JP5673146B2 - Decorative sheet and decorative resin molded product using the same - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative resin molded product using the decorative sheet.

  Decorated resin molded products decorated by laminating decorative sheets on the surface of molded products are used in various applications such as vehicle interior parts. As a molding method of such a decorative resin molded product, the decorative sheet is formed into a three-dimensional shape in advance by a vacuum mold, the molded sheet is inserted into an injection mold, and the resin in a fluid state is placed in the mold. An injection molding method in which the resin and the molded sheet are integrated by injection, or a decorative sheet inserted into the mold at the time of injection molding is integrated with the molten resin injected and injected into the cavity. The injection molding simultaneous decorating method etc. which decorate the surface are mentioned.

  Since the decorative resin molded product obtained by such a molding method is used in various applications such as vehicle interior parts as described above, the three-dimensional moldability that can sufficiently follow the three-dimensional molding, and the surface is scratch-resistant. In addition to surface properties such as chemical properties and chemical resistance, high-quality feeling has been demanded due to the recent trend toward consumer luxury products. The addition of texture by imparting matte or unevenness to a resin molded product in accordance with a specific part of the pattern, that is, design is also an important issue. For such a problem, a decorative sheet (for example, Patent Document 1) using a resin composition containing a predetermined ionizing radiation curable resin and a thermoplastic resin in the surface protective layer, or an ionizing radiation curable resin is used. A decorative sheet (for example, Patent Document 2) provided with a surface protective layer having a predetermined thickness used is proposed. However, the ionizing radiation curable resin used in the formation of these decorative sheets emphasizes the three-dimensional formability of the decorative sheets, so the surface may not have sufficient scratch resistance, chemical resistance, or design properties. there were.

JP 2009-132145 A JP 2010-30277 A

  Under such circumstances, the present invention provides a decorative sheet that has excellent three-dimensional formability and imparts excellent surface properties such as scratch resistance and chemical resistance to decorative resin molded products, and design properties. An object of the present invention is to provide a decorative resin molded product using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by the following invention. That is, the present invention provides the following decorative sheet and a decorative molded product using the same.

1. A second pattern layer provided partially on the base film layer, a region on the second pattern layer that is in contact with the second pattern layer, and the second pattern layer and the second pattern A decorative sheet having a surface protective layer covering the entire surface including a region where no layer is formed, wherein the binder resin of the second pattern ink forming the second pattern layer is a thermoplastic resin, The protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate as an ionizing radiation curable resin. The acrylic silicone (meth) acrylate is 1 In the molecule, a part of the structure of the acrylic resin is substituted with a siloxane bond (Si-O), and the side chain and / or main chain end of the acrylic resin is a functional group. (Meth) are those acrylate has acryloyloxy group two or more, during surface protective layer, mutual right above of the second pattern layer, the ionizing radiation curable resin and thermoplastic resin A decorative sheet in which a low gloss pattern layer having a low gloss region is formed by an action.
2. 2. The decorative sheet according to 1 above, wherein a transparent resin film layer is provided between the base film layer and the second pattern layer.
3. A decorative resin molded product using the decorative sheet according to 1 or 2 above.

  According to the present invention, a decorative sheet that has excellent three-dimensional moldability and imparts surface properties such as scratch resistance and chemical resistance to decorative resin molded products, and design properties, and uses the decorative sheet A decorative resin molded product can be obtained.

It is a schematic diagram which shows the cross section of the one aspect | mode of the decorating sheet of this invention. It is a schematic diagram which shows the cross section of the one aspect | mode of the decorating sheet of this invention.

[Decorative sheet]
The decorative sheet of the present invention has a second pattern layer partially provided on the base film layer, and is present on and in contact with the second pattern layer, and the second pattern layer is formed. A decorative sheet having a surface protective layer covering the entire surface including the region formed and the region where the second pattern layer is not formed, wherein the binder resin of the second pattern ink forming the second pattern layer is It is a thermoplastic resin, and the surface protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate as an ionizing radiation curable resin. In the protective layer, a low-gloss pattern layer having a low gloss region is formed immediately above the second pattern layer by the interaction between the ionizing radiation curable resin and the thermoplastic resin. It is intended to.

The structure of the decorating sheet of this invention is demonstrated in detail using FIG.1 and FIG.2.
FIG.1 and FIG.2 is a schematic diagram which shows the cross section of the one aspect | mode of the decorating sheet 10 of this invention. In the example shown in FIG. 1, a first pattern layer 12, a primer layer 14, a second pattern layer 15, and a surface protective layer 16 are sequentially laminated on the base film layer 11. A low gloss pattern layer 17 having a low gloss region is provided on the upper portion. 2 has a layer structure in which a transparent resin film layer 13 is further provided between the first pattern layer 12 and the primer layer 14 in the decorative sheet 10 shown in FIG. doing. Here, the surface protective layer 16 is formed by crosslinking and curing the above-mentioned ionizing radiation curable resin composition.

≪Base film layer≫
The base film layer 11 is selected in consideration of the three-dimensional moldability and compatibility with the injection resin, and a resin film made of a thermoplastic resin is typically preferably used. As the thermoplastic resin, generally, acrylonitrile / butadiene / styrene resin (hereinafter referred to as “ABS resin”), acrylonitrile / styrene / acrylic ester resin (hereinafter referred to as “ASA resin”), acrylic resin, polypropylene, Polyolefin resins such as polyethylene, polycarbonate resins, vinyl chloride resins, etc. are preferably used, among which ABS resin is preferable from the viewpoint of three-dimensional moldability, and the base film layer 11 is a single layer sheet of these resins. Alternatively, it can be used as a multilayer sheet made of the same or different resin.

