JP2020099998A - Decorative molded product, method of manufacturing decorative molded product, transfer sheet, and image display device - Google Patents

Abstract

The present invention provides a decorative molded article that suppresses glare and has excellent antiglare properties, contrast, and image clarity. A decorative molded product 10 having a protective layer 2 having unevenness on a resin molded body 1, the surface of the protective layer 2 having an arithmetic mean roughness of JIS B0601:1994 with a cutoff value of 0.8 mm. Rax1, the arithmetic average roughness of JIS B0601: 1994 with a cutoff value of 0.08 mm is defined as Ray1, and the ten-point average roughness of JIS B0601: 1994 with a cutoff value of 0.8 mm is defined as Rzx1. Ray1 and Rzx1 satisfy the following formulas (1) to (3). 0.050 μm≦Rax1<0.140 μm (1) 0.30≦(Rax1−Ray1)/Ray1 (2) Rzx1/Rax1≦15.0 (3) [Selection diagram] FIG.

Description

The present invention relates to a decorative molded product, a method for manufacturing a decorative molded product, a transfer sheet, and an image display device.

2. Description of the Related Art Conventionally, in the fields of household appliances, automobile interior parts, sundries, and the like, high functionality and design have been developed by decorating the surface of the transferred material with characters and pictures. As a method of decorating the surface of the transferred material, there is a transfer method. The transfer method uses a transfer sheet in which a transfer layer including a release layer, a pattern layer, an adhesive layer, etc. is formed on a base material, and heat and pressure are applied to bring the transfer layer into close contact with a transfer target, and then the base material is transferred. It is a method of peeling and transferring only the transfer layer to the surface of the transferred object for decoration.

Further, depending on the application, there is a case where excellent transferability is required on the surface of the transferred material by mixing different textures such as gloss and matte.
For example, in Patent Document 1, a release layer entirely containing a matting agent on a base sheet, a mask layer partially containing an active energy ray-curable resin, a release layer as a transfer layer, and a pattern layer. After making the transfer layer side of the partial mat transfer sheet on which the transfer layer has been formed adhere to the surface of the transferred material, and applying heat and pressure from the base sheet side of the partial mat transfer sheet to bond the transfer layer to the surface of the transferred material. A partial mat transfer molded article obtained by peeling a base sheet, a release layer and a mask layer is disclosed.

Japanese Patent No. 5095598

However, in the partial mat transfer molded article described in Patent Document 1, glare (a phenomenon in which a minute variation in brightness is visible in the image light due to the uneven structure on the surface is visible) is observed in the mat portion on the surface of the transfer layer after transfer. Many cases occurred.
Further, in the partial matte transfer molded article described in Patent Document 1, the characters or the like of the transferred object are whitish and the contrast is lowered, or the image clarity of the display element is impaired when the display element is visually recognized through the molded article. There was a problem that

The present invention has been made in view of such circumstances, while suppressing the glare, antiglare, contrast and image clarity is a decorative molded article, a method for producing the decorative molded article, An object of the present invention is to provide a transfer sheet used for the decorative molded product and an image display device using the decorative molded product.

The present invention provides the following [1] to [4].
[1] A decorative molded product in which a protective layer is provided on a resin molded body, wherein the protective layer has a region P having irregularities and a region Q adjacent to the region P, and the region P The arithmetic mean roughness of JIS B0601:1994 when the surface cutoff value λc is 0.8 mm is Ra _x1 , and the surface cutoff value λc of the area P is JIS B0601:1994. _Is defined as Ra _y1 , and the ten-point average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm is defined as Rz _x1 , Ra _x1 , ra _y1, and _{Rz x1} is represented by the following formula (1) to satisfy (3), decorative moldings.
0.050 μm≦Ra _x1 <0.140 μm (1)
0.30≦(Ra _x1 −Ra _y1 )/Ray _y1 (2)
Rz _x1 /Ra _x1 ≤15.0 (3)
[2] A base material having a region P′ and a region Q′ adjacent to the region P′, a concavo-convex layer having a concavo-convex shape provided on the region P′ of the base material, and the concavo-convex layer described above. On the first release layer formed on the uneven shape, the second release layer provided on the region Q′ of the base material, on the first release layer, and on the second release layer. And a protective layer formed on the first release layer, the arithmetic mean roughness of JIS B0601:1994 is Ra _x11 when the surface cutoff value λc of the first release layer is 0.8 mm, and the first release layer is When the cutoff value λc of the surface of the layer is 0.08 mm, the arithmetic mean roughness of JIS B0601:1994 is Ra _y11 and the cutoff value of the surface of the first release layer is 0.8 mm. JIS B0601: a ten-point average roughness of 1994 when defined as _{Rz x11, Ra x11, Ra y11} , and _{Rz x11} the following formulas (1) 'to (3)' meet, the transfer sheet.
0.050 μm≦Ra _x11 <0.140 μm (1)′
0.30≦(Ra _x11 −Ra _y11 )/Ray _y11 (2)′
Rz _x11 /Ra _x11 ≤15.0 (3)'
[3] A step of transferring the protective layer of the transfer sheet according to the above [2] to a resin molded body, and a step of peeling off the first release layer and the second release layer of the transfer sheet. , A method for producing a decorated molded product.
[4] An image display device having a display element and a front plate arranged on the light emitting surface side of the display element, wherein the front plate is the protective layer side of the decorative molded product according to the above [1]. The image display device is arranged so that its surface faces the side opposite to the display element.

According to the present invention, while suppressing glare, a decorative molded article having good antiglare properties, contrast and image clarity, a method for producing the decorative molded article, a transfer sheet used for the decorative molded article, and An image display device using the decorative molded product can be provided.

It is sectional drawing which shows one Embodiment of the decorative molded product of this invention. It is sectional drawing which shows one Embodiment of the decorative molded product of this invention. It is sectional drawing which shows one Embodiment of the decorative molded product of this invention. It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the transfer sheet of this invention.

Hereinafter, embodiments of the present invention will be described. In addition, in this specification, AA-BB means that it is AA or more and BB or less.
[Decorative molded products]
In the decorative molded product of the present invention, a protective layer is provided on the resin molded body, and the protective layer has a region P having irregularities and a region Q adjacent to the region P. In the decorative molded product of the present invention, the arithmetic average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm is Ra _x1 , and the cutoff value λc of the surface of the region P is Is set to 0.08 mm, and the arithmetic mean roughness of JIS B0601:1994 is Ra _y1 , and the ten-point average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm. When defined as Rz _x1 , Ra _x1 , Ra _y1 , and Rz _x1 satisfy the following formulas (1) to (3).
0.050 μm≦Ra _x1 <0.140 μm (1)
0.30≦(Ra _x1 −Ra _y1 )/Ray _y1 (2)
Rz _x1 /Ra _x1 ≤15.0 (3)

1 to 3 are sectional views showing an embodiment of a decorative molded product of the present invention. In the decorative molded product 10 of FIG. 1, the protective layer 2 is provided on the resin molded body 1. The protective layer 2 has a region P having irregularities and a region Q adjacent to the region P.
As shown in FIG. 2, the decorative molded product 20 of the present invention may have an anchor layer 13, a printed layer 14, and an adhesive layer 15 between the resin molded body 11 and the protective layer 12. ..
The positions of the regions P and Q are not particularly limited, and the regions P may be arranged between the regions Q or inside the region Q as shown in FIG. 2, or as shown in FIG. The region Q may be arranged between P or inside the region P. The area Q may be substantially smooth without any uneven portion, or may have an uneven portion like the area P.
Hereinafter, each layer constituting the decorative molded product of the present invention will be specifically described.

<Protective layer>
In the region P, Ra _x1 , Ra _y1 , and Rz _{x1 of the} protective layer used for the decorative molded article of the present invention satisfy the above formulas (1) to (3).

<Formula (1)>
Formula (1) shows that the arithmetic mean roughness (Ra _x1 ) of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm is 0.050 μm or more and less than 0.140 μm. Stipulates.

