JP5625548B2 - Decorative sheet manufacturing method, decorative sheet and decorative molded product using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for producing a decorative sheet used for decorative molded products for various uses such as for buildings, vehicles, and joinery, a decorative sheet, and a decorative molded product using the same.

A decorative molded product decorated by laminating a decorative sheet on the surface of the molded product is used in various applications such as building members and vehicle interior parts. A decorative sheet used for such a decorative molded product is usually manufactured by sequentially laminating a design layer and a surface protective layer on a substrate.
However, in such a manufacturing method, when the design layer is formed, unevenness is generated on the surface, and when the surface protective layer is laminated thereon, there is a concern that the smoothness of the surface protective layer surface is impaired.

By the way, in patent document 1, the skin material for motor vehicle interior containing the thermoplastic resin basecoat / transparent coat film joined to the outer surface of the semi-rigid resin backing sheet which can be thermoplastically formed is proposed. The base coat and transparent coat film are coated on a matte carrier and dried, and then transferred to the backing sheet and laminated. However, in Patent Document 1, since the gloss of the transparent coat depends on the smoothness of the matte carrier, there arises a problem that fine adjustment of the smoothness becomes difficult.
Further, if the decorative sheet is not smoothed at all as in the prior art, the smoothness and gloss of the decorative sheet surface and the smoothness and gloss of the decorative molded product after injection molding are significantly different. The design feeling of the decorative sheet and the design feeling of the decorative molded product sometimes differed greatly.

Special Table 2000-512225

  In order to solve the above-mentioned problem, as a method of imparting smoothness and gloss to the surface of the surface protective layer, smoothing treatment is performed by hot press processing or the like using a mirror-treated metal plate after laminating the surface protective layer. However, the unevenness of the design layer remains even if the surface of the surface protective layer is smoothed. Therefore, if the decorative sheet is heated in the simultaneous decoration of insert molding or injection molding, the surface protective layer is softened and the unevenness of the design layer May appear on the surface protective layer, and the smoothness and gloss of the surface of the decorative molded product may be impaired. That is, the high smoothness and gloss of the decorative sheet are reduced after injection molding, and the smoothness and gloss of the decorative sheet surface are different from the smoothness and gloss of the decorative molded article surface after injection molding. There is a possibility that the design feeling of the decorative design and the design feeling of the decorative molded product will be different.

In view of the above-mentioned problems, the present inventor is a high-gloss decorative sheet that retains surface smoothness and gloss even after three-dimensional molding such as insert molding and simultaneous injection molding, and maintains a sense of design. Although a patent application (Japanese Patent Application No. 2009-088092) related to a method for manufacturing a decorative sheet was filed, when both surfaces of the decorative sheet were smoothed by the process of making the surface of the design layer and primer layer smooth, It has been found that the roll of the decorative sheet has a problem that a small dust or dust is involved to form a dent or a scratch, and that the front and back surfaces of the decorative sheet are in close contact with each other, resulting in scratches and wrinkles.
Therefore, in view of the above problems, the present inventor is less likely to cause dents or scratches on the surface due to entrainment of foreign matter by applying a roughening treatment to the back surface side of the high gloss decorative sheet, and the surface and the back surface are mutually attached. Although a patent application (Japanese Patent Application No. 2010-071006) related to a method for producing a decorative sheet in which scratches and wrinkles are less likely to occur due to adhesion, the decorative sheet is heated depending on the thickness of the base material and the arithmetic average roughness Ra. It has been found that there is a problem that irregularities occur on the surface when the sheet is softened after being subjected to molding.
In addition, even if only the arithmetic average roughness Ra is adjusted to an appropriate value, if local unevenness is generated, friction occurs when the decorative sheets are overlapped with each other, and the decorative sheet is likely to be caught between the decorative sheets. It has been found that when the surface is damaged or insert molding is performed using a decorative sheet, irregularities appear on the surface layer and the smoothness may be impaired.

  In view of the above problems, the present invention is a high gloss decorative sheet, the surface smoothness and gloss are maintained even after three-dimensional molding such as insert molding and injection molding simultaneous decoration, the design feeling is maintained, and To provide a method for producing a decorative sheet which is less likely to cause dents or scratches on the surface due to the inclusion of foreign matter even when wound on a roll, and is less likely to be scratched or wrinkled due to the close contact between the front and back surfaces. Is an issue.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor smoothed the surface protective layer before laminating it, and the ten-point average roughness RzJIS of the back surface and the thickness of the base material, and It has been found that the above-mentioned problem can be solved by performing a roughening treatment so that the arithmetic average roughness Ra and the thickness of the base material each satisfy a specific formula. The present invention has been completed based on such findings.

