, polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) and the like. Among these, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Moreover, the base material layer 1 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 | species resin.

  The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a decorative resin by an insert molding method, the flexural modulus at 25 ° C. of the base material layer 1 in the decorative sheet of the present invention is preferably 500 to 4,000 MPa, preferably Is 750 to 3,000 MPa. Here, the flexural modulus at 25 ° C. is a value measured according to JIS K7171. When the flexural modulus at 25 ° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and even when subjected to the insert molding method, the surface characteristics and moldability are further improved. In addition, when the bending elastic modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied when manufacturing by roll-to-roll, and sagging does not easily occur. So that the so-called pattern registration is good.

  The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as necessary in order to improve adhesion with a layer provided thereon. May be. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of the base material layer 1, a sandblasting 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 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  The base material layer 1 may be subjected to a treatment such as forming a known adhesive layer.

  Furthermore, the base material layer 1 may be colored with a coloring agent or may not be colored. Moreover, the base material layer 1 may be any of colorless and transparent, colored and transparent, and translucent. Although it does not restrict | limit especially as a coloring agent used for the base material layer 1, Preferably the coloring agent which does not discolor also under the temperature conditions of 150 degreeC or more is mentioned, Specifically, the existing dry color, paste color, masterbatch resin Examples thereof include compositions.

Although the thickness of the base material layer 1 is suitably set according to the use of the decorative sheet, the molding method to be integrated with the molding resin, etc., usually about 25 to 1000 μm and about 50 to 700 μm are mentioned. More specifically, if the decorative sheet of the present invention is subjected to the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably 100 to 700 μm, more preferably 100 to 500 μm. Can be mentioned. Moreover, if it is a case where the decorating sheet of this invention is used for the injection molding simultaneous decorating method, as thickness of the base material layer 1, 25-200 micrometers normally, Preferably it is 50-200 micrometers, More preferably, 70-200 micrometers is mentioned. .
[Surface layer 2]
The surface layer 2 has an uneven shape and is formed of a cured product of a resin composition containing an ionizing radiation curable resin. Thus, by forming a surface layer having an uneven shape with a cured product of a resin composition containing an ionizing radiation curable resin, and covering the surface layer with a specific uneven protective layer described later, vacuum forming or It is possible to suppress deformation and disappearance of the concavo-convex shape that occurs at the time of injection molding, and to impart an excellent design feeling and touch feeling to the decorative resin molded product.
<Uneven shape>
The concavo-convex shape formed on the surface layer 2 is not particularly limited, and may be appropriately set according to the design feeling or the touch to be imparted. Examples of the uneven shape include a hairline pattern, a wood grain pattern, a geometric pattern (dots, stripes, carbon) and the like.

  Further, the height of the convex portion, the width of the convex portion, the pitch between the adjacent convex portions, the width of the concave portion, etc. in the concave-convex shape formed on the surface layer 2 are appropriately determined according to the design feeling or touch to be imparted. You only have to set it. For example, as the center line average roughness (Ra) of the surface layer 2, from the viewpoint of imparting an excellent design feeling and touch due to the uneven shape, it is usually 1.5 to 80 μm, preferably 1.5 to 70 μm, more preferably. 1.5-60 micrometers is mentioned. When the average roughness of the center line of the surface layer 2 is 80 μm or less, when the decorative sheet is wound and stored in a roll shape, the irregularities are excessively severe, resulting in damage or tear during transportation or collapse of the winding. It is preferable that the above does not occur.

Further, the uneven shape formed by the surface layer 2 may be such that the bottom surface of the recess is formed by the surface layer 2 as in the embodiment shown in FIG. 3, and the bottom surface of the recess is the surface as in the embodiment shown in FIG. The lower layer of the layer 2 may be exposed and a plurality of convex portions may be partially provided. 3 and 4 show a laminated structure in which the base material layer 1, the surface layer 2, and the concave / convex protective layer 3 are laminated in order.
<Ionizing radiation curable resin>
The ionizing radiation curable resin used for forming the surface layer 2 refers to a resin that crosslinks and cures when irradiated with ionizing radiation. Here, the 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. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included. Among ionizing radiation curable resins, electron beam curable resins can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics, which is suitable for forming a surface protective layer. used.