When Ra _x1 is less than 0.050 μm and the formula (1) is not satisfied, the person and the background are clearly reflected on the surface of the region P, and the antiglare property becomes insufficient. Further, when Ra _x1 is 0.140 μm or more and does not satisfy the formula (1), the image clarity of the display element is impaired when the display element is viewed through the decorative molded product. Further, when Ra _x1 is 0.140 μm or more and the formula (1) is not satisfied, whitening tends to lower the contrast.
Ra _x1 is preferably 0.055 to 0.135 μm, and more preferably 0.060 to 0.130 μm.

<Formula (2)>
Formula (2) is defined as the arithmetic average roughness (Ra _x1 ) of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm, and the cutoff value λc of the surface of the region P is 0. It defines the relationship with the JIS B0601:1994 arithmetic average roughness (Ra _y1 ) when it is set to 08 mm.

The cutoff value λc is a value indicating the degree to which the low frequency component is cut from the cross-sectional curve composed of the high frequency component (roughness component) and the low frequency component (waviness component). Therefore, when the cutoff value (reference length) is 0.08 mm, the low-frequency component of the roughness curve is cut to a greater extent than when the cutoff value (reference length) is 0.8 mm. Become. That is, the value of Ra _y1 can be regarded as a high frequency component on the uneven surface of the protective layer, and the value of (Ra _x1 −Ra _y1 ) can be regarded as a low frequency component on the uneven surface of the protective layer. Thus, _{"(Ra x1 -Ra y1) / Ra} y1 'of formula (2) can be regarded as the ratio of the low-frequency component to the high frequency component of the uneven surface.

When (Ra _x1 −Ra _y1 )/Ra _y1 is less than 0.30, the low frequency component on the uneven surface of the protective layer is too small, in other words, the high frequency component on the uneven surface of the protective layer is too large. In this case, since unevenness with many high frequency components is formed on the surface of the protective layer, diffusion of light on the uneven surface is intensified, whitening occurs, and contrast is lowered.
The ratio (Ra _x1 −Ra _y1 )/Ra _y1 is preferably 0.33 or more, and more preferably 0.35 or more.

_{Incidentally,} and thus the _{(Ra x1 -Ra y1) / Ra} y1 is too large, low-frequency components of the irregular surface of the protective layer is too large. In this case, it is difficult to distinguish between the substantially smooth region Q and the region P, and the designability tends to deteriorate.
_Therefore, it is preferable that _{(Ra x1 -Ra y1) / Ra} y1 is 0.82 or less, more preferably 0.60 or less, more preferably 0.50 or less.

<Formula (3)>
Formula (3) is the ratio [Rz _x1 /Ra of the ten-point average roughness (Rz _x1 ) of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm and the above Ra _{x1. x1} ] is 15.0 or less.

If Rz _x1 /Ra _x1 exceeds 15.0, the randomness (variation) of the unevenness of the protective layer will be too large. In this case, glare cannot be suppressed because the unevenness of the irregularities on the surface of the protective layer is too large.
Rz _x1 /Ra _x1 is preferably 14.0 or less, more preferably 12.0 or less, and further preferably 10.0 or less.

When Rz _x1 /Ra _x1 is increased, the irregularities of the protective layer can be provided with a certain randomness, and the defects of the protective layer can be made inconspicuous. In addition, the inconspicuousness of defects leads to a reduction in the designability and yield of the decorative molded product. Therefore, Rz _x1 /Ra _x1 is preferably 5.0 or more, more preferably 6.0 or more, and further preferably 7.0 or more.

In the present specification, for the surface shape (Ra, Rz, etc.) and optical characteristics (haze, transmitted image sharpness, total light transmittance), a sample cut out from a portion free from abnormal points such as dust and scratches is prepared. However, the average value of the measured values at 20 arbitrary points without defects or abnormal points is used.

<Other surface shapes>
In the decorative molded product of the present invention, Rz _x1 is preferably 0.25 to 5.00 μm, more preferably 0.40 to 2.50 μm, and further preferably 0.50 to 1.50 μm. More preferable.
By setting Rz _x1 to 0.25 μm or more, the unevenness of the region P has randomness (variation), and when a defect such as a scratch occurs in the region P, the defect can be made inconspicuous. The yield can be improved.
On the other hand, by setting Rz _x1 to be 5.00 μm or less, it is possible to suppress glare when visually recognizing the display element through the decorative molded product, and it is easy to suppress deterioration in image clarity of the display element. Further, by setting Rz _x1 to 5.00 μm or less, whitening can be easily suppressed.

In the present invention, the surface of the area Q of the protective layer may be substantially smooth without any uneven portion, or may have an uneven portion like the area P.
In the present invention, when the arithmetic average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region Q of the protective layer is 0.8 mm is defined as Ra _x2 , Ra _x1 and Ra _x2 are It is preferable that the following formula (4) is satisfied.
Ra _x2 <Ra _x1 (4)

When Ra _x1 and Ra _x2 satisfy the above expression (4), the distinction between the region P and the region Q becomes clear, and the decorative molded article can have good designability.
The difference between Ra _x1 and Ra _x2 (Ra _x1 −Ra _x2 ) is preferably 0.005 μm or more, more preferably 0.010 μm or more, and more preferably 0.030 μm or more, from the viewpoint of improving designability. Is more preferable and that of 0.050 μm or more is still more preferable.

Ra _x2 is preferably less than 0.050 μm from the viewpoint of clearly distinguishing it from the region P and improving the design.

The protective layer is a layer containing a cured product of the curable resin composition. The protective layer has a role of protecting the decorative molded product from abrasion, light, chemicals, etc. after the transfer layer is transferred from the transfer sheet to the transfer target.

The protective layer preferably contains a cured product of the curable resin composition as a main component. The main component means 50% by mass or more of the total solid content constituting the protective layer, the ratio is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Is more preferable.
Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation curable resin composition, and among these, a cured product of an ionizing radiation curable resin composition is preferable.
The protective layer may contain a thermoplastic resin, but the amount thereof is preferably a very small amount from the viewpoint of improving scratch resistance. Specifically, the content of the thermoplastic resin in the protective layer is preferably less than 5% by mass, more preferably less than 1% by mass, further preferably less than 0.1% by mass, It is even more preferably 0% by mass.

The curable resin composition as the protective layer is left in a semi-cured state at the time of forming the protective layer, and after being transferred to a transfer target, the curable resin composition is cured by heating, irradiation with ionizing radiation, or the like. It may be allowed to proceed and be completely cured. By doing so, the followability of the transfer sheet with respect to the transferred material becomes good, and the moldability can be made good.

Particles such as organic particles and inorganic particles may be contained in the protective layer. By containing particles in the protective layer, glare and defects can be made inconspicuous due to the development of internal haze due to the difference in refractive index from the resin component. These particles may be contained in an adhesive layer, an anchor layer, or the like, which will be described later, for the same purpose.
On the other hand, the internal haze tends to reduce the image clarity. Therefore, from the viewpoint of improving the image clarity, it is preferable that the protective layer contains substantially no particles. The term "substantially free" means 1% by mass or less of the total solid content of the protective layer, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and further preferably 0% by mass. ..

As the organic particles, polymethyl methacrylate, polyacryl-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin and polyester resin particles such as Can be mentioned.
Examples of the inorganic particles include particles made of silica, alumina, antimony, zirconia, titania and the like.

The average particle diameter of the particles is preferably 0.05 to 5.0 μm, more preferably 0.5 to 3.0 μm.
In the present specification, the average particle size is a 50% particle size (d50: median size) when the particles in a solution are measured by a dynamic light scattering method and the particle size distribution is represented by a volume cumulative distribution. The 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

The content of the particles is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the protective layer.

From the viewpoint of the balance between surface hardness and moldability, the thickness of the protective layer is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and further preferably 3 to 10 μm.

<Resin molding>
As the resin molded body, it is preferable to use an injection-moldable thermoplastic resin or thermosetting resin, and various known resins can be used.
When the decorative molded product of the present invention is manufactured by in-mold molding, it is preferable to use a thermoplastic resin. Examples of such thermoplastic resin include polystyrene resin, polyolefin resin, ABS resin (including heat resistant ABS resin), AS resin, AN resin, polyphenylene oxide resin, polycarbonate resin, polyacetal resin, acrylic resin, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

The decorative molded product of the present invention may have a functional layer such as an anchor layer, a printing layer, or an adhesive layer between the resin molded body and the protective layer.