That is, the present invention
(1) A step of forming a design layer on a substrate, a step of making the surface of the design layer a smooth surface, a step of laminating an ionizing radiation curable resin composition on the smooth surface of the design layer, and the ionization A method for producing a decorative sheet comprising a step of crosslinking and curing a radiation-curable resin composition to form a surface protective layer, and further comprising a ten-point average roughness RzJIS on the back surface of the decorative sheet and the base material. Including a roughening treatment step in which the thickness T satisfies the following formula (I) and the arithmetic average roughness Ra and the thickness T of the base material satisfy the following formula (II): Manufacturing method of decorative sheet,
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)
(2) The method for producing a decorative sheet according to the above (1), wherein the roughening treatment is performed by subjecting the base material to hot pressing using a satin board or embossing using a satin roll.
(3) A step of forming a design layer on the substrate, a step of forming a primer layer on the design layer, a step of smoothing the surface of the primer layer, and ionizing radiation on the smooth surface of the primer layer A method for producing a decorative sheet, comprising: a step of laminating a curable resin composition; and a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer, further comprising the decorative sheet The 10-point average roughness RzJIS and the base material thickness T satisfy the following formula (I), and the arithmetic average roughness Ra and the base material thickness T satisfy the following formula (II): A method for producing a decorative sheet, comprising a roughening treatment step,
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)
(4) The method for producing a decorative sheet according to the above (3), wherein the roughening treatment is performed by performing hot pressing using a satin board or embossing using a satin roll on the base material,
(5) A decorative sheet having a design layer on the substrate and a surface protective layer obtained by crosslinking and curing the ionizing radiation curable resin composition in this order, and the surface of the surface protective layer is smooth, The ten-point average roughness RzJIS and the base material thickness T on the back surface of the decorative sheet satisfy the following formula (I), and the arithmetic average roughness Ra and the base material thickness T are expressed by the following formula (II ), A decorative sheet characterized by satisfying
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)
(6) The decorative sheet according to (5), further including a primer layer between the design layer and the surface protective layer,
(7) The decorative sheet according to the above (5), wherein the arithmetic average roughness Ra of the surface of the surface protective layer is 0.01 μm or more and less than 1.0 μm, and (8) the above (5) to (7) A decorative molded product using the decorative sheet according to any one of
Is to provide.

  According to the method for producing a decorative sheet of the present invention, in a high-gloss decorative sheet, the surface smoothness and gloss are maintained even after three-dimensional molding such as insert molding and simultaneous injection molding, and the design feeling is maintained. In addition, even when wound on a roll, a decorative sheet was obtained in which dents and scratches on the surface due to the inclusion of foreign matter are less likely to occur, and scratches and wrinkles are less likely to occur due to the close contact between the front and back surfaces. . When this decorative sheet was actually produced, scratches and dents due to the inclusion of foreign matter were suppressed, and blocking between the decorative sheet surface and the back surface was suppressed.

It is process drawing which shows 1 aspect of 1st invention in the manufacturing method of the decorating sheet of this invention. It is process drawing which shows 1 aspect of 1st invention in the manufacturing method of the decorating sheet of this invention. It is process drawing which shows 1 aspect of 2nd invention in the manufacturing method of the decorating sheet of this invention. It is process drawing which shows 1 aspect of 2nd invention in the manufacturing method of the decorating sheet of this invention.

1st invention of the manufacturing method of the decorating sheet of this invention is the process of forming a design layer on a base material, the process of making this design layer surface smooth, and ionizing radiation on the smooth surface of this design layer A step of laminating a curable resin composition, a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer, a ten-point average roughness RzJIS on the back surface of the decorative sheet, and the thickness of the substrate A roughening treatment step in which the thickness T satisfies the above formula (I), and the arithmetic average roughness Ra and the thickness T of the base material satisfy the following formula (II): To do. Hereinafter, the manufacturing method of 1st invention is demonstrated in detail using FIG.1 and FIG.2.
FIG.1 and FIG.2 is process drawing which shows the outline of 1st invention of the manufacturing method of the decorating sheet of this invention. The production method of the first invention is a method including at least the following steps (1) to (5).

(1) The process of forming a design layer on a base material After printing or coating the design ink on the base material 11, the design layer 12 is formed by drying as needed. The design layer 12 is composed of a pattern layer and / or a solid solid colored layer. The design layer 12 usually has irregularities due to the pigment contained in the ink and irregularities of the printed portion and the non-printed portion that are generated by pattern printing of the pattern.

(2) Process of making the surface of the design layer smooth The surface of the design layer 12 is formed with a smooth surface by hot pressing using a mirror plate or roll pressing using a mirror roll. The hot pressing process and the roll pressing process are performed by using a known method to heat and soften the base sheet constituting the decorative sheet 10 to a temperature not lower than the softening temperature, the melting point or lower than the melting temperature. After pressurizing and shaping the surface side, cooling and solidifying to form a smooth surface, the surface of the design layer 12 becomes smooth as shown in FIGS. 1 (b) and 2 (b).
In the present invention, that the surfaces of the design layer 12 and the primer layer 14 are smooth means that the arithmetic average roughness (Ra) is 0.5 μm or less, and preferably 0.2 μm or less. Here, the arithmetic average roughness (Ra) refers to the arithmetic average roughness Ra defined in JIS B 0601: 2001.

(3) Step of laminating the ionizing radiation curable resin composition on the smooth surface of the design layer Next, a coating liquid comprising the ionizing radiation curable resin composition or a coating liquid containing the ionizing radiation curable resin composition is used. Lamination is performed by coating on the smooth surface of the design layer 12. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the design layer 12 by a coating method described later.
In the production method of the present invention, the prepared coating solution is applied to the surface of the design layer 12 so that the thickness after curing is 1 to 30 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer.
Here, the ionizing radiation curable resin has an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.