  Specific examples of the ionizing radiation curable resin include those obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

  Specific examples of the oligomer used as the ionizing radiation curable resin include polyfunctional urethane (meth) acrylate oligomers. Specific examples of the polyfunctional urethane (meth) acrylate oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, and the like. . Here, the urethane (meth) acrylate can be obtained, for example, by esterifying polyurethane obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. 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 having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or by adding an alkylene to a polyvalent carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an 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) acrylate acid to the side chain of polybutadiene. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol diene. (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) Chryrate, 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.

  Among these ionizing radiation curable resins, from the viewpoint of imparting an even better design feeling and feel to the decorative resin molded product while facilitating the peeling operation of the uneven protective layer, preferably in the molecule. An oligomer having a polymerizable unsaturated bond or an epoxy group, more preferably polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, particularly preferably polycarbonate (meth) acrylate.

  Among these ionizing radiation curable resins, (1) Polycarbonate (Metal) is preferable from the viewpoint of providing a much better design feeling and hand feeling while further facilitating the peeling operation of the uneven protective layer. ) Acrylates and (2) other polyfunctional (meth) acrylate (polyfunctional (meth) acrylate oligomers or monomers) combinations; more preferably (1) polycarbonate (meth) acrylate and (2) polyfunctional The combination of urethane (meth) acrylate is mentioned.

  When the ionizing radiation curable resin (1) and the ionizing radiation curable resin (2) are used in combination, these ratios may be set in consideration of the molecular weight, the number of functional groups, etc. For example, the mass ratio of the ionizing radiation curable resin (1) to the ionizing radiation curable resin (2) (ionizing radiation curable resin (1): ionizing radiation curable resin (2)) However, it is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and particularly preferably about 85:15 to 99: 1.

Below, the polycarbonate (meth) acrylate and polyfunctional urethane (meth) acrylate which are used suitably as an ionizing radiation curable resin for forming the surface layer 2 are explained in full detail.
The polycarbonate (meth) acrylate used as the polycarbonate (meth) acrylate ionizing radiation curable resin is particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Not. Moreover, the said (meth) acrylate is 2 or more normally as a number of the functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable, Preferably 2-6 are mentioned.

  The polycarbonate (meth) acrylate is obtained, for example, by converting 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 from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be 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 divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. 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, 1,5-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 are formed by an esterification reaction described later, and moderate flexibility is imparted to the 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.

  The molecular weight of the polycarbonate (meth) acrylate is not particularly limited. For example, the weight average molecular weight is 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but may be, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of further improving the moldability, the weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and not more than 50,000, and more preferably 5,000 to 20,000.

In addition, the weight average molecular weight of the polycarbonate (meth) acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.
<Multifunctional urethane (meth) acrylate>
A polyfunctional urethane (meth) acrylate will not be restrict | limited especially if it has a urethane bond in a polymer principal chain, and has a (meth) acrylate in the terminal or a side chain. Such 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. The urethane (meth) acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving crosslinking and curing. In addition to the polycarbonate (meth) acrylate, the ionizing radiation curable resin composition used for forming the surface protective layer 2 may further contain urethane (meth) acrylate. 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 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 urethane (meth) acrylate is not particularly limited, but is, 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 urethane (meth) acrylate in this specification is the value measured by the gel permeation chromatography method using polystyrene as a standard substance.
<Other additives>
Moreover, various additives can be mix | blended with the resin composition used for formation of the surface layer 2 according to the desired physical property with which the surface layer 2 is equipped. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, and leveling agents. , Thixotropic agent, coupling agent, plasticizer, antifoaming agent, filler, solvent, colorant and the like. 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.
<Thickness of surface layer 2>
Although it does not restrict | limit especially about the thickness after hardening of the surface layer 2, For example, 0.01-20 micrometers, Preferably it is 0.01-15 micrometers, More preferably, 0.01-12 micrometers is mentioned. By satisfying the thickness in such a range, the uneven shape can be more effectively expressed, and an excellent design feeling and hand feeling can be provided.
<Formation of surface layer 2>
The surface layer 2 may be formed on a predetermined layer so that the cured product of the resin composition containing the ionizing radiation curable resin has an uneven shape, and the specific method is not particularly limited. Absent. Examples of a method for providing the surface layer 2 with a concavo-convex shape include a method of embossing, a method of applying and curing the resin composition forming the surface layer 2 only on the portion where the convex portion is formed, and the like. An embossing method is preferred.