<Anchor layer>
The anchor layer is a layer provided to improve heat resistance when placed in a high temperature environment such as in-mold molding, and is formed using a curable resin. As the curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. As the ionizing radiation curable resin, a polymer having at least one ionizing radiation curable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, and an epoxy group can be used. For example, acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate can be mentioned, and urethane (meth)acrylate is particularly preferable. As the thermosetting resin, phenol-formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, resin obtained by curing acrylic polyol with isocyanate, resin obtained by curing polyester polyol with isocyanate, and curing acrylic acid with melamine. Resin.

The anchor layer preferably contains a resin obtained by reacting an acrylic polyol with an isocyanate. When the anchor layer contains a resin obtained by reacting an acrylic polyol and an isocyanate and the printing layer or the adhesive layer contains an acrylic polyol, the adhesion of the printing layer or the adhesive layer can be improved. Further, the affinity between the resin of the protective layer and the resin obtained by reacting the acrylic polyol and the isocyanate of the anchor layer can improve the adhesion between the protective layer, the anchor layer, and each layer of the printing layer or the adhesive layer. it can.

Further, the anchor layer is a coating solution for an anchor layer prepared by dissolving or dispersing the above resin with necessary additives added thereto, a gravure coating method, a roll coating method, a comma coating method, It can be formed by coating and drying by a known means such as a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the anchor layer is preferably in the range of 0.1 to 6 μm, more preferably in the range of 1 to 5 μm.

<Print layer>
The print layer is a layer for imparting a desired design property to the decorative molded product, and is a layer provided as desired. Although the design of the print layer is arbitrary, for example, a design composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters and the like can be mentioned. In addition, the printed layer can be provided with a pattern pattern layer expressing the above-mentioned pattern and an entire solid layer alone or in combination, and the entire solid layer is usually used as a hiding layer, a coloring layer, a colored hiding layer or the like.

The printing layer is usually on the protective layer or on the anchor layer, using a resin such as polyvinyl resin, polyester resin, acrylic resin, polyvinyl acetal resin, or cellulose resin as a binder, and a pigment of an appropriate color or It is formed by printing with a printing ink containing a dye as a colorant. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing, sublimation transfer printing, and inkjet printing.
The thickness of the printed layer is preferably 0.5 to 40 μm, more preferably 1 to 30 μm from the viewpoint of designability.

<Adhesive layer>
The adhesive layer is a layer formed to bring the resin molded body into close contact with another layer such as a protective layer. For this adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the resin molded body is appropriately used. For example, when the material of the resin molded body is an acrylic resin, it is preferable to use an acrylic resin. When the material of the resin molding is modified polyphenylene oxide, polycarbonate resin, or styrene resin, it is preferable to use an acrylic resin, polystyrene resin, polyamide resin, or the like that has an affinity for these resins. Further, when the material of the resin molding is polypropylene resin, it is preferable to use chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin.
When the resin molded body is injection molded, the adhesive layer preferably has heat sensitivity (heat sealability).
You may mix|blend additives, such as a ultraviolet absorber and an infrared absorber, with the said resin.

As a method for forming the adhesive layer, there are a coating method such as a gravure coating method and a roll coating method, and a printing method such as a gravure printing method and a screen printing method. If the printed layer has sufficient adhesiveness to the resin molded body, the adhesive layer may not be provided.
The thickness of the adhesive layer is usually preferably about 0.1 to 5 μm.

<Optical properties>
The total light transmittance according to JIS K7361-1:1997 of the region P of the decorative molded product of the present invention is preferably 80% or more, more preferably 85% or more, and 90% or more. Is more preferable.
Further, the haze of the region P of the decorative molded product of the present invention in accordance with JIS K7136:2000 is preferably 1 to 40%, more preferably 2 to 35%, and further preferably 3 to 30%. Is more preferable.

When the decorative molded product has a region P having an uneven surface and a region Q adjacent to the region P, the total light transmittance and haze of the region Q are not particularly limited. That is, the region Q may be substantially concealing and the total light transmittance and haze may not be measurable, or may have a predetermined total light transmittance and haze. Further, in the region Q, a part having a concealing property and a part having a predetermined total light transmittance and haze may be mixed.

The area S ₁ of the region P, the ratio between the area S ₂ of the regions Q _[S 2 _/ S _1] is not particularly limited to changes in relation to the design of imparting, the contrast between the region P and the region Q From the viewpoint of clarity, it is preferable to satisfy the relationship of 0.10≦S ₂ /S ₁ . Further, from the viewpoint of improving the antiglare property of the decorative molded product, it is preferable that the relationship of S ₂ /S ₁ ≦7.00 is satisfied. Further, from the viewpoint of showing various properties such as antiglare property of the decorative molded product in a wide range and clarifying the difference in texture between the two regions, 0.10≦S ₂ /S ₁ ≦1.00 It is preferable that 0.13≦S ₂ /S ₁ ≦0.67 be satisfied.

[Transfer sheet]
The transfer sheet of the present invention comprises a base material having an area P′ and an area Q′ adjacent to the area P′, an uneven layer having an uneven shape provided on the area P′ of the base material, On the first release layer formed on the uneven shape of the uneven layer, the second release layer provided on the region Q′ of the base material, the first release layer, and the second release layer And a protective layer formed on
When the cutoff value λc of the surface of the first release layer is 0.8 mm, the arithmetic mean roughness of JIS B0601:1994 is Ra _x11 , and the cutoff value λc of the surface of the first release layer is 0.08 mm. The arithmetic mean roughness of JIS B0601:1994 is Ra _y11 , and the ten-point mean roughness of JIS B0601:1994 when the cutoff value of the surface of the first release layer is 0.8 mm is Rz _x11 . When defined, Ra _x11 , _{Ray 11} and Rz _x11 satisfy the following formulas (1)′ to (3)′.
0.050 μm≦Ra _x11 <0.140 μm (1)′
0.30≦(Ra _x11 −Ra _y11 )/Ray _y11 (2)′
Rz _x11 /Ra _x11 ≤15.0 (3)'

4 to 6 are cross-sectional views showing an embodiment of the transfer sheet of the present invention. The transfer sheet 40 of FIG. 4 has a base material 31 having a region P′ and a region Q′ adjacent to the region P′. The uneven layer 32 having an uneven shape is provided on the region P′ of the base material 31, and the first release layer 33 is provided on the uneven shape of the uneven layer 32. Further, the second release layer 34 is provided on the region Q′ of the base material 31. Further, a protective layer 35 is provided on the first release layer 33 and the second release layer 34.

Further, as shown in FIG. 5, in the transfer sheet 50 of the present invention, the uneven layer 42 may be formed on the region Q′ of the base material 41. In this case, the relaxing layer 46 is provided on the uneven layer 42 formed on the region Q′ of the base material 41, and the second release layer 44 is provided on the relaxing layer 46. An anchor layer 47, a print layer 48, and an adhesive layer 49 may be provided on the protective layer 45. Thus, the transfer sheet 50 includes the release sheet X having the base material 41, the uneven layer 42, the first release layer 43, the second release layer 44, and the relaxation layer 46, the protective layer 45, and the anchor layer 47. , A print layer 48, and a transfer layer Y having an adhesive layer 49.
The positions of the regions P′ and Q′ are not particularly limited, and the regions P′ may be arranged between the regions Q′ or inside the region Q′ as shown in FIG. As shown, the region Q′ may be arranged between the regions P′ or inside the region P′.
Hereinafter, each layer constituting the transfer sheet of the present invention will be specifically described.

<Substrate>
The base material used in the transfer sheet of the present invention is a polyolefin resin such as polyethylene or polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl acetate copolymer, vinyl such as ethylene/vinyl alcohol copolymer. -Based resins, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as methyl poly(meth)acrylate and ethyl poly(meth)acrylate, styrene resins such as polystyrene, nylon 6 or Those made of polyamide resin such as nylon 66 are used. Of these, the base material is appropriately selected according to the physical properties to be emphasized. For example, polyethylene terephthalate or the like may be used from the viewpoint of heat resistance, and nylon or the like may be used from the viewpoint of conformability to the surface shape of the transferred object such as a curved shape.