(4) Step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer Next, an uncured resin layer made of the ionizing radiation curable resin composition is irradiated with ionizing radiation such as electron beams and ultraviolet rays. Thus, the ionizing radiation curable resin composition is crosslinked and cured to form the surface protective layer 13. Thereby, the decoration sheet | seat 10 in which the surface protective layer 13 was formed as shown in FIG.1 (c) and FIG.2 (c) can be obtained.
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 the base material 11 that deteriorates due to the electron beam, 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, it is possible to suppress the irradiation of the extra electron beam to the base material 11, and to minimize the deterioration of the base material due to the excess electron beam.
The irradiation dose is preferably such that the crosslinking 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 100 kGy (1 to 10 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, a high frequency type, etc. 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 smoothness of the surface protective layer 13 is preferably 0.01 μm or more and less than 1.0 μm, more preferably 0.01 to 0.5 μm, and more preferably 0.05 to 0.2 μm as the arithmetic average roughness Ra. More preferably. Here, the arithmetic average roughness Ra means the arithmetic average roughness Ra specified in JIS B 0601: 2001.

(5) Roughening treatment process of the back surface of a decoration sheet The roughening treatment process of the back surface of the decoration sheet in this invention is the back surface of a decoration sheet to such an extent that above-mentioned Formula (I) and Formula (II) are satisfy | filled. Although it will not specifically limit if it is the process which can be roughened, For example, the back surface side of the decorating sheet 10, specifically, the surface which does not contact the design layer 12 and the surface protective layer 13 of the base material 11 was used. Examples thereof include a method of roughening by embossing or sandblasting using a hot press or a satin roll. Known methods can be used as hot pressing and embossing, and the decorative sheet 10 is softened by heating it to a temperature not lower than the softening temperature of the base material constituting it and below the melting point or melting temperature. After pressurizing and shaping the back side of the sheet 10, the back side of the decorative sheet 10 is roughened by cooling and solidifying as shown in FIG.
Moreover, as a roughening process in this invention, as shown in FIG.2 (d), the method of roughening the back surface of the decorating sheet 10 by providing the fine particle containing resin layer 15 is also mentioned.

When roughening the back surface of the decorative sheet 10 by hot pressing or embossing, it is preferably performed together with the step (2). Specifically, a mirror plate is used on the front side of the decorative sheet 10 and a hot press process is performed using a satin board on the back side, or a mirror roll is used on the front side of the decorative sheet 10 and a satin side on the back side. By embossing using a roll, the surface of the decorative sheet 10 and the roughening of the back surface can be simultaneously performed (see FIG. 1B).
Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting hot press temperature and embossing temperature, or adjusting the surface roughness of a satin board or a satin roll. The hot pressing temperature and embossing temperature may be appropriately selected depending on the base material. For example, when vinyl chloride is 30 to 70 ° C., polypropylene resin is 160 to 180 ° C., and acrylic resin is 150 to 260 ° C. The uneven shape of the roll can be shaped well.

  Sandblasting can be performed by spraying inorganic particles such as silica and titania onto the surface to be treated (the back surface of the decorative sheet 10) using compressed air. The arithmetic average roughness Ra of the back surface of the decorative sheet 10 can be kept high, which is preferable. Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting the particle diameter and spraying amount of an inorganic particle.

Examples of the method for providing the fine particle-containing resin layer 15 on the back surface of the decorative sheet 10 include a method of laminating a resin composition containing a binder resin and fine particles by the above-described coating method or transfer method (FIG. 2 ( d)).
When the fine particle-containing resin layer 15 is provided on the back surface side of the decorative sheet 10, it can be performed before and after any of the steps (1) to (4), but after the step (2). This is preferable because the arithmetic average roughness Ra of the back surface of the decorative sheet 10 can be kept high. Adjustment of RzJIS and Ra of a to-be-processed surface can be performed by adjusting the compounding ratio of microparticles and binder resin, and the particle size of microparticles.

The roughening treatment of the back surface of the decorative sheet 10 of the present invention requires that the 10-point average roughness RzJIS of the back surface and the thickness T of the base material satisfy the following formula (I). It is preferable to satisfy (IA), and it is more preferable to satisfy the following formula (IB).
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ RzJIS (IA)
T × 0.18 ≧ RzJIS (IB)
When the ten-point average roughness RzJIS on the back surface of the decorative sheet 10 exceeds the above range, the back surface roughness also affects the surface when the decorative sheet 10 is softened. For example, insert molding using the decorative sheet 10 is performed. When the process is performed, problems such as inferior surface smoothness and surface gloss of the obtained molded product and inferior adhesion to the injection resin occur.

Furthermore, the roughening treatment on the back surface of the decorative sheet 10 of the present invention requires that the arithmetic average roughness Ra and the thickness T of the base material satisfy the following formula (II). It is preferable to satisfy -A), and it is more preferable to satisfy the following formula (II-B).
T × 0.20 ≧ Ra ≧ T × 0.005 (II)
T × 0.18 ≧ Ra ≧ T × 0.02 (II-A)
T × 0.15 ≧ Ra ≧ T × 0.03 (II-B)
If the arithmetic mean roughness Ra of the back surface of the decorative sheet 10 is less than the above range, there is a risk that surface dents or scratches due to entrainment of foreign matter or scratches or wrinkles due to the close contact between the front and back surfaces. is there. On the other hand, when the arithmetic average roughness Ra of the back surface of the decorative sheet 10 exceeds the above range, the arithmetic average roughness Ra of the back surface of the decorative sheet 10 is too large with respect to the thickness of the base material. When the surface of the molded product is softened, the roughness on the back side also affects the surface. For example, when insert molding is performed using the decorative sheet 10, the surface smoothness and surface gloss of the resulting molded product are inferior. Problems such as poor adhesion to the resin occur.
In addition, even if the arithmetic average roughness Ra is small, if the ten-point average roughness RzJIS exceeds the above range, there may be local irregularities, and friction occurs when the decorative sheets 10 are stacked. There is a risk of scratches and the like.
Here, the average roughness Ra means the arithmetic average roughness Ra defined in JIS B 0601: 2001. Further, the ten-point average roughness RzJIS means the ten-point average roughness RzJIS defined in JIS B 0601: 2001.