  The base film layer 11 preferably has a flexural modulus of 500 to 4,000 MPa at 25 ° C., more preferably 750 to 3,000 MPa. Here, the flexural modulus is a value measured according to JIS K7171. If the flexural modulus is 500 MPa or more, the decorative sheet has sufficient rigidity, and excellent surface characteristics and moldability can be obtained. In addition, when it is 3,000 MPa or less, sufficient tension can be applied in the case of manufacturing by roll-to-roll, and it is difficult for sagging to occur. That is, the pattern register is good.

  Although the thickness of the base film layer 11 is suitably selected according to a use, it is about 50-1000 micrometers normally, 100-700 micrometers is more preferable, and 100-500 micrometers is more preferable. When the thickness of the base film layer 11 is within the above range, in addition to excellent surface properties, three-dimensional formability and design properties, printing workability (productivity) is also obtained, which is advantageous from the viewpoint of cost. is there.

The base film layer 11 can be subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides, if desired, in order to improve the adhesion with the layer provided thereon. .
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the base film layer may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

  The base film layer 11 may be colored with a coloring agent or may not be colored from the viewpoint of adjusting the above-described colors or from a design viewpoint, and is colorless and transparent, colored and transparent, and translucent. Any of these embodiments may be used. Although it does not specifically limit as a coloring agent used for a base material, The coloring agent which does not discolor even if it is under high temperature 150 degreeC or more is preferable, and what is necessary is just to use the existing dry color, paste color, a masterbatch resin composition.

≪First pattern layer≫
The first pattern layer 12 gives decorativeness to the decorative resin molded product, is a layer provided as desired, and is usually provided on the base film layer 11. The first picture layer 12 is formed by various printing methods such as ink, gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and ink jet printing. Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.

As the ink composition used for the first picture layer 12, 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 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, Any one of butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like may be used alone or in combination of two or more.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

≪Hidden layer≫
The decorative sheet 10 of the present invention may be provided with a concealing layer (not shown) between the base film layer 11 and the first pattern layer 12 as desired. It is provided for the purpose of preventing the color of the pattern of the decorative sheet 10 from being affected by changes and variations in the color of the surface of the base film layer 11. The concealing layer is a normal printing method such as gravure printing, offset printing, silk screen printing, printing from a transfer sheet, inkjet printing, gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating. It is formed by the usual coating methods such as.
The hiding layer is usually formed with an opaque color, and a so-called solid printing layer having a thickness of about 1 to 20 μm is preferably used. The ink composition for forming the concealing layer can be appropriately selected and used from those used for the first pattern layer 12 described above.

≪Transparent resin film layer≫
The decorative sheet 10 of the present invention can preferably have a transparent resin film layer 13 from the viewpoint of improving chemical resistance, and the transparent resin film layer 13 includes a base film layer 11, a second pattern layer 15, and the like. Or a layer provided between the first pattern layer 12 and the second pattern layer 15 which are preferably provided if desired, or between the primer layer 14 as shown in FIG.

  The resin film forming the transparent resin film layer 13 is appropriately determined in consideration of transparency, three-dimensional formability, shape stability, chemical resistance, etc., but typically a thermoplastic resin film is preferably used. Is done. The thermoplastic resin is generally an acrylic resin, polyolefin resin such as polypropylene or polyethylene, polycarbonate resin, acrylonitrile / butadiene / styrene resin (hereinafter referred to as “ABS resin”), polyethylene terephthalate (PET) or polyethylene naphthalate. A polyester resin such as (PEN), a vinyl chloride resin, or the like is used. Among these, from the viewpoint of scratch resistance and chemical resistance, acrylic resins, polyolefin resins, polycarbonate resins, and polyester resins are preferable, acrylic resins and polyester resins are more preferable, and polyester resins are more preferable.

  The transparent resin film layer 13 can be subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as desired in order to improve the adhesion to the layer provided thereon. . These physical or chemical surface treatments are similar to the treatments that can be performed on the base film layer.

  The thickness of the transparent resin film layer 13 is not particularly limited, but is preferably 10 to 200 μm and more preferably 15 to 150 μm in view of cost, three-dimensional formability, shape stability, and the like.

≪Primer layer≫
The decorative sheet 10 of the present invention is preferably provided with a primer layer 14 between the first pattern layer 12 and the surface protective layer 16 if desired, in order to make it difficult for fine cracks and whitening to occur in the stretched portion of the surface protective layer 16. As shown in FIG. 1, it is preferably provided between the transparent resin film layer 13 and the second picture layer 15 provided as desired.
The thickness of the primer layer 14 is preferably 0.1 μm or more. When it is 0.1 μm or more, it has an effect of preventing the surface protective layer from cracking, breaking, and whitening. On the other hand, if the thickness of the primer layer 14 is 10 μm or less, it is preferable that when the primer layer is applied, the coating film is stable in drying and curing, and the three-dimensional formability does not vary. From this viewpoint, the thickness of the primer layer 14 is preferably 1 to 10 μm.

Further, the primer layer 14 preferably has a breaking elongation at 120 ° C. measured under the following measurement conditions of 150% or more, and more preferably 200% or more. When the elongation at break is 150% or more, fine cracks and whitening hardly occur in the stretched portion of the surface protective layer during vacuum forming.
(Measurement conditions for measuring elongation at break)
According to JIS K 7127: 1999, the primer composition constituting the primer layer was crosslinked and cured (heated at 50 ° C. for 72 hours) to form a film of 25 mm width × length (distance between chucks) 50 mm × thickness 40 ± 10 μm. After leaving the sample in an oven at 120 ° C. and leaving it for 120 seconds, the elongation at break is measured at a tensile rate of 50 mm / min.

  Since the primer layer 14 is a layer provided between the first pattern layer 12 and the second pattern layer 15 or preferably between the transparent resin film layer 13 and the second pattern layer 15 as described above, As shown in FIG. 1, the second pattern layer 15 and the surface protective layer 16 may be simultaneously touched. Therefore, by the interaction between the binder resin of the second pattern ink and the ionizing radiation curable resin that forms the surface protective layer, a low gloss pattern layer having a low gloss region is formed, and a gloss difference of the pattern is generated. The resin that forms the primer layer 14 is a thermoplastic resin that forms the second pattern layer, or a surface protective layer so as not to impair the effect of the design property of the present invention that expresses unevenness and improves the design property. It is preferable to select a material that does not cause interaction with the ionizing radiation curable resin, for example, a thermosetting resin.