The thickness of the substrate is preferably from 12 to 150 μm, more preferably from 25 to 100 μm, from the viewpoint of moldability, shape followability, and easy handling.
Further, on the surface of the base material, physical treatment such as corona discharge treatment or oxidation treatment, or application of a coating material called an anchor agent or a primer may be performed in advance in order to improve adhesion with the uneven layer or the like. ..

<Uneven layer>
The uneven layer is a layer having an uneven shape and is formed on the region P′ of the base material.
The uneven layer preferably contains as a main component a resin component such as a thermoplastic resin, a cured product of a thermosetting resin composition, or a cured product of an ionizing radiation curable resin composition. The term "main component" means 50% by mass or more of the total solid content of the concavo-convex layer, and the ratio is preferably 70% by mass or more, more preferably 90% by mass or more.
Among the above resin components, a cured product of an ionizing radiation curable resin composition, which has excellent strength and is capable of imparting an accurate and precise shape because it cures instantly, is suitable. From the viewpoint of making it easier to obtain the effect of the ionizing radiation curable resin composition, it is preferable that the cured product of the ionizing radiation curable resin composition is contained in an amount of 70% by mass or more, out of all the resin components constituting the uneven layer. The content is more preferably at least mass%, further preferably at least 95 mass%, further preferably at least 100 mass%.

The concavo-convex layer may be formed by applying a coating liquid containing particles and a binder resin, but it has a shape complementary to the regions P′ and Q′ from the viewpoint of forming an accurate and precise shape. It is preferably formed by printing using a plate. When the uneven layer has other regions, it is preferable that the plate further has a shape complementary to the other regions. Further, when the release sheet has another layer such as a release layer on the uneven layer, a plate having a shape considering that the unevenness is relaxed by the other layer may be used. Details of the method for forming the uneven layer using the plate will be described later.
When the uneven layer is formed by coating, the particles contained in the coating liquid are likely to aggregate to some extent, and various measures are required to prevent the Rz _x11 /Ra _x11 from increasing, which complicates the process. Therefore, it is not preferable.

The thermosetting resin composition is a composition containing at least a thermosetting resin and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation-curable functional group include an ethylenically unsaturated bond group such as a (meth)acryloyl group, a vinyl group and an allyl group, and an epoxy group and an oxetanyl group.
The ionizing radiation curable resin is preferably a compound having an ethylenically unsaturated bond group. From the viewpoint of suppressing damage to the concavo-convex layer in the process of producing the transfer sheet, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups, and among them, ethylenic A polyfunctional (meth)acrylate compound having two or more saturated bond groups is more preferable. As the polyfunctional (meth)acrylate compound, either a monomer or an oligomer can be used.
Incidentally, the ionizing radiation means, among electromagnetic waves or charged particle beams, one having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, but other Electromagnetic waves such as X-rays and γ-rays, and charged particle rays such as α-rays and ion rays can also be used.

Among the polyfunctional (meth)acrylate compounds, examples of the bifunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexane. Examples thereof include diol diacrylate.
Examples of the trifunctional or higher functional (meth)acrylate-based monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples thereof include pentaerythritol tetra(meth)acrylate and isocyanuric acid-modified tri(meth)acrylate.
The (meth)acrylate-based monomer may be one in which a part of the molecular skeleton is modified, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. It can also be used.

Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.
Urethane (meth)acrylate is obtained by, for example, reacting a polyhydric alcohol and an organic diisocyanate with hydroxy (meth)acrylate.
A preferable epoxy (meth)acrylate is a (meth)acrylate or a bifunctional compound obtained by reacting a trifunctional or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with (meth)acrylic acid. A (meth)acrylate obtained by reacting the above aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with a polybasic acid and (meth)acrylic acid, and a bifunctional or higher functional aromatic epoxy resin, It is a (meth)acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin, and the like with phenols and (meth)acrylic acid.
The ionizing radiation curable resins may be used alone or in combination of two or more.

When the ionizing radiation curable resin is an ultraviolet curable resin, the coating liquid for forming the uneven layer preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyl oxime ester, thioxanthones and the like.
Further, the photopolymerization accelerator is capable of reducing polymerization inhibition by air during curing and accelerating the curing rate, and examples thereof include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. At least one selected from the above is included.

The thickness of the uneven layer after drying (hereinafter referred to as the uneven layer thickness T ₁ ) is not particularly limited, but is preferably 1 to 15 μm, and more preferably 2 to 12 μm. In addition, the thickness T ₁ of the uneven layer refers to the thickness from the base to the top of the uneven layer.

From the viewpoint of improving the releasability between the release sheet and the transfer layer, it is preferable that the uneven layer contains substantially no particles. Specifically, the content of particles in the uneven layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, further preferably less than 0.01% by mass, It is even more preferably 0% by mass.

<First release layer>
The first release layer is a layer provided to easily separate the transfer layer from the base material and the concavo-convex layer and to improve the contrast of the decorative molded product, and is formed on the above-mentioned region P′. .. Therefore, the surface shape of the first release layer follows the uneven shape of the uneven layer, that is, the uneven shape.

By satisfying the above formulas (1)′ to (3)′ on the surface of the first release layer, the protective layer of the decorative molded article obtained by using the transfer sheet of the present invention has the above formulas (1) to ( 3) can be easily satisfied.
The unevenness of the high frequency component tends to make the peeling heavy. Therefore, by satisfying the above formula (2)′, other layers (base material, uneven layer, etc.) can be easily peeled from the protective layer.
The preferred ranges of the above formulas (1)′ to (3)′ are the same as the preferred ranges of the above formulas (1) to (3).

The thickness T ₁ of the uneven layer, the thickness T ₂ of the drying of the first releasing layer _{(hereinafter,} first referred to as the thickness T ₂ of the release layer) and the ratio of _[T 1 _/ T _2] is preferably 0 2 to 200, more preferably 1.0 to 100, still more preferably 2.0 to 50, still more preferably 3.0 to 10.
By setting the ratio to 0.2 or more, it is possible to allow the unevenness of the low frequency component to remain and to easily impart the antiglare property due to the unevenness of the low frequency component. Further, by setting the ratio to 200 or less, it is possible to reduce the unevenness of the high frequency component and improve the contrast of the decorative molded product. Further, by setting the ratio to 200 or less, the unevenness of the extreme height (depth) is reduced, and it is easy to suppress the glare.
The thickness T ₂ of the uneven layer thickness T ₁ and the first release layer, for example, from the captured cross-sectional image using a scanning transmission electron microscope (STEM) of 20 points thickness was measured, and the 20 locations It can be calculated from the average value. The accelerating voltage of STEM is preferably 10 kv to 30 kV. The STEM magnification is preferably 1,000 to 7,000 times when the measured film thickness is on the micron order, and is preferably 50,000 to 300,000 times when the measured film thickness is on the nano order.

The first release layer is not particularly limited as long as it has a low adhesive force with the protective layer and can easily peel off the transfer layer from the base material, and examples thereof include a fluororesin and an acrylic resin (for example, acryl- Melamine-based resins are included), polyester-based resins, polyolefin-based resins, polystyrene-based resins, polyurethane-based resins, cellulose-based resins, vinyl chloride-vinyl acetate-based copolymer resins, thermoplastic resins such as nitrification cotton, and the like. A copolymer of monomers forming a plastic resin or a resin obtained by modifying these resins with (meth)acrylic acid or urethane can be used alone or as a mixture of a plurality of resin compositions.
In the present invention, it is particularly preferable to use an ester group-containing curable resin. As the ester group-containing curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. The ionizing radiation curable resin may be any ionizing radiation curable resin having an ester group in the side chain, such as acryl (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate having an ester group in the side chain. And polyether (meth)acrylates. The thermosetting resin may be a resin obtained by reacting a polymer having an ester group and a hydroxyl group in the side chain with an isocyanate, for example, an acrylic resin having an ester group and a hydroxyl group in the side chain, an epoxy resin, and A resin obtained by reacting a phenol resin with an isocyanate can be used, and it is particularly preferable to use a resin obtained by reacting an acrylic polyol with an isocyanate.