2nd invention of the manufacturing method of the decorating sheet of this invention is the process of forming a design layer on a base material, the process of forming a primer layer on this design layer, and making this primer layer surface smooth A step of laminating an ionizing radiation curable resin composition on the smooth surface of the primer layer, a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer, and a decorative sheet The back surface ten-point average roughness RzJIS and the base material thickness T satisfy the above formula (I), and the arithmetic average roughness Ra and the base material thickness T satisfy the above formula (II). And a roughening treatment step.
Hereafter, the manufacturing method of 2nd invention is demonstrated in detail using FIG.3 and FIG.4.
FIG.3 and FIG.4 is process drawing which shows the outline of 2nd invention of the manufacturing method of the decorating sheet of this invention. The production method of the second invention is a method including at least the following steps (1) to (6).

(1) The process of forming a design layer on a base material After printing or coating the design ink on the base material 11, the design layer 12 is formed by drying as needed. The design layer 12 is composed of a pattern layer and / or an entire solid color layer as in the first invention.

(2) Step of forming primer layer on design layer Next, after laminating the primer composition on the design layer 12, the primer layer 14 is formed by drying as necessary. As shown in FIG. 3A and FIG. 4A, the surface of the primer layer 14 has irregularities reflecting the irregularities on the surface of the design layer 12.

  As a method of laminating the primer layer 14, it can be formed by a coating method, and a transfer method can also be used. When the primer layer 12 is formed by the coating method, gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, silk screen solid coating, wire bar coating , Flow coat, comma coat, pouring coat, brush coating, spray coating and the like can be used. In addition, the transfer method is a method in which a coating film of a primer layer is once formed on a thin sheet (film base material) and then coated on the surface of the base material. There are a laminating method for adhering to a three-dimensional object, a transferring method in which only a support sheet is peeled after adhering a transfer sheet once formed with a coating film and an adhesive layer on a releasable support sheet.

(3) Step of making the primer layer surface smooth A smooth surface is formed on the surface of the primer layer 14 by hot pressing using a mirror plate or roll pressing using a mirror roll. These hot press processing and roll press processing are the same as in the first invention, and the surface of the primer layer 14 is smoothed by this step as shown in FIGS. 3 (b) and 4 (b).

(4) Step of laminating the ionizing radiation curable resin composition on the smooth surface of the primer layer Next, a coating liquid comprising the ionizing radiation curable resin composition or a coating liquid containing the ionizing radiation curable resin composition is used. Lamination is performed by coating on the smooth surface of the primer layer 14. The coating method and the content of the ionizing radiation curable resin are as described in the first invention.

(5) Step of forming a surface protective layer by crosslinking and curing the ionizing radiation curable resin composition Next, an uncured resin layer made of the ionizing radiation curable resin composition is irradiated with ionizing radiation such as electron beams and ultraviolet rays. Thus, the ionizing radiation curable resin composition is crosslinked and cured to form the surface protective layer 13. Thereby, the decoration sheet | seat 10 in which the surface protective layer 13 was formed as shown in FIG.3 (c) and FIG.4 (c) can be obtained. Here, the curing conditions for ionizing radiation irradiation such as electron beam irradiation and ultraviolet irradiation, and the electron beam source and ultraviolet source used are as described in the first invention.

(6) Roughening treatment process on the back surface of the decorative sheet The contents of the roughening treatment process are as described in the first invention, but the rough surface on the back surface of the decorative sheet 10 by hot pressing or embossing. In the case of carrying out the modification, it is preferably carried out together with the above-mentioned step (3) (see FIG. 3 (b)). When roughening the back surface, it is preferable to carry out after the above step (3) (see FIG. 4D).

The substrate 11 in the production method of the present invention is selected in consideration of suitability for vacuum forming and suitability for simultaneous injection molding, and typically a resin sheet made of a thermoplastic resin is used. The thermoplastic resin is generally an acrylic resin, a polyolefin resin such as polypropylene or polyethylene, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), a vinyl chloride resin, a polyester resin, or the like. Is used. Moreover, the base material 11 can be used as a single layer sheet of these resins or a multilayer sheet of the same kind or different kind of resin.
Although the thickness of the base material 11 is selected according to a use, it is about 0.03-1.0 mm normally, and when considering the cost etc., about 0.03-0.5 mm is common.

In order to improve the adhesiveness with the layer provided on the base material 11 described above, the surface can be subjected to a surface treatment such as an oxidation method if desired.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method and the like. 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.

  Next, the design layer 12 including the pattern layer and / or the entire solid colored layer shown in FIGS. 1 and 2 gives decorativeness to the resin molded product. The pattern layer is formed by printing various patterns using ink and a printing machine. As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.