Specific examples of the method for forming the surface layer 2 having an uneven shape include the following first to third methods.
First method: A base material layer 1 and other layers provided as necessary are laminated in order to prepare a sheet having other than the surface layer 2, and embossing is performed on the side of the sheet on which the surface layer is laminated. Then, a method of applying the resin composition used for forming the surface layer 2 and curing the resin composition.
Second method: The base material layer 1 and other layers provided as necessary are laminated in order to prepare a sheet having other than the surface layer 2, and the surface layer 2 on the side on which the surface layer of the sheet is laminated. A method of embossing the surface layer 2 side after applying the resin composition used for formation and curing the resin composition.
Third method: The base material layer 1 and other layers provided as necessary are sequentially laminated to prepare a sheet having other than the surface layer 2, and a convex portion on the side where the surface layer of the sheet is laminated is formed. A method in which a resin composition used for forming the surface layer 2 is applied only to a portion to be cured and the resin composition is cured.

  The method for applying the resin composition used for forming the surface layer 2 on the predetermined layer is not particularly limited, and examples thereof include gravure coating, bar coating, roll coating, reverse roll coating, and comma coating. A gravure coat is preferable.

  In this way, the resin composition (uncured resin layer) applied on the predetermined layer is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the resin composition to form the surface layer 2. . 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 addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material layer, and to minimize the deterioration of the base material due to the excess electron beam.

  The irradiation dose is preferably such that the crosslink density of the resin layer 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).

  Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. 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.
[Unevenness protection layer 3]
The concave / convex protective layer 3 is a layer provided on the surface layer 2 so as to be in contact with the surface layer 2, is laminated so as to be peelable from the interface with the surface layer 2, and is integrally formed with the molding resin. It is a layer to be peeled later. Moreover, the uneven | corrugated protective layer 3 is formed from the hardened | cured material of the resin composition containing ionizing radiation curable resin. In this way, the surface layer 2 having a specific composition on which irregularities are formed is covered with the irregularity protective layer having a specific composition, so that the irregular shape of the surface layer 2 is deformed or lost during vacuum molding or injection molding. It is possible to suppress and impart an excellent design feeling and hand feeling to the decorative resin molded product.
<Ionizing radiation curable resin>
About the kind of ionizing radiation curable resin used for formation of the uneven | corrugated protective layer 3, a preferable thing, etc. are the same as that used for formation of the said surface layer 2. FIG. In particular, among the ionizing radiation resins, the combination of the ionizing radiation curable resin (1) and the ionizing radiation curable resin (2) exemplified in the section of the surface layer 2 is the surface layer during vacuum molding or injection molding. 2 can be used not only for suppressing the deformation and disappearance of the concavo-convex shape, but also for ease of detachment when it is integrally formed with the molding resin, so that the concavo-convex protective layer 3 is preferably used. Further, the ionizing radiation curable resin used for forming the uneven protective layer 3 and the ionizing radiation curable resin used for forming the surface layer 2 may be the same type or different types. .
<Other additive components>
In addition to the ionizing radiation curable resin, other resin components may be included in the resin composition used for forming the unevenness protection layer 3 as necessary for improving the moldability. Examples of the resin component other than the ionizing radiation curable resin include acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; Polyolefin such as polypropylene, styrene resin such as polystyrene and α-methylstyrene, polyamide, polycarbonate, acetal resin such as polyoxymethylene, fluorine resin such as ethylene-4 fluoroethylene copolymer, polyimide, polylactic acid, polyvinyl Acetal resin; thermoplastic resin such as liquid crystalline polyester resin. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type.