The first release layer may further include a release agent. Examples of the release agent include waxes such as synthetic wax and natural washes. The synthetic wax is preferably a polyolefin wax such as polyethylene wax or polypropylene wax. The first release layer can improve releasability by including a release agent.

The first release layer preferably does not contain a filler having an average particle diameter of 0.5 μm or more, and more preferably does not contain a filler having an average particle diameter of 0.2 μm or more. Since the first release layer does not contain a filler having an average particle diameter of 0.5 μm or more, the high frequency component of the unevenness on the first release layer can be reduced. Therefore, the decorative molded article obtained by using the transfer sheet of the present invention has an uneven shape in which the unevenness of the high-frequency component of the uneven layer is alleviated by the first release layer (the unevenness of the surface of the first release layer). By forming the (shape), the contrast of the uneven portion can be improved, and the designability can be improved. Further, it is possible to suppress glare on the uneven portion.

The first release layer may add a filler of less than 0.5 μm in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing the unevenness of the high frequency component, the average particle diameter of the filler is preferably less than 0.2 μm, and the content thereof is preferably 10 parts by mass or less based on 100 parts by mass of the resin component. ..

The first release layer is prepared by preparing a coating liquid for the first release layer containing a resin that constitutes the first release layer, an appropriate solvent, etc., and applying the coating solution onto the uneven shape of the uneven layer by the gravure printing method. It can be formed by coating and drying by means such as a screen printing method, a slit reverse method or a reverse coating method using a gravure plate.

The thickness T ₂ of the first release layer is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm.

<Second release layer>
The second release layer is a layer provided to easily separate the transfer layer from the base material and the relaxation layer, and is provided on the region Q′ of the base material.

In the present invention, the surface of the area Q′ of the second release layer may be substantially smooth without any uneven portion, or may have an uneven portion like the area P′.
In the present invention, when the arithmetic average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region Q′ of the second release layer is 0.8 mm is defined as Ra _x22 , the above Ra _x11 and It is preferable that Ra _x22 satisfies the following formula (4)′.
Ra _x22 <Ra _x11 (4)'

When Ra _x11 and Ra _x22 satisfy the formula (4)′, the distinction between the region P′ and the region Q′ becomes clear, and the decorative molded article can have good _{designability} .
Further, by satisfying the expression (4)' and satisfying the above expression (3)', it is possible to suppress an increase in the difference between the peel strength of the region P'and the peel strength of the region Q', and It is possible to easily suppress the formation of streak patterns when peeling.

From the viewpoint of improving _{designability} , the difference between Ra _x11 and Ra _x22 (Ra _x11 −Ra _x22 ) is preferably 0.005 μm or more, more preferably 0.010 μm or more, and 0.030 μm or more. Is more preferable and that of 0.050 μm or more is still more preferable.

Ra _x22 is preferably less than 0.050 μm from the viewpoint of clearly distinguishing it from the region P′ and improving the design.

The second release layer is not particularly limited as long as it has a low adhesive force with the protective layer and can easily peel off the transfer layer from the base material. For example, the resin exemplified in the section of the first release layer is used. The resin composition may be formed by using the same, and may be the same as or different from the resin composition used for the first release layer.

The second release layer preferably does not contain a filler having an average particle size of 0.5 μm or more, and more preferably does not contain a filler having an average particle size of 0.2 μm or more. Since the second release layer does not contain a filler having an average particle diameter of 0.5 μm or more, the smoothness of the surface of the second release layer is improved, whereby the protective layer provided on the second release layer. The smoothness of the surface can be improved. As a result, when the transfer layer including the protective layer is transferred to the transfer target (resin molded body), a smooth surface of the protective layer is formed on the surface of the decorative molded product, so that the uneven layer and the first release layer are formed. It is possible to express a texture different from the uneven shape formed by the layers.

The second release layer may add a filler of less than 0.5 μm in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing the unevenness of the high frequency component, the average particle diameter of the filler is preferably less than 0.2 μm, and the content thereof is preferably 10 parts by mass or less based on 100 parts by mass of the resin component. ..

The second release layer is prepared by preparing a coating solution for the second release layer containing the above-mentioned resin and a suitable solvent and the like, and applying this to a substrate by a gravure printing method, a screen printing method, a slit reverse method or a gravure method. It can be formed by coating and drying by a means such as a reverse coating method using a plate.

The thickness T ₃ after drying of the second release layer when the uneven layer is not provided on the region Q′ of the base material and when the uneven layer and the relaxation layer are provided on the region Q′ of the base material (hereinafter, referred to as the The thickness of the second release layer, which is referred to as thickness T ₃ , is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. On the other hand, the thickness T ₃ of the second release layer having the uneven layer on the region Q′ of the base material and having no relaxation layer is preferably 0.05 to 10 μm, more preferably 0.1 to 10 μm. It is 5 μm.

<Relaxation layer>
In the transfer sheet of the present invention, when an uneven layer is formed on the region Q′ of the base material, in order to make the uneven shape of the uneven layer smoother, the transfer sheet is provided between the uneven layer and the second release layer. In addition, it is preferable to further provide a relaxation layer.
The relaxation layer may be formed only from a resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and these resins are used as a binder, and a pigment or dye of an appropriate color is used. You may form with the coloring ink which contains as a coloring agent. When the relaxation layer contains a coloring agent, a marker for aligning the pattern when printing a pattern on the transfer layer and for aligning with the transfer target (resin molding) should be formed at the same time when the relaxation layer is formed. You can In this case, the color is not limited to a color that a person can feel, but includes a color that can be mechanically detected, such as infrared rays. Above all, the relaxation layer is preferably black from the viewpoint of being reliably detected regardless of the type of light source of the photoelectric tube. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing, sublimation transfer printing, and inkjet printing. Incidentally, by containing a colorant in the relaxing layer without containing the colorant in the second release layer, it is possible to make it difficult to form irregularities due to the colorant on the surface of the second release layer, The peelability between the mold layer and the protective layer can be easily improved.

The thickness of the relaxing layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. The average particle diameter of the colorant is preferably 5 nm to 500 nm from the viewpoint of reducing irregularities. Here, the average particle size is a 50% particle size (d50: median size) when the colorant in a solution is measured by a dynamic light scattering method and the particle size distribution is represented by a cumulative distribution. It can be measured using an analyzer (manufactured by Nikkiso Co., Ltd.).

Ratio of the thickness of the concavo-convex layer when forming the concavo-convex layer on the region Q′ of the substrate and the total thickness of the layers constituting the release sheet present on the concavo-convex layer [thickness of the concavo-convex layer/on the concavo-convex layer The total thickness of the layers constituting the release sheet present] is preferably 0.01 to 70, more preferably 0.1 to 15.

The transfer sheet of the present invention may further have functional layers such as an anchor layer, a printing layer, and an adhesive layer on the surface of the protective layer opposite to the substrate. The materials of the anchor layer, the printing layer, and the adhesive layer are the same as those described in the "Decorative molded article".

[Manufacturing method of decorative molded product]
The method for producing a decorative molded product of the present invention comprises the following steps (1) and (2) in order.
(1) The surface of the transfer sheet of the present invention described above, which is on the side of the protective layer based on the release sheet (base material, uneven layer, first release layer, and second release layer), and the transfer target (resin) A step of obtaining a laminated body in which a molded body) is closely attached,
(2) A step of peeling the release sheet of the transfer sheet from the laminate.

A known transfer method can be used for the method for producing the decorated molded product. For example, (i) a method in which a transfer sheet is attached to a pre-transferred body (resin molded body), the transfer layer of the transfer sheet is transferred, and then the release sheet of the transfer sheet is peeled off. ) A transfer sheet is attached to a plate-shaped transfer target (resin molding), the transfer layer of the transfer sheet is transferred, the release sheet of the transfer sheet is peeled off, and then the transfer layer is transferred to the resin molding. And (iii) a method of performing bending processing on the laminated body in which is laminated, and (iii) a method of integrating the transferred sheet (resin molding) with a transfer sheet at the time of injection molding, and then peeling the release sheet of the transfer sheet [ In-mold molding (simultaneous injection molding and decorative method)] and the like. Among them, in-mold molding (injection molding simultaneous transfer decoration method) can perform decoration molding on a resin molded body having a complicated surface shape such as a three-dimensional curved surface.