As the ink used for the design layer 12, an ink obtained by appropriately mixing a binder, a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent is used. The binder is not particularly limited, and examples thereof include polyurethane resins (acrylic urethane copolymer resins, etc.), vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, and chlorinated polypropylene. Resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., any one can be used alone or in combination of two or more Used as a mixture.
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, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

  In the present invention, a concealing layer may be provided between the design layer 12 and the substrate 11 as necessary. The concealing layer is provided for the purpose of preventing the pattern color of the decorative sheet from being affected by changes and variations in the color of the surface of the substrate 11. Usually, it is often 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 binder, colorant, and the like used are the same as those used for the design layer 12. In addition, when the design layer 12 has a whole surface solid colored layer, you may use it as a concealment layer.

In the production method of the second invention, the primer layer 14 formed on the design layer 12 has a function of improving the adhesion between the design layer 12 and the surface protective layer 13 on the substrate 11. Furthermore, by smoothing the surface of the primer layer 14, it is possible to smooth the surface of the surface protective layer 13 without affecting the surface protective layer 13 with the unevenness of the design layer 12.
Moreover, it has the effect of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface protective layer 13.
The primer composition constituting the primer layer 14 is (meth) acrylic resin, urethane resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, Chlorinated polyethylene or the like is used.

Moreover, it is preferable that the thickness of the primer layer 14 is about 0.1-10 micrometers.
When the thickness is 0.1 μm or more, it is possible to sufficiently exert the effect of preventing the surface protective layer from being cracked, broken, whitened or the like. On the other hand, if the thickness of the primer layer is 10 μm or less, when the primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not fluctuate. From the above points, the thickness of the primer layer is more preferably 0.1 to 10 μm.

In the production method of the present invention, a polymerizable monomer and a polymerizable oligomer and / or prepolymer (hereinafter, abbreviated as oligomer / prepolymer) as an ionizing radiation curable resin used in the ionizing radiation curable resin composition. ) Is described below.
As the polymerizable monomer, typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specific examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate and ethyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the polymerizable oligomer / prepolymer, an oligomer / prepolymer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, Examples include polyether (meth) acrylates and polycarbonate (meth) acrylates.

  Furthermore, as the polymerizable oligomer / prepolymer, other polybutadiene (meth) acrylate oligomer / prepolymer having a (meth) acrylate group in the side chain of the polybutadiene oligomer / prepolymer and a polysiloxane bond in the main chain Silicone (meth) acrylate oligomer / prepolymer with amino acid, aminoplast resin (meth) acrylate oligomer / prepolymer modified with aminoplast resin with many reactive groups in a small molecule, or novolak epoxy resin, bisphenol There are oligomers / prepolymers having cationically polymerizable functional groups in the molecule such as epoxy resin, aliphatic vinyl ether and aromatic vinyl ether.

  As the ionizing radiation curable resin composition in the present invention, when at least polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and a polyfunctional (meth) acrylate are used, excellent chemical resistance and Since scratch resistance and good three-dimensional formability are satisfied at the same time, it is preferable in that a decorative sheet that does not crack in the surface protective layer and can be easily three-dimensionally formed can be obtained.

When using an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and polyfunctional (meth) acrylate, the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is preferably 98: It is 2-70: 30, More preferably, it is 95: 5-80: 20.
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 has (meth) acrylate in the terminal or side chain. This (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing.
The polycarbonate (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and more than 2,000. Is more preferable. 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.

When using an ionizing radiation curable resin composition containing acrylic silicone (meth) acrylate and polycyclic (meth) acrylate, the mass ratio of acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is preferred. Is from 50:50 to 95: 5, more preferably from 95: 5 to 80:20.
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. Any of those having two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the above.
The acrylic silicone (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 1,000 or more, and more preferably 2,000 or more. 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.

The polyfunctional (meth) acrylate used for this invention should just be bifunctional or more (meth) acrylate, and there is no restriction | limiting in particular. However, trifunctional or higher functional (meth) acrylates are preferred from the viewpoint of curability. Here, bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule.
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.
The polyfunctional (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and more than 2,000. More preferably. The upper limit of the weight average molecular weight of the polyfunctional (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.

  Examples of the polyfunctional (meth) acrylate oligomer include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.

  Furthermore, other polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meta-methacrylate) having polysiloxane bonds in the main chain. ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules.

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin 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.

  In the said ionizing radiation curable resin composition, other resin can be contained in the range with the effect of this invention. For example, when it is desired to impart flexibility to the decorative sheet 10 obtained by the production method of the present invention, a thermoplastic resin can be added. On the other hand, when resistance to a solvent is required, it is preferable not to contain a thermoplastic resin.

  Examples of the additive used in the ionizing radiation curable resin composition include a weather resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, Examples include a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and an abrasion resistance improver.

  The surface protective layer 13 thus formed has various functions by adding various additives, for example, a so-called hard coat function, antifogging function, and antifouling function having high hardness and scratch resistance. Further, an antiglare function, an antireflection function, an ultraviolet shielding function, an infrared shielding function, and the like can be provided.

  In this invention, it is preferable that the thickness after hardening of the surface protective layer 13 is 1-30 micrometers. When the thickness of the surface protective layer 13 after curing is 1 μm or more, excellent design properties such as transparency and glossiness can be obtained, and further sufficient as a protective layer such as stain resistance, scratch resistance and weather resistance. Physical properties can be obtained. On the other hand, when the thickness is 30 μm or less, there is no cracking or whitening of the protective layer at the time of molding, and the desired shape can be followed, and good design properties can be obtained even after three-dimensional molding. From this viewpoint, the thickness of the surface protective layer 13 after curing is preferably in the range of 2 to 20 μm, and more preferably in the range of 3 to 10 μm.