Furthermore, various additives can be mix | blended with the resin composition which forms the uneven | corrugated protective layer 3 according to the desired physical property with which the uneven | corrugated protective layer 3 is equipped. 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.
<Thickness of uneven protective layer 3>
Although it does not restrict | limit especially about the thickness of the uneven | corrugated protective layer 3, For example, 5-100 micrometers is mentioned. Moreover, from the viewpoint of facilitating peeling of the uneven protective layer after being integrated with the molding resin, the thickness of the uneven protective layer 3 is preferably 10 to 100 μm, more preferably 15 to 100 μm. In addition, the thickness of the uneven | corrugated protective layer 3 means the thickness of the protective layer after hardening, when using cured resin here.
<Formation of uneven protective layer 3>
The protective layer is formed by applying a resin composition containing an ionizing radiation curable resin to the surface layer 3 after curing by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and the like. The resin composition may be cured by irradiating with ionizing radiation. The irradiation conditions of ionizing radiation are the same as in the case of forming the surface layer 2.
[Primer layer 4]
The primer layer 4 has a pattern layer 5 when the pattern layer 5 is provided between the base layer 1 and the surface layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface layer 2. And / or the surface layer 2 and / or between the base material layer 1 and the pattern layer 5 as necessary.

  Primer compositions constituting the primer layer 4 include urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene. Those using chlorinated polyethylene as a binder resin are preferably used, and these resins can be used alone or in combination of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

  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. As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. 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, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

  From the viewpoints of adhesion with the surface protective layer after crosslinking, difficulty of interaction after laminating the surface layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as polyol, and hexamethylene diisocyanate as crosslinking material, It is preferable to combine with 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use acrylic polyol and hexamethylene diisocyanate in combination.

  (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers. Polymers, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.

  As the (meth) acryl-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the above-mentioned various isocyanates are used. The acrylic-urethane (polyester urethane) block copolymer resin adjusts the acrylic / urethane ratio (mass ratio) in the range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.

  Although it does not restrict | limit especially about the thickness of the primer layer 4, For example, it is about 0.5-20 micrometers, Preferably, 1-5 micrometers is mentioned.

The primer layer 4 is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat with a silk screen, a wire bar coat, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating method. 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.
[Picture layer 5]
The pattern layer 5 is provided between the base material layer 1 and the surface layer 2 or between the base material layer 1 and the primer layer 4 or a concealing layer when the primer layer 4 is provided for the purpose of imparting decorativeness to the decorative sheet. 6 is a layer provided between the masking layer 6 and the surface layer 2 as necessary.

  The picture layer 5 is a layer in which a desired picture is formed using the ink composition. As the ink composition used for forming the pattern layer 5, a binder and 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 binder used in the ink composition is not particularly limited. For example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin , Polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like. These binders may be used individually by 1 type, and may be used in combination of 2 or more type.

  The colorant used in the ink composition is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue Inorganic pigments such as: organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue; metal pigments composed of scaly foils such as aluminum and brass; scaly foils such as titanium dioxide-coated mica and basic lead carbonate Examples include pearlescent (pearl) pigments composed of pieces.

  The pattern formed by the pattern layer 5 is not particularly limited. For example, a pattern of a stone pattern, a texture pattern or a cloth pattern imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern) is simulated. Examples include fabric patterns, tiled patterns, brickwork patterns, and the like, and patterns such as parquets, patchwork, etc., which are a combination of these. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but also by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. Can be formed.