  Examples of the primer composition constituting the primer layer 14 include urethane resin, (meth) acrylic resin, (meth) acrylic / urethane copolymer resin, vinyl chloride / vinyl acetate copolymer, polyester resin, butyral resin, What uses chlorinated polypropylene, chlorinated polyethylene, etc. as a binder resin is used preferably, These resin can be used 1 type or in mixture of 2 or more types. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic / urethane copolymer resin are preferable. Further, from the viewpoint of making the effect of gloss difference expression by the second pattern layer 15 and the surface protective layer 16 described later more remarkable, it is preferable to use a crosslinking agent in the formation of the primer layer 14.

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 to the surface protective layer 16 after crosslinking, difficulty of interaction after lamination of the surface protective layer 16, physical properties, and moldability, acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate as a crosslinking material Alternatively, a combination of 4,4-diphenylmethane diisocyanate is preferable, and a combination of acrylic polyol and hexamethylene diisocyanate is particularly preferable.

  (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 composed of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as is preferably used. Here, (meth) acryl means acryl or methacryl.

  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. If desired, the acrylic / urethane (polyester urethane) block copolymer resin can be adjusted to an acrylic / urethane ratio (mass ratio) of preferably 9/1 to 1/9, more preferably 8/2 to 2/8. Since it can be used for various decorative sheets, it is particularly preferable as a resin used in the primer composition.

<Inorganic particles>
Moreover, it is preferable that the primer layer 14 contains an inorganic particle from a viewpoint of producing a gloss difference and improving the designability. Preferred inorganic particles include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin.
The average particle diameter of the inorganic particles is preferably from 0.1 to 5 μm, more preferably from 1 to 5 μm, and even more preferably from 2 to 5 μm, from the viewpoint of improving design properties. Moreover, 0.01-5 mass parts is preferable with respect to 100 mass parts of resin, and, as for content of an inorganic particle, 0.1-1 mass part is more preferable.

  The primer layer 14 is composed of 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 the like, or transfer coating. Here, the transfer coating method is a method of forming a primer layer 14 or a coating film of an adhesive layer on a thin sheet (film substrate), and thereafter coating the surface of the target layer in the decorative sheet 10.

≪Adhesive layer≫
The decorative sheet 10 of the present invention is provided with an adhesive layer (not shown) on the back surface (surface opposite to the surface protective layer 14) of the decorative sheet 10 as desired in order to improve the adhesion with the injection resin. be able to. A thermoplastic resin or a curable resin is used for the adhesive layer depending on the injection resin. Examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride / vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, etc. Can be used alone or in combination of two or more. Examples of the thermosetting resin include urethane resin and epoxy resin.

≪Second pattern layer≫
The decorative sheet 10 of the present invention has a second pattern layer 15 formed of a second pattern ink having a thermoplastic resin as a binder resin. The second pattern layer 15 is formed by the interaction between a thermoplastic resin, which is a binder resin of the ink forming the pattern layer 15, and an ionizing radiation curable resin, which forms the surface protection layer 16 described later. 16 is a layer for forming a low gloss pattern layer 17 having a low gloss region immediately above the pattern layer 15. The second pattern layer 15 is a layer partially provided on the base film layer 11 or on the primer layer 14 as shown in FIG. 1, and the low gloss pattern layer having the low gloss region described above. By forming the pattern, a difference in gloss of the pattern is generated to express a feeling of unevenness.

Although the mechanism of gloss difference generation in the present invention has not yet been fully elucidated, ionizing radiation for forming the surface protective layer 16 on the surface of the second pattern layer 15 based on the results of various experiments, observations and measurements. When an uncured product of the curable resin composition is applied, the binder resin and ionizing radiation curable property of the second pattern ink for forming the second pattern layer 15 are selected by appropriately selecting the combination of the materials and the coating conditions. It is presumed that this is due to the interaction between the resin and some components such as elution, dispersion, and mixing. At this time, the respective resins in the second pattern ink and the uncured product of the ionizing radiation curable resin composition are not completely compatible in a short time but in a suspended state, so that the second pattern layer 15 It is considered that the portion that is present directly above and is in a suspended state scatters light to form a low gloss region. While this suspended state is maintained, the ionizing radiation curable resin composition is crosslinked and cured to form a surface protective layer. When this state is fixed, the surface protective layer has a low gloss region having a low gloss region. It is presumed that the pattern layer 17 is partially formed, and that part is visually perceived as if it is a concave portion by the optical illusion. At that time, as the coating amount of the second pattern layer 15 is relatively increased, the amount of elution of the second pattern layer 15 into the surface protective layer 16 is relatively increased and the suspension is suspended. The degree of state is higher, and the gloss of the low gloss pattern layer 17 is considered to be lower.
As described above, the low gloss region is formed by the interaction between the binder resin of the second pattern ink and the ionizing radiation curable resin. The low-gloss pattern layer 17 having a low gloss region formed immediately above the second pattern layer 15 may be formed on the “immediately upper portion” of the second pattern layer 15. It may be formed so as to have a spread in “the vicinity”. The low gloss pattern layer 17 having a low gloss region formed in the “vicinity” portion is also formed by the interaction between the binder resin of the second pattern ink and the ionizing radiation curable resin.

  In the present invention, the low gloss pattern layer 17 having a low gloss region includes a thermoplastic resin that is a binder resin of the second pattern ink that forms the second pattern layer 15 and an ionizing radiation curable resin that forms the surface protective layer 16. It is formed by interactions such as partial elution, dispersion, and mixing. Therefore, the second pattern ink forming the second pattern layer 15 is required to be a binder resin having a property capable of exhibiting an interaction with the ionizing radiation curable resin composition forming the surface protective layer 16. Examples of such a binder resin include resins that are usually used without using a crosslinking agent such as isocyanate, preferably thermoplastic resins.