  Examples of the binder resin used for the fine particle-containing resin layer 15 include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyurethane resins, acrylic resins, acrylic urethane resins, polycarbonate resins, and vinyl chloride / vinyl acetate copolymers. In addition to resins such as polyvinyl butyral resin and nitrocellulose resin (nitrified cotton), compounds such as alkyl titanate and ethyleneimine can also be used, and are selected as appropriate from the viewpoint of adhesion to the adherend and injection resin. Can be used.

Examples of the fine particles used in the fine particle-containing resin layer 15 include silica, talc, calcium carbonate, precipitated barium sulfate, alumina, acidic clay, clay, magnesium carbonate, carbon black, tin oxide, titanium white, and urea powder resin. Inorganic fine particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, and organic polymers such as polyamide (nylon) are used. Of these, silica, acrylic beads, polyethylene wax and the like that are easy to handle and inexpensive are suitable.
The average particle size of the fine particles is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and the addition amount is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. The range of 0.5 to 5 parts by mass is more preferable. The shape of the particles is a polyhedron, a sphere, a scale shape, or the like.

The decorative sheet 10 obtained by the production method of the present invention can be used for various injection molding methods such as an insert molding method, an injection molding simultaneous decorating method, a blow molding method, and a gas injection molding method. It is suitably used for the injection molding simultaneous decoration method.
In the insert molding method, in the vacuum forming step, the decorative sheet obtained by the manufacturing method of the present invention is vacuum-formed into a molded product surface shape in advance (off-line pre-molding) with a vacuum forming die, and then an extra portion is removed as necessary. Trimming to obtain a molded sheet. 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 a thermoplastic resin such as a polyolefin resin such as polyethylene or polypropylene, an ABS resin, a styrene resin, a polycarbonate resin, an acrylic resin, or a vinyl chloride resin is representative. In addition, thermosetting resins such as urethane resins and epoxy resins can be used depending on applications.

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 heat pressure from the injection resin, and therefore, if the decorative sheet is close to a 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 product manufactured as described above is a molded product with excellent surface smoothness and gloss and high design. 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 these examples.
Details of each evaluation method and measurement method are shown below.
(Arithmetic mean roughness Ra)
Using a surface roughness measuring instrument manufactured by Tokyo Seimitsu Co., Ltd., trade name "Handy Surf E-35A", the roughness curve of length L is folded from the center line in accordance with JIS B 0601: 2001, and each roughness A value obtained by dividing the total area obtained by the curve and the center line by the length L was expressed in micrometers (μm).
(10-point average roughness RzJIS)
Ten-point average roughness RzJIS was measured according to JIS B 0601: 2001 with a measurement length of 4 mm and a cutoff value of 0.8 mm.
(Blocking resistance)
Two decorative sheets were used, one surface side and the other back side were overlapped, a load of 2.94 MPa was applied by a blocking tester, and left at 40 ° C. for 72 hours, and then the contacted surfaces adhered to each other -The degree of joining was evaluated by the following index.
○: There is no resistance when peeling the stacked decorative sheets.
X: There was resistance when peeling the laminated decorative sheet, and scratches and wrinkles derived from blocking were confirmed on the surface side of the decorative sheet.
(Scratches and dents due to foreign matter)
The decorative sheet was wound up in a roll shape in which the front surface side of one layer and the back surface side of the other layer were overlapped, and allowed to stand at 20 ° C. for 168 hours. Twenty decorative sheets were cut out from the roll, and the number of sheets with scratches and dents in the surface protective layer was confirmed. These scratches and dents are considered to be caused by foreign matters such as fine dust caught in the roll.
○: Decorative sheet with scratches and dents 0 sheets △: Decorative sheet with scratches and dents less than 10 x: Decorative sheets with scratches and dents 10 sheets or more (surface gloss)
Using a gloss meter (Micro-tri-gloss manufactured by Big Gardner), the gloss value was measured under the condition of an incident angle of 60 °. The higher the value, the higher the gloss.
(Smoothness)
The surface of the molded product obtained by insert-molding the decorative sheet was visually evaluated.
○: Excellent surface smoothness and sharp image on the surface of the molded product.
X: The surface smoothness was poor, and the image reflected on the surface of the molded product was distorted.
(Haze)
The haze value defined in ASTM D4039 was used for evaluation. Using a gloss meter (Micro-Tri-Gloss manufactured by Big Gardner), the respective gloss values were measured under the conditions of an incident angle of 60 ° and 20 °, and the haze value was determined by the following equation.
Haze value = Gloss value (60 °) −Gloss value (20 °)
A smaller haze value indicates higher glossiness and transparency, and a larger haze value indicates lower haze transparency.
(Adhesion with injection resin)
After insert molding, use a cutter knife on the surface of the sheet to make 10 vertical and 10 horizontal grid cuts at 2 mm intervals, and then apply Nichiban's cello tape (registered trademark) to the cuts. It peeled.
○: There was no peeling, or very slight peeling was observed along the notches of the grid.
X: Peeling was observed between the sheet and the injection resin.