As an embodiment of a method for producing a decorated molded product using the transfer sheet of the present invention by in-mold molding,
(A) a step of arranging the transfer layer side of the above transfer sheet toward the inside of the in-mold molding die;
(B) a step of injecting a resin into the in-mold molding die,
(C) a step of integrating the transfer sheet and the resin, and transferring the transfer layer of the transfer sheet onto the surface of a transfer target (resin molding).
(D) A step of removing the transfer sheet (resin molded article) from the mold and then peeling off the release sheet of the transfer sheet.
By manufacturing a decorative molded product by such a manufacturing process, a complicated design can be expressed on the surface of the resin molded body.

<Method of manufacturing release sheet>
The release sheet having the area P′ and the area Q′ can be manufactured, for example, by the following steps (A1) to (A2).

(A1) A step of applying a coating liquid for forming a concavo-convex layer containing an ionizing radiation curable resin composition on a substrate to form a layer containing the ionizing radiation curable resin composition.
(A2) A step of shaping an uncured uneven layer using a plate having a shape complementary to the regions P′ and Q′ and simultaneously irradiating it with ionizing radiation to cure the shaped uneven layer.

When the ionizing radiation curable resin composition contains a solvent, it is preferable to dry the solvent in the step (A1).
When the release sheet has a release layer (first release layer, second release layer), after the step (A2), the step (A3) of forming the release layer on the uneven layer may be performed. ..

When the release sheet has other regions, a plate having a shape complementary to the regions P′, Q′ and the other regions may be used as the plate for the step (A2).

The plate used in the step (A2) can be obtained by engraving the surface of the cylinder into a desired shape by, for example, etching, sandblasting, cutting and laser processing, or a combination thereof. Alternatively, it is obtained by producing a long male plate (a plate having the same shape as the regions P′ and Q′) by laser engraving, stereolithography, etc., and inverting this and winding it around the surface of the cylinder. be able to.
The surface of the plate used in the step (A2) is preferably plated with nickel, chromium or the like, more preferably hard chromium.

Among the means for producing the plate described above, sandblasting is preferable from the viewpoint of easy control of Rz _x11 /Ra _x11 , which is an index of unevenness of unevenness.
In sandblasting, for example, the material of the cylinder surface, the particle size of the abrasive, the material of the abrasive, the number of collisions of the abrasive with the cylinder, the distance between the injection nozzle and the cylinder, the diameter of the injection nozzle, the diameter of the injection nozzle for the workpiece. The uneven shape can be adjusted by controlling the angle, the injection pressure, the injection frequency, and the like. The number of times for making unevenness closer to averaging varies depending on the sandblasting conditions, but under the sandblasting conditions of the examples, it is preferable to perform the sandblasting treatment about 3 to 8 times on the same location on the cylinder surface.
Among the control means described above, the “number of collisions of the abrasive with the cylinder” is the simplest and effective for controlling “Rz _x11 /Ra _x11 ”. That is, the number of collisions abrasive to the cylinder surface is less _"Rz x11 _{/ Ra x11"} increases, showing a low frequency percentage _{"(Ra x11 -Ra y11) / Ra} y11 " tends to decrease. Moreover, it _"Rz x11 _{/ Ra x11"} smaller as the number of collisions abrasive to the cylinder surface increases, tend to show a low frequency percentage _{"(Ra x11 -Ra y11) / Ra} y11 " is increased. However, even if the number of collisions is increased and “Rz _x11 /Ra _x11 ” becomes small, there is a limit, and the decrease of “Rz _x11 /Ra _x11 ” gradually becomes saturated.
Further, if the material of the cylinder surface is made hard, the cylinder is less likely to be deeply ground by the abrasive, so that “Rz _x11 /Ra _x11 ” tends to be small.
Further, if the particle diameter of the abrasive is large, the irregularities are averaged, and “Rz _x11 /Ra _x11 ” tends to be small. Further, if the abrasive has a spherical shape, it becomes difficult to form specific irregularities, the irregularities are averaged, and “Rz _x11 /Ra _x11 ” tends to be small.
Further, when the distance between the injection nozzle and the cylinder is shortened, both Ra _x11 and Rz _x11 tend to increase, and the rate of increase is about the same. That is, even if the distance between the injection nozzle and the cylinder is changed, “Rz _x11 /Ra _x11 ” tends to show substantially the same value.
Further, when the injection pressure is increased, both Ra _x11 and Rz _x11 tend to increase, and the rate of increase is about the same. That is, even if the injection pressure is changed, "Rz _x11 /Ra _x11 " tends to show substantially the same value.
From the above, in order to satisfy the equations (1) to (3), a large spherical abrasive is used, the number of collisions of the abrasive with the cylinder surface is set to be large, and the injection pressure is set to be low. Preferably.

When another layer such as a release layer is formed on the uneven layer, the surface unevenness of the transfer sheet is more relaxed than the surface unevenness of the uneven layer. Therefore, when forming another layer on the uneven layer, the plate used in the step (A2) may be a plate having a shape in which unevenness is alleviated.
For example, when a release layer having a thickness of 0.4 μm is formed on the uneven layer, Ra and Rz on the surface of the release layer are about 60% of the surface of the protective layer, and a release layer having a thickness of 0.8 μm is formed on the uneven layer. When forming the mold layer, Ra and Rz on the surface of the release layer are about 50% of the surface of the uneven layer, and when forming a release layer having a thickness of 1.3 μm on the uneven layer, the Ra and Rz of the surface of the release layer are small. Ra and Rz are about 40% of the surface of the uneven layer. The above-mentioned ratio is a standard, and may be slightly changed depending on conditions such as the viscosity of the release layer coating liquid.
Note that the reduction rates of Ra and Rz when the other layer is formed on the uneven layer are almost the same. Therefore, Rz/Ra on the surface of the uneven layer and Rz/Ra on the other layers have almost the same value. Therefore, the value of Rz _x11 /Ra _x11 can be roughly adjusted by the shape of the mold.

Further, the release sheet having the area P′ and the area Q′ can also be manufactured, for example, by the following steps (B1) to (B2).
(B1) A step of filling the plate having a shape complementary to the regions P'and Q'with the coating liquid for forming the uneven layer.
(B2) A step of forming an uneven layer by transferring the coating solution for forming an uneven layer, which has been filled in the plate, onto a substrate, and drying and curing it if necessary.

From the viewpoint of forming an accurate and precise shape, the above-mentioned steps (A1) to (A2) are preferable.

[Image display device]
The image display device of the present invention is an image display device having a display element and a front plate arranged on the light emitting surface side of the display device, wherein the front plate is the decorated molded product of the present invention described above. The protective layer side surface is arranged so as to face the side opposite to the display element. In other words, the image display device of the present invention is arranged such that the resin molded body side of the decorative molded article with the protective layer as a reference and the light emitting side of the display element face each other.

Examples of the display element include a liquid crystal display element, an EL display element (organic EL display element, inorganic EL display element), a plasma display element, and the like, and further an LED display element such as a micro LED display element. The liquid crystal display element may be an in-cell touch panel liquid crystal display element having a touch panel function inside the element.

When the display element of the display device is a liquid crystal display element, a backlight is required on the surface of the liquid crystal display element opposite to the resin sheet.

Further, the image display device of the present invention may be an image display device with a touch panel.
Examples of the touch panel include resistance film type, capacitance type, electromagnetic induction type, infrared type, ultrasonic type and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the form described in the embodiments.

1. Production of plate 1-1. Preparation of Plate A A cylinder having a metal layer made of hard copper and having a thickness of 200 μm on the surface thereof was prepared. Next, while masking the parts other than the processed part, while rotating the cylinder, the surface of the non-masking part of the cylinder is repeatedly sandblasted under the following conditions until the surface unevenness approaches average, and the region P′ is formed in the center part. A plate A having a region Q′ arranged in the peripheral portion was produced.
[Sandblast conditions]
・Cylinder diameter: 300mm
・Abrasive particles: Glass beads with an average particle size of 83 μm ・Diameter of injection nozzle: 9 mm
・Angle of jet nozzle to work piece: vertical ・Distance between jet nozzle and work piece: 400mm
・Injection pressure: 0.17 MPa
・Pump frequency: 90Hz

1-2. Preparation of Plates B to D Plates B to F were prepared in the same manner as plate A except that the sandblasting conditions (injection pressure) were changed to those shown in Table 1.