  Preferable examples of such thermoplastic resins include acrylic resins, polyester resins, unsaturated polyester resins, nitrocellulose resins such as nitrified cotton, thermoplastic urethane resins, and polyvinyl acetal resins such as polyvinyl butyral. Among these, compatibility with polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate employed as an ionizing radiation curable resin of an ionizing radiation curable resin composition for forming a surface protective layer 16 described later, that is, whitening From the standpoint that it is difficult to occur, nitrocellulose resins such as acrylic resin and nitrified cotton are preferable, and acrylic resin is particularly preferable. The acrylic resin preferably has a weight average molecular weight of 100,000 to 1,000,000, more preferably 150,000 to 700,000, and even more preferably 200,000 to 500,000. . When the weight average molecular weight is 100,000 or more, the thixotropy is low, and the unevenness of the low gloss pattern layer is not easily expressed. On the other hand, if it is 1,000,000 or less, it is preferable that the second pattern ink does not become difficult to form, and that a film is difficult to form during printing and transfer failure does not occur.

From the viewpoint of improving the designability, only the second pattern layer 15 is suspended, and the primer layer 14 and the first pattern layer 12 are suspended in relation to the ionizing radiation curable resin forming the surface protective layer 16. In order to avoid this, it is preferable that the binder resin of the second pattern ink is different from the binder resin of the primer composition and the ink composition forming the first pattern layer 12. From this point of view, it is particularly preferable to use a crosslinking agent for the primer composition constituting the primer layer 14 as described above, and to use the above thermoplastic resin for the binder resin of the second pattern ink. Is preferable, and it is preferable not to use a crosslinking agent.
If necessary, unsaturated polyester resin, acrylic resin, vinyl chloride / vinyl acetate copolymer, etc. to adjust the degree of expression of the low gloss area and the contrast of the gloss difference between the low gloss area and the surrounding area. Can be mixed.

  Like the ink used for the first pattern layer 12, the second pattern ink forming the second pattern layer 15 has a colorant and can give a pattern pattern by itself, but the second pattern ink as shown in FIG. In the case of having one pattern layer 12, since a color or pattern has already been given to the base film layer 11, the second pattern ink composition for forming the second pattern layer 15 is not necessarily a colorant. It is not necessary to add and color. In other words, when the first pattern layer 12 is provided, the second pattern layer 15 is synchronized with the portion of the pattern to be expressed by the first pattern layer 12 by removing the gloss and visually expressing the concave portion. As a result, a pattern having a visual recess due to a gloss difference is obtained. For example, when the wood pattern is to be expressed by the first pattern layer 12, the conduit portion is visually visibly caused by gloss difference by synchronizing the second pattern ink portion of the second pattern layer 15 with the conduit portion of the wood. The pattern which became the recessed part is obtained. Alternatively, when the tile pattern is to be expressed by the first pattern layer 12, the joint groove is caused by the gloss difference by synchronizing the second pattern ink portion of the second pattern layer 15 with the joint groove portion of the tile. A pattern in which the portion is visually concave is obtained.

  About the application | coating film thickness of the 2nd pattern ink which forms the 2nd pattern layer 15, it is preferable that it is 0.1-10 micrometers. When the thickness is 0.1 μm or more, the interaction between the second pattern ink and the ionizing radiation curable resin composition described above occurs, and a low gloss region is sufficiently obtained, so that a sufficient gloss difference on the decorative sheet surface can be obtained. On the other hand, if it is 10 μm or less, there is no mechanical restriction when printing the second pattern ink, and it is economically advantageous. From the above viewpoint, the coating thickness of the second pattern ink is preferably in the range of 0.6 to 7 μm.

  In the present invention, by changing the coating amount of the second pattern ink forming the second pattern layer 15, the gradation pattern in which the gloss difference on the cosmetic material surface changes stepwise, or the gloss difference on the cosmetic material surface is continuous. It can be given freely as a continuous pattern that changes with time. For example, the upper part of the second pattern layer 15 (low gloss pattern layer 17) on the outermost surface of the surface protective layer 15 can be raised with the formation of the second pattern layer 15 to form a convex shape 18. Since the surface of the surface protective layer 16 has the convex shape 18 in this manner, light is scattered in this portion, the surface area is increased, and the viewing angle that can recognize low gloss is widened. In cooperation with the effect, a sense of visual unevenness is further emphasized, and a unique design feeling is visually recognized as a concave portion even though it is physically convex.

<External pigment>
Moreover, it is preferable that the 2nd pattern layer 15 contains extender pigment inorganic particle from a viewpoint of producing a glossiness difference and improving the designability. The extender pigment is not particularly limited, and examples thereof include silica, talc, clay, barium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, etc., but the degree of freedom in material design such as oil absorption, particle size, pore volume, etc. Silica is preferable because it is high and has excellent design properties and coating stability as an ink. Silica in a fine powder is particularly preferable.

  The oil absorption amount of the extender pigment (based on JIS K 5101-13-1: 2004) is preferably 150 to 350 ml / 100 g, and more preferably 150 to 300 ml / 100 g. If the oil absorption amount of the extender pigment is 150 ml / 100 g or more, the gloss value of the surface protective layer / second pattern layer does not become too high, so that only the surface protective layer part and the surface protective layer / second pattern layer part Since the difference in gloss between the two becomes large, it becomes easy to exhibit high design properties. On the other hand, when the oil absorption of the extender pigment is 350 ml / 100 g or less, the ability to lower the gloss value of the surface protective layer / second picture layer can be effectively utilized. In addition, since the increase in thixotropy is suppressed, the suitability for coating is not impaired, and printing with high design properties is facilitated.