Although the thickness in particular of the pattern layer 5 is not restrict | limited, For example, 1-30 micrometers, Preferably 1-20 micrometers is mentioned.
[Hidden layer 6]
The concealing layer 6 is provided between the base material layer 1 and the surface layer 2 for the purpose of suppressing the color change and variation of the base material layer 1. If the pattern layer 5 is provided between the substrate layer 1 and the pattern layer 5, it is a layer provided as necessary.

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

  The masking layer 6 is formed by using an ink composition in which 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 appropriately mixed. The ink composition for forming the masking layer 6 is appropriately selected from those used for the pattern layer described later.

  The concealing layer 6 is normally set to a thickness of about 1 to 20 μm and is desirably formed as a so-called solid printing layer.

The concealing layer 6 is a normal printing method such as gravure printing, offset printing, silk screen printing, printing from a transfer sheet, inkjet printing, etc .; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse It is formed by a normal coating method such as roll coating.
[Transparent resin layer 7]
For the purpose of improving chemical resistance and scratch resistance, the transparent resin layer 7 is provided between the base layer 1 and the surface layer 2. 5 is provided between the pattern layer 5 and the surface layer 2, or when the primer layer 4 and the pattern layer 5 are provided in this order on the base material layer 1, between the primer layer 4 and the pattern layer 5 as required. It is a layer provided. The transparent resin layer 7 is a layer suitably provided in a decorative sheet that is integrated with a molding resin by an insert molding method.

  The resin component forming the transparent resin layer 7 is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, etc., but a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited, and examples thereof include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, ABS resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and vinyl chloride resins. Etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, scratch resistance, etc., preferably acrylic resins, polyolefin resins, polycarbonate resins, polyester resins; more preferably acrylic resins, polyester resins; more preferably polyesters. Resin.

  The transparent resin layer 7 is subjected to a 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 other layers that are in contact with each other. May be. These physical or chemical surface treatments are the same as the surface treatments applied to the base material layer.

  Although it does not restrict | limit especially about the thickness of the transparent resin layer 7, For example, 10-200 micrometers, Preferably 15-150 micrometers is mentioned.

The transparent resin layer 7 may be laminated via an adhesive, or may be laminated directly without using an adhesive. When laminating via an adhesive, examples of the adhesive used include polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, and polyresin. Examples thereof include vinyl acetate resin, cellulose resin, (meth) acrylic resin, polyimide resin, amino resin, rubber, and silicon resin. Moreover, when laminating | stacking without using an adhesive agent, it can carry out by methods, such as an extrusion method, a sand lamination method, and a thermal lamination method.
[Adhesive layer 8]
The adhesive layer 8 is provided on the back surface (surface opposite to the surface layer 2) of the base material layer 1 as necessary for the purpose of enhancing the adhesion with the molding resin when molding a decorative resin molded product. It is a layer provided.

  A thermoplastic resin or a curable resin is used for the adhesive layer 8 according to the molding resin used for the decorative resin molded product.

  Examples of the thermoplastic resin used for forming the adhesive layer 8 include an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, a vinyl chloride / vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, and a polyamide. Examples thereof include resins and rubber 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 used for formation of the contact bonding layer 8, 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.
The decorative sheet manufacturing method The decorative sheet of the present invention can be manufactured through the following first and second steps, for example.

In the first step, the first step of forming a laminate on which the surface layer 2 having a concavo-convex shape and a cured product of a resin composition containing an ionizing radiation curable resin is laminated on the base material layer 1, The 2nd process of forming the uneven | corrugated protective layer 3 by apply | coating and hardening the resin composition containing ionizing radiation-curable resin on the surface layer 2 of the obtained laminated body.