2. Preparation of transfer sheet [Example 1]
On the surface of the polyethylene terephthalate film (base material) having a thickness of 50 μm, which had been subjected to easy adhesion treatment, a coating solution for forming an uneven layer having the following formulation was applied and dried to form uncured unevenness.
<Coating liquid for forming uneven layer>
・Urethane acrylate 60 parts by mass ・Methyl ethyl ketone 40 parts by mass ・Silicone leveling agent 0.5 parts by mass

Then, using the plate A produced in the above “1”, uncured unevenness is shaped, and at the same time, the shaped unevenness is cured by irradiating ionizing radiation from the polyethylene terephthalate film side to cure the shaped unevenness. An uneven layer was formed. When the thickness T ₁ of the uneven layer after drying was measured by the method described in the specification, it was 5.0 μm.

Then, a release layer-forming coating solution having the following formulation was applied on the entire surface of the uneven layer, dried and cured to form a release layer, to obtain a release sheet used in Example 1. The release sheet had a region P'in the center and a region Q'in the periphery. When the thickness of the first release layer on the region P′ was measured by the method described in the text of the specification, it was 0.7 μm.
<Release layer forming coating liquid>
・Acrylic polyol 70 parts by mass ・Isocyanate 25 parts by mass ・Ethyl acetate 161 parts by mass ・Methyl isobutyl ketone 56 parts by mass

Then, a coating solution for forming a protective layer having the following formulation was applied onto the release layer of the release sheet so that the amount of adhesion after drying was 6.5 g/m ² (6.0 μm) to form a coating film. After that, a fusion UV lamp system was used to irradiate the light source under the conditions of an H bulb, a conveying speed of 20 m/min, and an output of 40% to semi-cure the protective layer. When the integrated light amount at this time was measured by an illuminometer (trade name: UVPF-A1) manufactured by Eye Graphics Co., it was 15 mJ/m ² .
<Coating liquid for forming protective layer>
-Urethane acrylate-based UV curable resin composition 100 parts by mass (solid content 35% by mass, toluene/ethyl acetate mixed solvent)

Next, a coating solution for forming an anchor layer having the following formulation was applied onto the protective layer so that the amount of adhesion after drying was 3.0 g/m ² , dried to form a coating film, and then aged at 40° C. for 72 hours. Then, it was cured to form an anchor layer having a thickness of 2 μm.
<Coating liquid for forming anchor layer>
-Acrylic polyol 100 parts by mass (solid content 25% by mass)
(Toluene/ethyl acetate/methyl ethyl ketone mixed solvent)
*Xamethylene diisocyanate 10 parts by mass (solid content 75% by mass, solvent: ethyl acetate)

Next, an adhesive layer-forming coating liquid having the following formulation was applied onto the anchor layer so that the amount of adhesion after drying was 2.5 g/m ² , to form a coating film. The coating film was dried to form an adhesive layer having a thickness of 2 μm, and the transfer sheet of Example 1 was obtained.
<Coating liquid for adhesive layer>
-Acrylic resin 100 parts by mass (solid content 20% by mass)
(Ethyl acetate/acetic acid-n-propyl/methyl ethyl ketone mixed solvent)
・Methyl ethyl ketone 40 parts by mass

A transfer sheet is superposed on a transparent acrylic sheet (made by Kuraray Co., Ltd., trade name: Comograss DK3, thickness 2 mm), which is the transfer target (resin molding), with the adhesive layer side facing the transfer target side. Then, the transfer sheet was heated and pressure-bonded from the support side, and the transfer target and the transfer sheet were brought into close contact with each other and laminated. Next, after separating (peeling) the release sheet of the transfer sheet from the laminate, ultraviolet irradiation (in the air, H bulb, 800 mJ/cm ² ) was performed to completely cure the protective layer, and the decorative molding of Example 1 was performed. I got the goods.

[Examples 2-3, Comparative Examples 1-6]
Transfer sheets of Examples 2 to 3 and Comparative Examples 1 to 6 were obtained in the same manner as in Example 1 except that the thicknesses of the plate and the first release layer were changed to those shown in Table 2. Moreover, except that the transfer sheet of Example 1 was changed to the transfer sheets of Examples 2 to 3 and Comparative Examples 1 to 6, the steps of Examples 2 to 3 and Comparative Examples 1 to 6 were performed in the same manner as Example 1. A decorative molded product was obtained.

[Comparative Example 7]
A polyethylene terephthalate film (base material) having a thickness of 50 μm was coated with a coating solution for forming a mat layer having the following formulation so that the thickness after drying was 2.5 μm to form a coating film. A smooth film having releasability having an opening corresponding to the region P was attached. With the smooth film stuck together, aging was carried out at room temperature (25° C.) for 72 hours to obtain a laminate A in which the mat layer was pre-cured. The laminate A was aged at 40° C. for 96 hours to completely cure the matte layer, and then the smooth film was peeled off to obtain a release sheet of Comparative Example 7. The surface of the release sheet had an uneven surface P′ and a substantially smooth area Q′ surrounding the area P′.
Then, a transfer sheet and a decorative molded article of Comparative Example 7 were obtained in the same manner as in Example 1 except that the release sheet of Example 1 was changed to the release sheet of Comparative Example 7.

<Mat layer coating liquid>
-Acrylic polyol 40 parts by mass (solid content 50% by mass)
・Filler 4 parts by mass (melamine-formaldehyde condensate particles, average particle diameter 1.2 μm)
・Isocyanate 14 parts by mass (solid content: 75%)
・Ethyl acetate 40 parts by mass

[Comparative Example 8]
The smooth film of the laminate A obtained in Comparative Example 7 was peeled off, and the release layer coating solution having the above formulation was applied on the peeled surface so that the thickness after drying was 0.5 μm. The release layer used in Comparative Example 8 was obtained by aging it at 96° C. for 96 hours to cure it, completely curing the pre-cured mat layer, and forming a release layer.
Next, a transfer sheet and a decorated molded article of Comparative Example 8 were obtained in the same manner as in Example 1 except that the release sheet of Example 1 was changed to the release sheet of Comparative Example 8.

3. Measurement and Evaluation The following evaluations and measurements were performed on the decorative molded products obtained in the examples and comparative examples. The results are shown in Table 1.

3-1. Measurement of surface shape 3-1-1. Measurement with a cut-off value of 0.8 mm Using a surface roughness measuring device (model number: SE-3400/manufactured by Kosaka Laboratory Co., Ltd.), the decorative molded articles produced in Examples and Comparative Examples under the following measurement conditions. Ra _x1 and Rz _x1 of JIS B0601:1994 were measured on the surface of the region P of the protective layer (portion corresponding to the region P′ of the transfer sheet). Similarly, Ra _x2 of JIS B0601:1994 was measured for the surface of the area Q (the portion corresponding to the area Q′ of the transfer sheet).
[Stylus of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip curvature radius: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness tester]
・Reference length (cutoff value λc of roughness curve): 0.8 mm
-Evaluation length (reference length (cut-off value λc) x 5): 4.0 mm
・Feeding speed of stylus: 0.5 mm/s
・Spare length: (cutoff value λc) x 2
・Vertical magnification: 2000 times ・Horizontal magnification: 10 times

3-1-2. Measurement with a cut-off value of 0.08 mm Using a surface roughness measuring device (model number: SE-3400/manufactured by Kosaka Laboratory Ltd.), the decorative molded articles manufactured in Examples and Comparative Examples under the following measurement conditions. With respect to the surface of the region P of the protective layer (portion corresponding to the region P′ of the transfer sheet), Ra _y1 of JIS B0601:1994 was measured.
[Stylus of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip curvature radius: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness tester]
・Reference length (roughness curve cutoff value λc): 0.08 mm
-Evaluation length (reference length (cutoff value λc) x 5): 0.4 mm
・Feeding speed of stylus: 0.5 mm/s
・Spare length: (cutoff value λc) x 2
・Vertical magnification: 2000 times ・Horizontal magnification: 10 times

3-1-3. Calculated Value Based on Measured Value Based on the measured value of the surface shape, (Ra _x1 −Ra _y1 )/Ra _y1 and Rz _x1 /Ra _x1 were calculated.