Example 1
A sheet of ABS resin (thickness: 300 μm) was used as the base material, and an acrylic urethane copolymer resin ink was used on the surface of the sheet to form a woodgrain design layer by gravure printing. Next, a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 μm is provided on the design layer side (front side), and an arithmetic average roughness Ra of 4.0 μm and ten-point average roughness RzJIS 16 μm on the side having no design layer (back side). Using a hot press machine using a stainless steel metal plate containing a satin pattern, the surface of the design layer of the obtained sheet was subjected to hot press processing at 150 ° C. under a pressure of 5 kgf / cm ² for 10 minutes.
An electron beam curable resin composition composed of a bifunctional urethane acrylate (weight average molecular weight; 2,000) is applied to the surface of the design layer after hot pressing by gravure reverse so that the thickness after curing is 6 μm. did. This uncured resin 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 electron beam curable resin composition to obtain a decorative sheet.
The ten-point average roughness RzJIS of the obtained decorative sheet was 1.0 μm on the front side and 14 μm on the back side. The arithmetic average roughness Ra was 0.1 μm on the front side and 2.0 μm on the back side.
Next, the obtained decorative sheet was heated with an infrared heater until the temperature of the sheet reached 170 ° C., softened, and then vacuum-formed. When the decorative sheet was released from the mold and the back surface was confirmed, the embossing disappeared and became smooth. Unnecessary portions of the vacuum-formed decorative sheet were trimmed by pressing the die-cut mold with hydraulic pressure. Using this trimmed decorative sheet, it is inserted into an injection mold, then clamped, ABS resin is injected into the mold, and the decorative sheet is laminated and integrated on the surface of the molded product. A resin molded product was obtained.

Example 2
Example 1 with the exception of using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 8.5 μm and a ten-point average roughness Rz JIS of 39 μm on the side having no design layer (back side) in the hot pressing step. Similarly, a decorative sheet and a decorative resin molded product were obtained.

Example 3
As a base material, a sheet made of ABS resin having a thickness of 200 μm is used, and in the hot press process, the side having no design layer (the back side) has an arithmetic average roughness Ra of 6.9 μm and a ten-point average roughness RzJIS of 28 μm. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that a stainless steel metal plate with a handle was used.

Example 4
As a base material, a sheet made of ABS resin having a thickness of 400 μm is used, and in the hot press process, the side having no design layer (back side) has an arithmetic average roughness Ra of 4.0 μm and a ten-point average roughness of RzJIS 23 μm. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that a stainless steel metal plate with a handle was used.

Example 5
A sheet of ABS resin (thickness: 300 μm) was used as the base material, and an acrylic urethane copolymer resin ink was used on the surface of the sheet to form a woodgrain design layer by gravure printing. Next, a two-component curable urethane resin having an acrylic / urethane block copolymer as a main component and an isocyanate added as a curing agent was applied onto the design layer to form a transparent primer layer having a thickness of 2 μm.
Next, a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 μm is provided on the design layer side (front side), and an arithmetic average roughness Ra of 4.0 μm and ten-point average roughness RzJIS 16 μm on the side having no design layer (back side). Using a hot press machine using a stainless steel metal plate with a satin pattern, the surface of the primer layer of the obtained sheet was subjected to hot press processing at 150 ° C. under a pressure of 5 kgf / cm ² for 10 minutes.
An electron beam curable resin composition composed of bifunctional urethane acrylate (weight average molecular weight; 2,000) is applied to the surface of the primer layer after hot pressing by gravure reverse so that the thickness after curing is 6 μm. did. On this uncured resin layer, the electron beam curable resin composition was cured under the same conditions as in Example 1 to obtain a decorative sheet.
The ten-point average roughness RzJIS of the obtained decorative sheet was 1.0 μm on the front side and 14 μm on the back side. The arithmetic average roughness Ra was 0.1 μm on the front side and 2.0 μm on the back side.
Next, using the obtained decorative sheet, a decorated resin molded product was obtained in the same manner as in Example 1.

Example 6
Example 5 with the exception of using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 8.5 μm and a ten-point average roughness Rz JIS of 39 μm on the side having no design layer (back side) in the hot pressing step Similarly, a decorative sheet and a decorative resin molded product were obtained.

Example 7
As a base material, a sheet made of ABS resin having a thickness of 300 μm is used, and in the hot pressing process, the side having no design layer (back side) has an arithmetic average roughness Ra of 6.9 μm and a ten-point average roughness RzJIS of 26 μm. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 5 except that a stainless steel metal plate with a handle was used.

Example 8
As a base material, a sheet made of ABS resin having a thickness of 400 μm is used, and in the hot press process, the side having no design layer (back side) has an arithmetic average roughness Ra of 4.0 μm and a ten-point average roughness of RzJIS 23 μm. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 5 except that a stainless steel metal plate with a handle was used.

Example 9
A sheet made of ABS resin having a thickness of 400 μm was used as a base material, and bifunctional polycarbonate acrylate (weight average molecular weight; 10,000) and hexafunctional urethane acrylate (weight average molecular weight; 6,000) were 94: A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that an electron beam curable resin mixed at a ratio of 6 was used.

Example 10
A sheet made of an ABS resin having a thickness of 400 μm was used as a base material, and a bifunctional acrylic silicone acrylate (weight average molecular weight; 20,000) and a hexafunctional urethane acrylate (weight average molecular weight; 5,000) were 70. : A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that the electron beam curable resin mixed at a ratio of 30 was used.

