JP7275562B2 - DECORATIVE MOLDED PRODUCT, METHOD FOR MANUFACTURING DECORATIVE MOLDED PRODUCT, TRANSFER SHEET, AND IMAGE DISPLAY DEVICE - Google Patents

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.

BACKGROUND ART Conventionally, in the fields of home electric appliances, automotive interior goods, miscellaneous goods, etc., high functionality and design have been expressed by applying decorations such as characters and patterns to the surface of a material to be transferred. A transfer method is available as a method for decorating the surface of an object to be transferred. The transfer method uses a transfer sheet in which a transfer layer consisting of a release layer, a pattern layer, an adhesive layer, etc. is formed on a base material, is heated and pressed to adhere the transfer layer to the material to be transferred, and then the base material is removed. In this method, only the transfer layer is transferred to the surface of the material to be transferred by peeling off the transfer layer.

In some applications, the surface of the material to be transferred is required to have an excellent design property in which different textures such as gloss tone and matte tone are mixed.
For example, Patent Document 1 discloses a release layer containing a matting agent over the entire surface of a base sheet, a mask layer partially containing an active energy ray-curable resin, and a release layer and a pattern layer as a transfer layer. is formed on the partial matte transfer sheet, the transfer layer side is brought into close contact with the surface of the material to be transferred, and heat and pressure are applied from the base sheet side of the partial matte transfer sheet to adhere the transfer layer to the surface of the material to be transferred. A partial mat transfer molding 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 product described in Patent Document 1, glare (a phenomenon in which fine variations in luminance appear in image light due to the uneven structure of the surface) occurs in the mat portion of the surface of the transfer layer after transfer. A lot of cases happened.
In addition, in the partial mat transfer molded article described in Patent Document 1, the characters and the like of the transferred material become whitish and the contrast is lowered, and when the display element is viewed through the molded article, the image clarity of the display element is impaired. There was a problem that

The present invention has been made in view of such circumstances, and a decorative molded product that suppresses glare and has good anti-glare properties, contrast and image clarity, a method for producing the decorative molded product, 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, the protective layer has a region P having unevenness and a region Q adjacent to the region P, and the region P Ra _x1 is the arithmetic mean roughness of JIS B0601: 1994 when the cutoff value λc of the surface of the region P is 0.8 mm, and JIS B0601: 1994 when the cutoff value λc of the surface of the region P is 0.08 mm _{Ra x1 ,} A decorative molded product in which 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 )/Ra _y1 (2)
Rz _x1 /Ra _x1 ≤ 15.0 (3)
[2] A substrate 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 substrate, and the uneven layer A first release layer formed on the uneven shape, a second release layer provided on the region Q' of the base material, the first release layer, and the second release layer The arithmetic mean 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 , the first release layer _Ray11 is the arithmetic mean roughness of JIS B0601: 1994 when the cutoff value λc of the surface of the layer is 0.08 mm, and the cutoff value of the surface of the first release layer is 0.8 mm. A transfer sheet wherein Ra _x11 , Ra _y11 , and Rz _x11 satisfy the following formulas (1)' to (3)' when the ten-point average roughness of JIS B0601:1994 is defined as Rz _x11 .
0.050 μm≦Ra _x11 <0.140 μm (1)′
0.30≦(Ra _x11 −Ra _y11 )/Ra _y11 (2)′
Rz _x11 /Ra _x11 ≤ 15.0 (3)'
[3] A step of transferring the protective layer of the transfer sheet according to [2] above to a resin molding, and a step of peeling off the first release layer and the second release layer of the transfer sheet. , a method for manufacturing a decorative molded product.
[4] An image display device having a display element and a front plate disposed 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 [1] above. is arranged so that the surface of the display element faces the opposite side of the display element.

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

1 is a cross-sectional view showing an embodiment of a decorative molded product of the present invention; FIG. 1 is a cross-sectional view showing an embodiment of a decorative molded product of the present invention; FIG. 1 is a cross-sectional view showing an embodiment of a decorative molded product of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG.

Embodiments of the present invention will be described below. In this specification, AA to BB means from AA to BB.
[Decorative molding]
In the decorative molded product of the present invention, a protective layer is provided on a resin molded product, and the protective layer has a region P having unevenness and a region Q adjacent to the region P. In the decorative molded product of the present invention, the arithmetic mean 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 _Ray1 is the arithmetic mean roughness of JIS B0601:1994 when the is 0.08 mm, 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 )/Ra _y1 (2)
Rz _x1 /Ra _x1 ≤ 15.0 (3)

1 to 3 are sectional views showing one embodiment of the decorative molded product of the present invention. A decorative molded product 10 shown in FIG. 1 has a protective layer 2 provided on a resin molded body 1 . The protective layer 2 has a region P having unevenness and a region Q adjacent to the region P. As shown in FIG.
Further, as shown in FIG. 2, the decorative molded product 20 of the present invention may be provided with an anchor layer 13, a printed layer 14, and an adhesive layer 15 between the resin molded body 11 and the protective layer 12. .
Note that the positions of the region P and the region Q are not particularly limited, and the region P may be arranged between the regions Q or inside the region Q as shown in FIG. Regions Q may be located between P or within regions P. FIG. The region Q may be substantially smooth without an uneven portion, or may have an uneven portion like the region P.
Each layer constituting the decorative molded product of the present invention will be specifically described below.