  The content of the extender pigment in the second pattern ink forming the second pattern layer 15 is preferably 0.2 to 1.5 as the extender pigment / resin mass ratio (P / V ratio). When the P / V ratio is 0.2 or more, high designability is easily exhibited. When the P / V ratio is 1.5 or less, the flexibility of the second pattern ink is not impaired, and the surface protective layer is cracked during molding. It is because it becomes difficult to occur. From the same viewpoint, the P / V ratio is preferably 0.2 to 1.2.

  In this invention, it is preferable that the average particle diameter of the silica used preferably as an extender for the 2nd pattern layer 15 is 0.1-7 micrometers. When it is 0.1 μm or more, the thixotropy of the ink does not become extremely high when it is added to the ink, and the viscosity of the ink does not increase too much, so that printing can be controlled easily. Further, when trying to express the matte of the conduit pattern portion, the preferred thickness of the second pattern layer 15 of the conduit pattern portion is 7 μm or less, so the average particle diameter of silica is the thickness of the second pattern layer 15. This is because the head of the particles is relatively suppressed and less noticeable if it is below, and the visual discomfort is less likely to occur.

≪Surface protective layer≫
The surface protective layer 16 is present on and in contact with the second pattern layer 15 described above, and an area where the second pattern layer 15 is formed and an area where the second pattern layer 15 is not formed. A layer provided so as to cover the entire surface, and obtained by crosslinking and curing an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate as an ionizing radiation curable resin. It is. The surface protective layer 16 imparts excellent surface characteristics to the decorative sheet of the present invention, and at the same time causes the low gloss pattern layer 17 having a low gloss region due to the presence of the second pattern layer 15 described above. Thus, it is a layer that imparts excellent design properties.

<Ionizing radiation curable resin composition>
The ionizing radiation curable resin composition refers to a composition containing an ionizing radiation curable resin. An ionizing radiation curable resin 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 rays (UV) or electron beams (EB) are used. However, it also includes electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.
In the present invention, polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate is used as the ionizing radiation curable resin. In the present invention, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning.

(Polycarbonate (meth) acrylate)
The polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and (meth) acrylate in the terminal or side chain. In addition, this (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing.

  This polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl groups of 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) the 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 at the terminal or side chain. A typical method for producing this polycarbonate polyol is 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 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, , 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 admixture of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpurpan, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Furthermore, alcohols having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide are added to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or in combination of two or more.

  The compound (C) serving as the carbonyl component is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formates such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Etc. These may be used alone or in admixture of two or more.

  The polycarbonate polyol is synthesized by subjecting the above-described 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. . For example, the charged molar ratio of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound (C) as the carbonyl component ( The charged molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents with respect to the hydroxyl group of the diol compound and polyhydric alcohol.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charge ratio is 3 or more on average in one molecule, preferably 3 to 50, more preferably 3 to 20. Within this range, a necessary amount of (meth) acrylate groups are formed by the 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 used in the present invention is preferably 500 or more, more preferably 1,000 or more, as measured by GPC analysis and converted to standard polystyrene. More preferably, it exceeds 2,000. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably more than 2,000 and not more than 50,000, and particularly preferably 5,000 to 20,000.

(Acrylic silicone (meth) acrylate)
The acrylic silicone (meth) acrylate used in the present invention is not particularly limited, and a part of the acrylic resin structure is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group. As long as it has two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the. As an example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned preferably, for example.

The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator.
Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These (meth) acrylate monomers are used alone or in combination of two.

  The silicone macromonomer is synthesized, for example, by living anionic polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator and capping with a radically polymerizable unsaturated group-containing silane. As a silicone macromonomer, following formula (1);

Is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a methyl group or an n- butyl group are preferable. R ² represents a monovalent organic group, —CH═CH ₂ , —C ₆ H ₄ —CH═CH ₂ , — (CH ₂ ) ₃ O (CO) CH═CH ₂ or — (CH ₂ ) _3. O (CO) C (CH ₃ ) ═CH ₂ is preferred. R ^{3 s} may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group. The numerical value of n is not particularly limited, and for example, the number average molecular weight of the silicone macromonomer is preferably 1,000 to 30,000, and more preferably 1,000 to 20,000.

  The acrylic silicone (meth) acrylate obtained using the above-mentioned raw materials has structural units represented by the following formulas (2), (3) and (4), for example.

In formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the (meth) acrylate. An alkyl group or glycidyl group in the monomer, or an alkyl group which may have a functional group such as an alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ is an organic compound having a (meth) acryloyloxy group. Indicates a group.
The above-mentioned acrylic silicone (meth) acrylates are used alone or in combination of two.

  The molecular weight of the acrylic silicone (meth) acrylate is preferably 1,000 or more, more preferably 2,000 or more, as measured by GPC analysis and converted to standard polystyrene. . The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of establishing three-dimensional formability, chemical resistance, and scratch resistance, it is particularly preferably 2,000 to 100,000.

  Moreover, it is preferable that the average molecular weight between crosslinking points of acrylic silicone (meth) acrylate is 100-2,500. If the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional formability, and if it is 2,500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, still more preferably 100 to 1,000.

  In the ionizing radiation curable resin composition of the present invention, the polycarbonate (meth) acrylate and the acrylic silicone (meth) acrylate may be used alone or in combination.

(Multifunctional (meth) acrylate)
The ionizing radiation curable resin composition used in the present invention may contain a polyfunctional (meth) acrylate. In the present invention, the polyfunctional (meth) acrylate is not particularly limited as long as it is a bifunctional or higher (meth) acrylate. However, trifunctional or higher functional (meth) acrylates are preferred from the viewpoint of curability. Here, bifunctional means having two (meth) acryloyl groups which are ethylenically unsaturated bonds in a molecule | numerator.
The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.