In the first and second steps, the components used for forming each layer, the specific conditions of the method for forming each layer, the method for forming the uneven shape of the surface layer 2, and the like are as described in the section of the composition of each layer. .
2. Uneven protective layer-decorated resin molded article uneven protective layer-decorated resin molded article of the present invention is formed is molded by integrally molding a resin in the decorative sheet of the present invention. That is, the decorative resin molded product with an uneven protective layer of the present invention has at least a molded resin layer 9, a base material layer 1, an uneven surface layer 2, and an uneven protective layer 3 in this order. And the uneven | corrugated protective layer 3 is formed from the hardened | cured material of the resin composition containing ionizing radiation curable resin, It is characterized by the above-mentioned. In FIG. 5, about the suitable one aspect | mode of the decorative resin molded product with an uneven | corrugated protective layer of this invention, the cross-sectional structure is shown.

  The decorative resin molded product with a concavo-convex protective layer of the present invention is, for example, various injection moldings such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. It is produced by the method. The decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded product with a concave-convex protective layer, thereby exhibiting the above-described effect of suppressing the concave-convex shape from being damaged during injection molding. Therefore, as a suitable example of the molded resin layer 9 constituting the decorative resin molded product with a concave-convex protective layer of the present invention, an injection resin layer formed by injection molding can be given. 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 process, 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 extra portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, a resin in a fluid state is injected into the mold and solidified, and at the same time as the injection molding, a decorative sheet is formed on the outer surface of the resin molded product. By integrating the material layer 1 side, a decorative resin molded product with an uneven protective layer is produced.

  More specifically, the decorative resin molded product with an uneven protective layer of the present invention is produced 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 excess portions of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above process into an injection mold, closing the injection mold, and molding the fluid resin The process of injecting 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. For example, the temperature is usually about 100 to 250 ° C, preferably about 130 to 200 ° C. Moreover, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° 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 the injection mold is clamped, the resin in a fluid state is injected and filled into the mold and solidified, and the base material layer of the decorative sheet of the present invention is formed on the outer surface of the resin molding simultaneously with the injection molding By integrating the one side, a decorative resin molded product with a concavo-convex protective layer is produced.

  More specifically, the decorative resin molded product with a concavo-convex protective layer of the present invention is produced by an injection molding simultaneous decorating method including the following steps.

After the decorative sheet of the present invention is installed so that the base material of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. And vacuum suction from the movable mold side, the step of preforming the decorative sheet by adhering the softened decorative sheet along the molding surface of the movable mold,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a movable molded mold is separated from the fixed mold, and the entire decorative sheet is laminated. The process of taking out.

  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. 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. In the injection molding process, the temperature of the resin in the fluidized state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° 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 press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. 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 with a concave-convex protective layer of the present invention, the molded resin layer may be formed by selecting a molded resin according to the application. The molding resin may be a thermoplastic resin or a thermosetting resin.

  Examples of the thermoplastic resin used as the molding 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.

  Examples of the thermosetting resin used as the molding resin include urethane resins and epoxy resins. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

A decorative resin molded product can be obtained by peeling and removing the concave / convex protective layer from the decorative resin molded product with the concave / convex protective layer of the present invention. In addition, in a decorative resin molded product with a concavo-convex protective layer, the concavo-convex protective layer plays a role as a protective sheet for the decorative resin molded product, so that it is stored as it is without being peeled after manufacturing, and the concavo-convex protective layer is used during use. May be peeled off. By using in such a mode, it is possible to prevent the decorative resin molded product from being damaged due to rubbing during transportation.
3. Decorative resin molded product A decorative resin molded product having a concavo-convex shape on its surface is obtained by removing the concavo-convex protective layer from the decorative resin molded product with the concavo-convex protective layer. When the support is peeled and removed from the decorative resin molded product with a concave-convex protective layer, the surface layer 2 appears on the surface of the decorative resin molded product, and an excellent design feeling and touch feeling are expressed by the concave-convex shape. In FIG. 6, the cross-sectional structure is shown about the suitable one aspect | mode of the decorative resin molded product from which the uneven | corrugated protective layer was removed.

  Since the decorative resin molded product of the present invention has an excellent design feeling and touch feeling due to the uneven shape, for example, interior or exterior materials for vehicles such as automobiles; It can be used as fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; housings for home appliances such as television receivers and air conditioners; containers and the like.