3-2. Antiglare property A sample (horizontal 180 mm, vertical 100 mm) in which a black plate is bonded to the surface of the decorative molded article obtained in the Examples and Comparative Examples on the resin molded body side (the surface of the transparent acrylic sheet side) via a transparent adhesive. ) Was produced. The sample was placed on a horizontal surface, a fluorescent lamp was placed 1.5 m above the sample, and the sample was observed from various angles under an environment in which the illuminance on the sample was 800 to 1200 Lx, and evaluated according to the following criteria.
A: The image of the fluorescent lamp is reflected in the uneven area, but the outline of the fluorescent lamp is blurred and the boundary portion of the outline cannot be recognized.
C: The image of the fluorescent lamp is reflected in the uneven area like a mirror surface, and the outline of the fluorescent lamp (boundary of the outline) can be clearly recognized.

3-3. Glitter The surface on the transparent acrylic sheet side of the decorative molded product obtained in the examples and comparative examples is arranged on the surface of an image display device (trade name iPad (registered trademark) Air manufactured by Apple Inc., resolution: 264 ppi), and a screen is displayed. Was displayed as green, and whether or not bright spots were conspicuous was visually evaluated. The evaluation environment was a bright room environment in which a fluorescent lamp was provided (the environment in which the illuminance on the decorative molded product was 800 to 1200 Lx when the image display device was powered off).
The regions P and Q were visually observed from the front, and 3 points were those where the minute brightness variation was not noticed, 2 points were those that could not be said, and 2 points where the minute brightness variation was noticed. Was evaluated as 20 points and the average point was calculated.
<Evaluation criteria>
A: Average score is 2.5 or more B: Average score is 1.5 or more and less than 2.5 C: Average score is less than 1.5

3-4. Contrast A sample was prepared by bonding the transparent acrylic sheet side surface of the decorative molded products obtained in the Examples and Comparative Examples to the printed surface of a black acrylic resin plate on which an image was printed. In a bright room equipped with a fluorescent lamp (illuminance on the sample is 800 to 1200 Lx), the uneven portion on the region P of the sample is visually observed, and 3 points have good contrast between the printed image and the black background, An average of 20 subjects was evaluated based on 2 points that could not be said to be neither and 1 point that had a poor contrast between the printed image and the black background.
<Evaluation criteria>
AA: Average score is 2.7 or more A: Average score is 2.5 or more and less than 2.7 B: Average score is 1.5 or more and less than 2.5 C: Average score is less than 1.5

3-5. Image sharpness The transparent acrylic sheet side surface of the decorative molded products obtained in Examples and Comparative Examples is arranged on the surface of an image display device (trade name iPad (registered trademark) Air by Apple Inc., resolution: 264 ppi). , The moving image was displayed, and the visibility of the moving image visually recognized through the region P was evaluated. The evaluation environment was a bright room environment equipped with a fluorescent lamp (an environment in which the illuminance on the decorative molded product was 800 to 1200 Lx when the image display device was powered off).
There were 3 points for those who felt the power of motion in a clear image, 2 points for which they could not say anything, and 1 point for those who felt that the image clarity was insufficient and the power of motion was insufficient. The subject evaluated and the average score was calculated.
<Evaluation criteria>
A: Average score is 2.5 or more B: Average score is 1.5 or more and less than 2.5 C: Average score is less than 1.5

3-6. Designability The decorative molded articles obtained in Examples and Comparative Examples were visually observed from the protective layer side to evaluate the designability. The environment for visual observation was a bright room equipped with a fluorescent lamp (illuminance on the protective layer was 800 to 1200 Lx). Two design evaluation points were "the contrast between the region P and the region Q was clear (the distinction between the two regions was clear)" and "there was no whitening". An average of 20 subjects evaluated the product with a good overall design of 3 points, a poor design with 2 points, and a poor design with 1 point. The points were calculated.
<Evaluation criteria>
A: Average score is 2.5 or more B: Average score is 1.5 or more and less than 2.5 C: Average score is less than 1.5

From the results in Table 1, it can be confirmed that the transfer sheets of Examples 1 to 3 satisfying the formulas (1) to (3) suppress glare and are excellent in antiglare property, contrast and image clarity.

The decorative molded product of the present invention can be suitably used in the fields of communication devices such as mobile phones, information devices inside automobiles, and home electric appliances. In particular, since the contrast is good and the glare on the surface is suppressed, it can be suitably used for a display of a communication device such as a mobile phone and an information device inside a car.

10, 20, 30 Decorative molded product 40, 50, 60 Transfer sheet 1, 11, 21 Resin molded product 2, 12, 22, 35, 45, 55 Protective layer 13, 23, 47, 57 Anchor layer 14, 24, 48, 58 Printing layer 15, 25, 49, 59 Adhesive layer 31, 41, 51 Base material 32, 42, 52 Concavo-convex layer 33, 43, 53 First release layer 34, 44, 54 Second release layer 46, 56 Relaxation layer P Protective layer region P
Q Protective layer area Q
P'Substrate area P'
Q'Substrate area Q'
X Release sheet Y Transfer layer

Claims (6)

A decorated molded article having a protective layer provided on a resin molded body,
The protective layer has a region P having irregularities and a region Q adjacent to the region P,
The JIS B0601:1994 arithmetic mean roughness Ra _x1 when the surface cut-off value λc of the region P is 0.8 mm, and the JIS when the surface cut-off value λc of the region P is 0.08 mm When the arithmetic average roughness of B0601:1994 is Ra _y1 and the ten-point average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm is defined as Rz _x1 , A decorated molded article in which Ra _x1 , Ra _y1 , and Rz _x1 satisfy the following formulas (1) to (3).
0.050 μm≦Ra _x1 <0.140 μm (1)
0.30≦(Ra _x1 −Ra _y1 )/Ray _y1 (2)
Rz _x1 /Ra _x1 ≤15.0 (3) When the arithmetic mean roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region Q is 0.8 mm is defined as Ra _x2 , the Ra _x1 and the Ra _x2 are expressed by the following formula (4). The decorated molded product according to claim 1, which satisfies the condition.
Ra _x2 <Ra _x1 (4) A base material having a region P′ and a region Q′ adjacent to the region P′,
An uneven layer having an uneven shape provided on the region P′ of the base material,
A first release layer formed on the uneven shape of the uneven layer,
A second release layer provided on the region Q′ of the substrate,
Having the first release layer and a protective layer formed on the second release layer,
The arithmetic average roughness of JIS B0601:1994 when the cutoff value λc of the surface of the first release layer is 0.8 mm is Ra _x11 , and the cutoff value λc of the surface of the first release layer is 0. JIS when used as a 08mm B0601: arithmetic average roughness _{Ra y11} 1994, and the first release layer JIS at the time of the cut-off value of the surface with 0.8mm of B0601: a ten-point average roughness of 1994 A transfer sheet in which when defined as Rz _x11 , Ra _x11 , _{Ray 11} and Rz _x11 satisfy the following formulas (1)′ to (3)′.
0.050 μm≦Ra _x11 <0.140 μm (1)′
0.30≦(Ra _x11 −Ra _y11 )/Ray _y11 (2)′
Rz _x11 /Ra _x11 ≤15.0 (3)' When the arithmetic mean roughness of JIS B0601:1994 when the cutoff value λc of the surface of the second release layer is 0.8 mm is defined as Ra _x22 , Ra _x11 and Ra _x22 are _expressed by the following formula ( The transfer sheet according to claim 3, which satisfies 4)′.
Ra _x22 <Ra _x11 (4)' A step of transferring the protective layer of the transfer sheet according to claim 3 or 4 to a resin molded body;
Peeling the first release layer and the second release layer of the transfer sheet,
A method for producing a decorated molded article, comprising: An image display device comprising a display element and a front plate disposed on the light emitting surface side of the display element, wherein the front plate is the surface of the decorative molded article on the protective layer side according to claim 1 or 2. The image display device is arranged so as to face the side opposite to the display element.