Preferred examples of the polyfunctional (meth) acrylate oligomer include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
In addition, polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones that have polysiloxane bonds in the main chain (meta ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules. Further, in combination with a polyfunctional (meth) acrylate oligomer, an oligomer having a cation polymerizable functional group in a molecule such as a novolak type epoxy resin, a bisphenol type epoxy resin, an aliphatic vinyl ether, or an aromatic vinyl ether may be used. .
The weight average molecular weight of these oligomers is preferably 1,000 to 20,000, and more preferably 1,000 to 10,000.

  Examples of the polyfunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and 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 dipentaeryth Such Ritoruhekisa (meth) acrylate. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, the content of the polyfunctional (meth) acrylate is such that the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and the polyfunctional (meth) acrylate is 98: 2 to 60:40. It is preferable. When the mass ratio is smaller than 98: 2 (that is, when the amount of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate is 98% by mass or less), the scratch resistance is not lowered. On the other hand, when the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is larger than 60:40 (that is, the amount of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate) 3), the three-dimensional formability does not deteriorate. Preferably, the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is 95: 5 to 65:35, more preferably 90:10 to 65:35.

  In the present invention, a monofunctional (meth) acrylate can be appropriately used in combination with the polyfunctional (meth) acrylate and the like within a range that does not impair the object of the present invention, for the purpose of reducing the viscosity. . These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  When using an ultraviolet curable resin composition as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator to 100 parts by mass of the ultraviolet curable resin. . The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.

  In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

Moreover, various additives can be mix | blended with the ionizing radiation curable resin composition which comprises the surface protective layer in this invention according to the desired physical property of the cured resin layer obtained. Examples of the 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, matting agent and the like. These additives can be appropriately selected from those commonly used.
Further, 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. Moreover, it can also be copolymerized and used to such an extent that the performance (scratch resistance and three-dimensional moldability) as a surface protective layer of the polymer of this invention is not impaired.

(Formation of surface protective layer)
Formation of the surface protective layer 16 can be obtained by preparing a coating liquid containing the above-mentioned ionizing radiation curable resin composition, applying it, and crosslinking and curing it. In addition, the viscosity of a coating liquid should just be a viscosity which can form a non-hardened resin layer on the surface of a base material by the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the prepared coating solution is cured on the base film layer 11, the first pattern layer 12, the transparent resin film layer 13 or the primer layer 14 on which the second pattern layer 15 is formed. The uncured resin layer is formed by coating by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating, so that the thickness becomes 1 to 1000 μm.

In the present invention, the surface-protecting layer 16 is formed by irradiating the thus formed uncured resin layer with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to an electron beam as the base film layer 11, the penetration depth of the electron beam and the resin layer By selecting the accelerating voltage so that the thicknesses are substantially equal, it is possible to suppress the irradiation of the extra electron beam to the base film layer 11 and minimize the deterioration of the base material due to the extra electron beam. You can stay.
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).
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. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  The cured resin layer thus formed has various functions by adding various additives, for example, high hardness and scratch resistance, so-called hard coat function, anti-fogging coating function, anti-fouling coating. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can be provided.

In this invention, it is preferable that the thickness after the hardening of the surface protective layer 16 is 1-1000 micrometers. If the thickness of the surface protective layer 16 after curing is 1 μm or more, sufficient physical properties as a protective layer such as scratch resistance and weather resistance can be obtained. On the other hand, if the thickness of the surface protective layer 16 after curing is 1000 μm or less, it is easy to uniformly apply ionizing radiation, it is easy to obtain uniform curing, and this is economically advantageous.
Further, the thickness of the surface protective layer 16 after curing is more preferably 1 to 50 μm, and further preferably 1 to 30 μm, so that the three-dimensional formability is improved, and a complicated three-dimensional shape such as automobile interior use is obtained. High followability can be obtained. Therefore, in the decorative sheet of the present invention, even if a hard ionizing radiation curable resin is blended, excellent three-dimensional formability can be expressed, and the coating film is hardened without impairing the three-dimensional formability. Therefore, it is possible to provide excellent scratch resistance that is preferable in terms of processing and practical use.
Since the decorative sheet of the present invention can provide a sufficiently high three-dimensional formability even if the surface protective layer 16 is thicker than the conventional one, a high film thickness is particularly required for the surface protective layer. It is also useful as a decorative sheet for a member such as a vehicle exterior part.

≪Low gloss pattern layer≫
The low gloss pattern layer 17 having a low gloss region is partially eluted with a thermoplastic resin that is a binder resin of the ink that forms the second pattern layer 15 and an ionizing radiation curable resin that forms the surface protective layer 16. It is formed by an interaction such as dispersion and mixing, and is a layer formed immediately above the second pattern layer 15 in the surface protective layer 16. The decorative sheet of the present invention has a low gloss due to the presence of the low gloss pattern layer 17 formed immediately above the second pattern layer 15 and a difference in gloss from the portion where the low gloss pattern layer 17 does not exist. A portion where the pattern layer 17 exists is visually recognized as a concave portion, and expresses a feeling of unevenness.

The decorative sheet of the present invention includes an area where the second pattern layer 15 is formed, a surface protective layer 16 covering the area (hereinafter referred to as “second pattern layer forming area / surface protective layer”), and a second pattern. By having a gloss difference between the region where the layer 15 is not formed and the surface protective layer 16 covering the region (hereinafter referred to as “second pattern layer non-formation region / surface protective layer”), that is, a difference in glossiness, An uneven feeling can be obtained, and an excellent design property is obtained.
Depending on the type of design expression, a decorative sheet with good design characteristics is manufactured by utilizing various differences in glossiness. However, the design pattern formation area / surface protection is not limited as follows. When the glossiness (gross value) of the layer is 20 or less, it is preferable in terms of increasing the designability. Further, it is more preferable that the difference in glossiness between the second pattern layer forming region / surface protective layer and the second pattern layer non-forming region / surface protective layer is 10 or more in that the design property can be further increased.