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.
[Manufacture of decorative sheets]
Examples 1-6
An ABS resin film (thickness: 200 μm) was used as the base material layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the base material layer by gravure printing using an ink composition containing an acrylic resin. A primer layer resin composition comprising a binder resin composed of a two-component curable resin containing 100 parts of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate) on a pattern layer. It was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which a base material layer / picture layer / primer layer was laminated in order was obtained.

  On the primer layer side of the laminate obtained above, embossing is performed with the embossing plate depth shown in Table 1 (height from the bottom surface of the recess to the top surface of the protrusion), and the uneven pattern of the dot pattern is formed on the primer layer. To form. Thereafter, the resin composition having the composition shown in Table 1 was applied on the primer layer having the uneven shape so that the thickness after curing was 8 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface layer having an uneven shape.

  Next, the resin composition having the composition shown in Table 1 was applied on the surface layer formed as described above so that the thickness after curing was a predetermined value shown in Table 1. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form an uneven protective layer.

Thus, a decorative sheet having a laminated structure in which the base layer / the pattern layer / the primer layer / the surface layer having an uneven shape / the uneven protective layer was sequentially laminated was obtained.
Comparative Example 1
A decorative sheet was produced under the same conditions as in Example 1 except that the uneven protective layer was not formed.
Comparative Example 2
A decorative sheet was produced under the same conditions as in Example 6 except that the uneven protective layer was not formed.
Comparative Example 3
In the formation of the surface layer, a decorative sheet was produced under the same conditions as in Example 1 except that it was cured using a thermosetting solvent-based acrylic resin.
Comparative Example 4
In the formation of the surface layer, except that it was cured using a two-part curable acrylic urethane resin containing 100 parts of the main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate). A decorative sheet was produced under the same conditions as in Example 1.
Comparative Example 5
In the formation of the concavo-convex protective layer, except that it was cured using a two-part curable acrylic urethane resin containing 100 parts of the main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate). Manufactured the decorating sheet on the same conditions as Example 1.
[Manufacture of decorative resin molded products]
Each decorative sheet was heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 100%), preformed along the internal shape of the die, and clamped. Thereafter, a mixed resin of polycarbonate and ABS was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded product with an uneven protective layer. Subsequently, the decorative resin molded product was obtained by peeling the concave / convex protective layer by hand from the obtained decorative resin molded product with the uneven protective layer.
[Performance evaluation]
About the decorative sheet and the decorative resin molded product obtained in each example and comparative example, the following methods evaluated the uneven shape, the texture of the uneven surface, the peeling workability of the uneven protective layer, and the three-dimensional formability. .
<Evaluation of uneven shape>
In order to evaluate the uneven shape of the surface of the decorative resin molded product, the center line average roughness (Ra), maximum, using a surface roughness / contour shape measuring machine (Hardy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.) The height (Rmax) and the ten-point average height (Rz) were measured.
<Evaluation of touch feeling>
The surface of the decorative resin molded product was touched by hand, and the touch feeling was evaluated according to the following criteria.
A: A feeling of unevenness was strongly recognized.
○: A feeling of unevenness was recognized.
Δ: Slight unevenness was recognized.
×: Unevenness was not recognized.
<Peeling workability of uneven protective layer>
The workability when the concave / convex protective layer was peeled off from the decorative resin molded product with the concave / convex protective layer was evaluated according to the following criteria.
(Circle): The uneven | corrugated protective layer could be peeled in the state of one film | membrane, and all the uneven | corrugated protective layers could be peeled by one peeling operation | work.
(Triangle | delta): Although the uneven | corrugated protective layer was peeled, the uneven | corrugated protective layer was not able to be peeled in the state of one film | membrane, but the peeling operation | work of multiple times was required.
X: The uneven protective layer was strongly bonded to the surface layer, and could not be peeled off.
<Three-dimensional formability>
Each decorative sheet was heated to 120 ° C. with an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 100%) to form the internal shape of the die. After the molded decorative sheet was cooled, it was released from the mold, and the three-dimensional formability was evaluated according to the following criteria.
○: No cracking or whitening was observed in the surface protective layer. Alternatively, fine coating cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, but there was no practical problem.
(Triangle | delta): The coating film crack and whitening were seen in the surface layer, without being able to follow the shape of a type | mold.
X: Remarkable coating cracking and whitening were observed on the surface layer without following the shape of the mold.
<Evaluation results>
The results are shown in Table 1. From this result, a surface layer having irregularities formed on the base material layer is formed with a cured product of ionizing radiation curable resin, and an uneven protective layer formed with a cured product of ionizing radiation curable resin is laminated thereon. Thus, even when subjected to injection molding, deformation and disappearance of the concavo-convex shape could be suppressed, and an excellent design feeling and hand feeling could be imparted to the decorative resin molded product. In addition, by forming the concave / convex protective layer with a cured product of ionizing radiation curable resin, the workability of peeling off the concave / convex protective layer after injection molding is good, and in particular, the concave / convex protective layer uses a combination of polycarbonate acrylate and urethane acrylate. It was also confirmed that when the thickness of the ionizing radiation curable resin was 25 μm or more, the workability of peeling the uneven protective layer was extremely good. On the other hand, when any one of the concavo-convex protective layer and the surface layer was formed with a material other than the ionizing radiation curable resin, the concavo-convex protective layer could not be peeled off and used as a decorative sheet. Although not shown in Table 1, when the concave / convex protective layer is formed of a cured product of ionizing radiation curable resin, it has dimensional stability, and even if stored for a long time, the concave / convex protective layer shrinks or peels off. It has also been confirmed that this does not occur.