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

<Formula (1)>
Formula (1) indicates 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. stipulated.

If Ra _x1 is less than 0.050 μm and does not satisfy the formula (1), the person and the background are clearly reflected on the surface of the region P, resulting in insufficient antiglare properties. Further, when Ra _x1 is 0.140 μm or more and does not satisfy the formula (1), the image sharpness of the display element is impaired when the display element is viewed through the decorative molded article. In addition, when Ra _x1 is 0.140 μm or more and does not satisfy the formula (1), the contrast tends to decrease due to whitening.
Ra _x1 is preferably 0.055 to 0.135 μm, more preferably 0.060 to 0.130 μm.

<Formula (2)>
Formula (2) is 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 0.8 mm. 08 mm and the arithmetic mean roughness (Ra _y1 ) of JIS B0601:1994.

The cutoff value λc is a value indicating the degree to which low frequency components are cut from a profile curve composed of high frequency components (roughness components) and low frequency components (undulation components). Therefore, when the cutoff value (reference length) is set to 0.08 mm, the degree to which the low frequency components of the roughness curve are cut is greater than when the cutoff value (reference length) is set to 0.8 mm. Become. That is, the value of Ra _y1 can be regarded as the high frequency component on the uneven surface of the protective layer, and the value of (Ra _x1 -Ra _y1 ) can be regarded as the low frequency component on the uneven surface of the protective layer. Therefore, "(Ra _x1 -Ra _y1 )/Ra _y1 " in the formula (2) can be regarded as the ratio of the low frequency component to the high frequency component of the uneven surface.

If (Ra _x1 -Ra _y1 )/Ra _y1 is less than 0.30, the uneven surface of the protective layer has too little low frequency components, in other words, the uneven surface of the protective layer has too many high frequency components. 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 enhanced, whitening occurs, and contrast is lowered.
(Ra _x1 -Ra _y1 )/Ra _y1 is preferably 0.33 or more, more preferably 0.35 or more.

If (Ra _x1 -Ra _y1 )/Ra _y1 is too large, the uneven surface of the protective layer will have too many low-frequency components. In this case, it becomes difficult to distinguish the region Q and the region P, which are substantially smooth, and the designability tends to deteriorate.
Therefore, (Ra _x1 -Ra _y1 )/Ra _y1 is preferably 0.82 or less, more preferably 0.60 or less, and even more preferably 0.50 or less.

<Formula (3)>
_{Formula (3) is the ratio [Rz x1 /} Ra _x1 ] is 15.0 or less.

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

By increasing Rz _x1 /Ra _x1 , a certain degree of randomness can be imparted to the unevenness of the protective layer, and defects in the protective layer can be made inconspicuous. In addition, inconspicuous defects lead to a decrease 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 even more preferably 7.0 or more.

In this specification, the surface shape (Ra, Rz, etc.) and optical properties (haze, transmitted image clarity, total light transmittance) are determined by preparing a sample cut out from a place where there is no abnormal point such as dust or scratches visually. and the average value of the measured values at arbitrary 20 points with no defects or abnormal points.

<Other surface shapes>
Rz _x1 of the decorative molded article of the present invention is preferably 0.25 to 5.00 μm, more preferably 0.40 to 2.50 μm, and more preferably 0.50 to 1.50 μm. More preferred.
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 5.00 μm or less, glare can be suppressed when the display element is visually recognized through the decorative molded product, and deterioration of image clarity of the display element can be easily suppressed. Further, by setting Rz _x1 to 5.00 μm or less, whitening can be easily suppressed.

In the present invention, the surface of the region Q of the protective layer may be substantially smooth without any irregularities, or may have irregularities like the region P.
In the present invention, when the arithmetic mean 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 , the Ra _x1 and the Ra _x2 are It is preferable to satisfy the following formula (4).
Ra _x2 <Ra _x1 (4)

When Ra _x1 and Ra _x2 satisfy the above formula (4), the distinction between the region P and the region Q becomes clear, and the design of the decorative molded product can be improved.
From the viewpoint of improving 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 0.030 μm or more. is more preferable, and 0.050 μm or more is even more preferable.

Ra _x2 is preferably less than 0.050 μm from the viewpoint of making the distinction from the region P clear and improving designability.

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 material to be transferred.