[Decorative resin molded product]
The decorative resin molded product of the present invention is produced using the decorative sheet of the present invention. More specifically, the decorative resin molded product of the present invention uses the decorative sheet of the present invention, and various types of injection molding such as insert molding, simultaneous injection molding, blow molding, and gas injection molding. And preferably by the insert molding method and the simultaneous injection molding method.

  In the insert molding method, in the vacuum forming process, the decorative sheet of the present invention is vacuum formed into a surface shape of the molded product in advance (off-line pre-molding) with a vacuum forming die, and then the excess portion is trimmed as necessary to form a molded sheet. Get. 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. To produce decorative resin molded products.

  As the injection resin, a resin corresponding to the application is used, and thermoplastic resins such as polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins are typical. In addition, thermosetting resins such as urethane resins and epoxy resins can be used depending on the application.

Next, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) with this female mold ), The injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated with the outer surface of the resin molding simultaneously with the injection molding, Manufactures decorative resin molded products.
In the injection molding simultaneous decorating method, the decorative sheet receives the thermal pressure from the injection resin, so if the decorative sheet is close to the flat plate and the aperture of the decorative sheet is small, the decorative sheet may or may not be preheated. .
In addition, as injection resin used here, the thing similar to what was demonstrated by the insert molding method can be used.

  The decorative resin molded body produced as described above has good three-dimensional moldability without cracking in the surface protective layer during the molding process, and the surface has high scratch resistance. In addition, the solvent resistance and chemical resistance are high. Furthermore, in the production method of the present invention, the surface protective layer is completely cured at the production stage of the decorative sheet, and therefore a step of crosslinking and curing the surface protective layer after producing the decorative resin molded body is unnecessary.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

Evaluation method (1) Three-dimensional formability (vacuum forming)
About the decorative sheet obtained by each Example and the comparative example, it vacuum-formed by the method shown below, and evaluated by the external appearance after shaping | molding. The evaluation criteria are as follows.
A: No coating film cracking or whitening was observed on the surface protective layer, and the shape of the mold was followed well.
○: Although a fine coating crack or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, there was no practical problem.
Δ: Slight coating cracking or whitening occurred in a part of the three-dimensional shape portion or the maximum stretched portion.
X: The coating film cracking and whitening were observed in the surface protective layer without following the shape of the mold.
<Vacuum forming>
The decorative sheet is heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming is performed using a vacuum forming die (maximum draw ratio: 100%) to form the internal shape of the die. After the sheet is cooled, the decorative sheet is released from the mold.

(2) Scratch resistance About the decorative sheet obtained in each Example and Comparative Example, the appearance of the test piece after 5 reciprocations with a load of 1.5 kgf was evaluated using # 0000 steel wool. The evaluation criteria are as follows.
A: There was no scratch.
○: Although fine scratches were observed on the surface, the coating film was not scraped or whitened.
Δ: Minor scratches on the surface.
X: There was a remarkable scratch on the surface.

(3) Chemical resistance About the decorative sheet | seat obtained by each Example and the comparative example, insect repellent spray (diet (N, N-diethyl-m-toluamide): 10% solution) is set to 0. 10cm. 05 g was applied and left at room temperature (23 ° C.) for 30 minutes. Next, the coated part was washed with a neutral detergent and the appearance of the part was evaluated. The evaluation criteria are as follows.
◎: There was no change in appearance. ○: Very slight whitening and swelling were observed on the surface. △: Whitening, swelling and dissolution were observed on the surface, but there were no practical problems. ×: Remarkable whitening and swelling on the surface. And dissolution was observed

(4) Design property About the decorating sheet obtained by each Example and the comparative example, the design property was evaluated with the following evaluation criteria.
◎: The conduit part has a low gloss, and the non-conduit part does not have a low gloss, so that a visually excellent texture is produced, the texture of the wood is obtained, and the design is very high. ○: The conduit part is low It became glossy, and the impression of unevenness was visually expressed as a recess, and the design was high. △; The conduit part was slightly low glossed, and the impression of slight unevenness was visually recognized and recognized as a recess. The properties were practically unproblematic. ×; The texture was flat and inferior in design.

(5) Measurement of molecular weight A high-speed GPC apparatus manufactured by Tosoh Corporation was used. The column used was “TSKgel αM” manufactured by Tosoh Corporation, the solvent was N-methyl-2-pyrrolidinone (NMP), and the measurement was performed at a column temperature of 40 ° C. and a flow rate of 0.5 cc / min. . In addition, the weight average molecular weight in this invention performed polystyrene conversion.

Example 1
An ABS resin film (flexural modulus: 1,800 MPa, thickness: 400 μm, hereinafter referred to as “ABS”) is used as a printing film, and the surface of the film is made of a vinyl chloride / vinyl acetate copolymer resin composition. The first pattern layer of wood grain pattern was formed by gravure printing using printing ink.
First obtained by blending 100 parts by mass of acrylic resin printing ink (weight average molecular weight; 100,000) with silica (average particle diameter: 5 μm, oil absorption: 200 ml / 100 g) at a P / V ratio of 1.0. Using two-pattern ink A, coating was performed by gravure printing so as to synchronize with the conduit pattern of the grain pattern of the first pattern layer to obtain a second pattern layer having a thickness of 1 μm. Next, an ionizing radiation curable resin composition (hereinafter referred to as “EB1”) having the following composition was applied on the second pattern layer so as to have a thickness after curing of 3 μm. The layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin composition to form a surface protective layer, thereby obtaining a decorative sheet. About the obtained decorating sheet, it evaluated by the said method. The evaluation results are shown in Table 1.

(Ionizing radiation curable resin composition (EB1))
Polycarbonate acrylate (weight average molecular weight; 10,000, bifunctional): 80 parts by mass Urethane acrylate oligomer (weight average molecular weight; 6,000, hexafunctional): 20 parts by mass Silica (average particle size: 5 μm, surface silane coupling Silica hydrophobized by: 10 parts by mass Olefin wax (average particle size: 5 μm, polypropylene wax): 5 parts by mass

Example 2 and Comparative Examples 1-3
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin composition shown in Table 1 was used. About the obtained decorating sheet, it evaluated by the said method.