[Footnotes in Table 1]
The abbreviations of the resin composition used for forming the surface layer and the uneven protective layer are as shown below.
(EB1)
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 95 parts by mass Tetrafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass (EB2)
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 30 parts by mass acrylic polymer (weight average molecular weight 120,000): 70 parts by mass (solvent acrylic)
Thermosetting solvent acrylic resin (two-component curable acrylic / urethane)
Two-part curable acrylic urethane resin containing 100 parts of main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of curing agent (hexamethylene diisocyanate)

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Surface layer 3 Concavity and convexity protection layer 4 Primer layer 5 Picture layer 7 Transparent resin layer 9 Molding resin layer

Claims (9)

A base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The decorative sheet, wherein the surface layer and the protective layer are formed of a cured product of a resin composition containing an ionizing radiation curable resin.   The decorative sheet according to claim 1, comprising polycarbonate (meth) acrylate as the ionizing radiation curable resin.   Furthermore, the decorating sheet of Claim 2 containing polyfunctional urethane (meth) acrylate as said ionizing radiation curable resin.   The decorative sheet according to claim 3, wherein a mass ratio of the polycarbonate (meth) acrylate and the multifunctional urethane (meth) acrylate is 50:50 to 99: 1.   The decorative sheet according to any one of claims 1 to 4, wherein the uneven protective layer has a thickness of 10 to 100 µm. A first step of forming a laminate in which a surface layer made of a cured product of a resin composition having an uneven shape and containing an ionizing radiation curable resin is laminated on a base material layer, and obtained in the first step The second step of forming a concavo-convex protective layer by applying and curing a resin composition containing an ionizing radiation curable resin on the surface layer of the laminated body according to claim 1. A method for producing a decorative sheet. A molded resin layer, a base material layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The decorative resin molded article with an uneven protective layer, wherein the surface layer and the protective layer are formed of a cured product of a resin composition containing an ionizing radiation curable resin.   The manufacturing method of the decorative resin molded product with an uneven | corrugated protective layer including the process of forming a molded resin layer by inject | pouring resin to the base material layer side of the decorating sheet in any one of Claims 1-5.   The manufacturing method of a decorative resin molded product including the process of peeling an uneven | corrugated protective layer from the decorative resin molded product with an uneven | corrugated protective layer of Claim 7.