Comparative Example 1
In the hot press processing of Example 10, on the back side, hot press processing was performed at 140 ° C. using a stainless steel metal plate with a satin pattern having an arithmetic average roughness Ra of 19 μm and a ten-point average roughness RzJIS 130 μm. Except for the above, a decorative sheet and a decorative resin molded product were obtained in the same manner as Example 5.

Comparative Example 2
As a base material, a sheet made of ABS resin having a thickness of 200 μm was used, and in the hot press processing of Example 10, instead of a stainless steel metal plate with a satin pattern on the back side, arithmetic average roughness Ra1. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 5 except that hot pressing was performed using a stainless steel specular plate with 8 μm and 10-point average roughness RzJIS 6 μm.

Comparative Example 3
In Comparative Example 2, a sheet made of ABS resin having a thickness of 400 μm was used as a base material, and a composition comprising 100 parts by mass of acrylic resin and 10 parts by mass of silica (average particle size: 3.0 μm) on the surface side. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Comparative Example 1 except that gravure printing was performed at a coating amount of 1 g / m ² to provide a fine particle-containing resin layer.

Comparative Example 4
As a base material, a sheet made of ABS resin having a thickness of 100 μm was used, and in the hot press processing of Example 10, an arithmetic average roughness Ra28. A decorative sheet and a decorative resin molded product were obtained in the same manner as in Example 5 except that hot pressing was performed using a stainless steel specular plate having a 2 μm, 10-point average roughness RzJIS of 97 μm.

  Next, the arithmetic average roughness Ra and the ten-point average roughness RzJIS were measured for the front and back surfaces of the decorative sheets of Examples 1 to 10 and Comparative Examples 1 to 4, and the emboss fastness was measured for the back surface. The results are shown in Tables 1 to 3. In addition, the blocking resistance of the decorative sheets obtained in Examples 1 to 10 and Comparative Examples 1 to 4, scratches and dents due to foreign matter, and the surface gloss, smoothness, haze, and injection resin of the decorative resin molded product The adhesion was evaluated. The results are shown in Tables 1 to 3.

As shown in Tables 1 to 3, the decorative sheets of Examples 1 to 10 did not cause scratches or dents due to blocking or entrainment of foreign matter even when wound on a roll. On the other hand, in the comparative example 1 which was Tx0.30 <RzJIS, the smoothness of the surface of a decorative resin molded product was impaired. On the other hand, in Comparative Example 2 in which Ra <T × 0.005, scratches or dents due to blocking or foreign matter entrainment occurred.
Moreover, in the comparative example 3 which provided the microparticle containing resin layer in the decorating sheet surface side, the smoothness of the decorating resin molded product surface was impaired.
In Comparative Example 4, since Ra and RzJIS were too large, the surface gloss of the decorated resin molded product was remarkably lowered, and haze was generated.

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

10. Decorative sheet Base material 12. Design layer 13. Surface protective layer 14. Primer layer 15. Resin layer containing fine particles

Claims (8)

A step of forming a design layer on a substrate, a step of making the surface of the design layer a smooth surface, a step of laminating an ionizing radiation curable resin composition on the smooth surface of the design layer, and the ionizing radiation curable property A method for producing a decorative sheet comprising the step of forming a surface protective layer by crosslinking and curing the resin composition, and further comprising a ten-point average roughness RzJIS and a thickness T of the substrate on the back surface of the decorative sheet. And a roughening treatment step that satisfies the following formula (I) and that the arithmetic average roughness Ra and the thickness T of the base material satisfy the following formula (II): Sheet manufacturing method.
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)   The method for producing a decorative sheet according to claim 1, wherein the roughening treatment is performed by subjecting the base material to hot pressing using a satin board or embossing using a satin roll. A step of forming a design layer on a substrate, a step of forming a primer layer on the design layer, a step of smoothing the surface of the primer layer, and an ionizing radiation curable resin on the smooth surface of the primer layer A method for producing a decorative sheet, comprising a step of laminating a composition and a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer, and further comprising a back surface of the decorative sheet. The 10-point average roughness RzJIS and the base material thickness T satisfy the following formula (I), and the arithmetic average roughness Ra and the base material thickness T satisfy the following formula (II). The manufacturing method of the decorating sheet | seat characterized by including a surface treatment process.
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)   The said roughening process is a manufacturing method of the decorating sheet of Claim 3 performed by performing the hot press process which used the satin board for the said base material, or the embossing which used the satin roll. A decorative sheet having a design layer and a surface protective layer formed by crosslinking and curing an ionizing radiation curable resin composition on a substrate in this order, the surface of the surface protective layer being smooth, The ten-point average roughness RzJIS and the base material thickness T on the back surface of the sheet satisfy the following formula (I), and the arithmetic average roughness Ra and the base material thickness T satisfy the following formula (II). A decorative sheet characterized by that.
T × 0.30 ≧ RzJIS (I)
T × 0.20 ≧ Ra ≧ T × 0.005 (II)   The decorative sheet according to claim 5, further comprising a primer layer between the design layer and the surface protective layer.   The decorative sheet according to claim 5, wherein the surface of the surface protective layer has an arithmetic average roughness Ra of 0.01 μm or more and less than 1.0 μm.   The decorative molded product which uses the decorating sheet in any one of Claims 5-7.

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