Example 3
In Example 1, after providing the first pattern layer and before providing the second pattern layer, acrylic polyol and hexamethylene diisocyanate (hexamethylene diisocyanate is equivalent to the OH equivalent of the acrylic polyol) on the first pattern layer. A primer composition (hereinafter referred to as “P1”) was applied by gravure reverse so as to have a thickness of 2 μm, and a primer layer was provided. Were the same as in Example 1 to obtain a decorative sheet. About the obtained decorating sheet, it evaluated by the said method.

Examples 4 and 5
In Example 3, a decorative sheet was obtained in the same manner as in Example 3 except that the primer composition, the second pattern ink, and the ionizing radiation curable resin composition shown in Table 1 were used. About the obtained decorating sheet, it evaluated by the said method.

Example 6
In Example 3, after providing the first pattern layer and before providing the primer layer, a transparent resin film layer (acrylic resin film, thickness: 100 μm, tensile elastic modulus: 1500 MPa, hereinafter referred to as “acrylic”. The decorative sheet was obtained in the same manner as in Example 3 except that it was provided. About the obtained decorating sheet, it evaluated by the said method.

Example 7
In Example 7, the resin film used for the transparent resin film layer was the same as Example 7 except that a polyethylene terephthalate film (thickness: 100 μm, double-sided corona treatment, hereinafter referred to as “PET”) was used. To obtain a decorative sheet. About the obtained decorating sheet, it evaluated by the said method.

[note]
Second pattern ink B: ink containing nitrocellulose resin and silica (oil absorption: 200 ml / 100 g, average particle size: 5 μm) (P / V ratio: 1.0)
EB2: 70 parts by mass of acrylic silicone acrylate (weight average molecular weight; 20,000, molecular weight between cross-linking points after curing; 200) and 30 parts by mass of urethane acrylate oligomer (weight average molecular weight; 5,000, hexafunctional) Mixture (total resin content; 100 parts by mass)
Silica (average particle size: 5 μm, silica whose surface has been hydrophobized by silane coupling): 10 parts by mass Olefin wax (average particle size: 5 μm, polypropylene wax): 5 parts by mass EB3: Urethane acrylate (weight average molecular weight; 10, 000, trifunctional) and 30 parts by mass of thermoplastic acrylic resin (polymethyl methacrylate, weight average molecular weight; 70,000) (total resin content: 100 parts by mass)
Silica (average particle size: 5 μm, silica whose surface has been hydrophobized by silane coupling): 10 parts by mass Olefin wax (average particle size: 5 μm, polypropylene wax): 5 parts by mass EB4: Urethane acrylate (weight average molecular weight; 50, 000, bifunctional) 100 mass EB5: urethane acrylate (weight average molecular weight; 3,000, hexafunctional) 100 mass silica (average particle size: 5 μm, silica whose surface has been hydrophobized by silane coupling): 10 mass parts Olefin wax (average particle size: 5 μm, polypropylene wax): 5 parts by mass

  The decorative sheet of the present invention has a rapid temperature drop, a rapid stretching speed, and a high degree of stretching from a heating temperature of about 160 ° C. to a temperature at the time of contact with the mold in a normal insert molding method and injection molding simultaneous decoration method. Even under these conditions, cracks and cracks do not occur, the three-dimensional formability is good, and the surface of the manufactured decorative resin molded product has excellent scratch resistance and chemical resistance. confirmed. Further, the decorative sheet of the present invention is a low gloss pattern layer having a low gloss region visually recognized as a concave portion due to the interaction between the thermoplastic resin of the second pattern ink and the ionizing radiation curable resin of the surface protective layer. It was also confirmed that it has a design with excellent texture.

  The decorative sheet of the present invention is used for various decorative resin molded products, for example, interior materials or exterior materials of vehicles such as automobiles, construction members such as baseboards, and rims, joinery such as window frames and door frames, and walls. It is suitably used for decorative resin molded products for uses such as interior materials for buildings such as floors and ceilings, casings and containers of household electrical appliances such as television receivers and air conditioners.

10. Decorative sheet Base film layer 12. First pattern layer 13. Transparent resin film layer 14. Primer layer 15. Second pattern layer 16. Surface protective layer 17. Low gloss pattern layer 18. Convex shape

Claims (7)

A second pattern layer provided partially on the base film layer, a region on the second pattern layer that is in contact with the second pattern layer, and the second pattern layer and the second pattern A decorative sheet having a surface protective layer covering the entire surface including a region where no layer is formed,
The binder resin of the second pattern ink forming the second pattern layer is a thermoplastic resin,
The surface protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate as an ionizing radiation curable resin,
In the acrylic silicone (meth) acrylate, a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O) in one molecule, and the side chain and / or main chain terminal of the acrylic resin is a functional group. Having two or more (meth) acryloyloxy groups,
In the surface protective layer, a low gloss pattern layer having a low gloss region is formed immediately above the second pattern layer by the interaction between the ionizing radiation curable resin and the thermoplastic resin. Decorative sheet characterized by.   The decorative sheet according to claim 1, wherein the binder resin of the ink forming the second pattern layer is at least one selected from a nitrocellulose resin and an acrylic resin.   The decorative sheet according to claim 1 or 2, wherein the polycarbonate (meth) acrylate has a weight average molecular weight exceeding 2,000.   The decorative sheet according to any one of claims 1 to 3, further comprising a transparent resin film layer between the base film layer and the second pattern layer.   The decorative sheet according to any one of claims 1 to 4, wherein the acrylic silicone (meth) acrylate has a weight average molecular weight of 2,000 to 10,000.   The decorative sheet according to any one of claims 1 to 5, wherein an average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is 100 to 2,500.   A decorative resin molded product using the decorative sheet according to claim 1.