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, and the ratio is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. is even more preferable.
The cured product of the curable resin composition includes a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition. 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 is preferably very small 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, and even more preferably less than 0.1% by mass. 0% by mass is even more preferable.

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

The protective layer may contain particles such as organic particles and inorganic particles. By containing the particles in the protective layer, glare and defects can be made inconspicuous by developing an 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, etc., which will be described later, for the same purpose.
On the other hand, internal haze tends to reduce image sharpness. Therefore, from the viewpoint of improving image sharpness, it is preferred that the protective layer contains substantially no particles. “Contain substantially no” 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 still more preferably 0% by mass. .

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

The average particle diameter of the particles is preferably 0.05-5.0 μm, more preferably 0.5-3.0 μm.
As used herein, the average particle size is the 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 volume cumulative distribution. The 50% particle size can be measured, for example, using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

The content of the particles is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component of the protective layer.

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

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

The decorative molded article of the present invention may have functional layers such as an anchor layer, a printed layer, and an adhesive layer between the resin molded article 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 vinyl groups, (meth)acryloyl groups, allyl groups, and epoxy groups can be used. Examples include acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate, and urethane (meth)acrylate is particularly preferred. Thermosetting resins include phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, acrylic polyol cured with isocyanate, polyester polyol cured with isocyanate, and acrylic acid cured with melamine. resins.

Moreover, the anchor layer preferably contains a resin obtained by reacting an acrylic polyol and an isocyanate. The anchor layer contains a resin obtained by reacting an acrylic polyol and an isocyanate, and the printed layer or the adhesive layer contains the acrylic polyol, whereby the adhesiveness of the printed layer or the adhesive layer can be improved. In addition, the affinity between the resin of the protective layer and the resin formed by reacting acrylic polyol and isocyanate of the anchor layer improves the adhesion between the protective layer, the anchor layer, and the print layer or adhesive layer. can.

Further, the anchor layer is prepared by dissolving or dispersing the necessary additives in the above-mentioned resin in an appropriate solvent, and the anchor layer coating solution is prepared by gravure coating, roll coating, comma coating, It can be formed by coating and drying by known means such as gravure printing, screen printing, and gravure reverse roll coating. Generally, the thickness of the anchor layer is preferably in the range of 0.1-6 μm, more preferably in the range of 1-5 μm.

<Print layer>
The printed layer is a layer for imparting a desired design property to the decorative molded product, and is a layer provided as desired. Although the pattern of the printed layer is arbitrary, for example, a pattern consisting of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, and the like can be mentioned. The printed layer can be provided with a patterned layer expressing the above picture and a solid layer on the entire surface, either alone or in combination.

The printed layer is usually formed on the protective layer or the anchor layer with a resin such as polyvinyl resin, polyester resin, acrylic resin, polyvinyl acetal resin, or cellulose resin as a binder, and an appropriate color pigment or pigment. It is formed by printing with a printing ink containing a dye as a coloring agent. Examples of printing methods 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 adhere the resin molding to other layers such as a protective layer. A heat-sensitive or pressure-sensitive resin suitable for the material of the resin molding is appropriately used for this adhesive layer. For example, when the material of the resin molding is acrylic resin, it is preferable to use acrylic resin. When the material of the resin molded body is modified polyphenylene oxide, polycarbonate resin, or styrene resin, it is preferable to use acrylic resin, polystyrene resin, polyamide resin, or the like, which has affinity with these resins. Furthermore, 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 molding is injection molded, the adhesive layer preferably has heat sensitivity (heat sealability).
Additives such as an ultraviolet absorber and an infrared absorber may be added to the above resin.

Methods for forming the adhesive layer include coating methods such as gravure coating and roll coating, and printing methods such as gravure printing and screen printing. In addition, when the printed layer has sufficient adhesiveness to the resin molding, the adhesive layer may not be provided.
The thickness of the adhesive layer is 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 article 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 article of the present invention in accordance with JIS K7136:2000 is preferably 1 to 40%, more preferably 2 to 35%, and 3 to 30%. is more preferred.

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 have a substantially opaque property and the total light transmittance and haze cannot be measured, or may have a predetermined total light transmittance and haze. Also, the area Q may include a portion having a hiding property and a portion having a predetermined total light transmittance and haze.

The ratio [S ₂ /S ₁ ] of the area S ₁ of the region P and the area S ₂ of the region Q is not particularly limited because it changes depending on the design to be imparted, but the contrast between the region P and the region Q From the point of view of clarity, it is preferable to satisfy the relationship 0.10≦S ₂ /S ₁ . Moreover, from the viewpoint of improving the antiglare properties of the decorative molded product, it is preferable to satisfy the relationship S ₂ /S ₁ ≦7.00. In addition, from the viewpoint of exhibiting various performances such as anti-glare properties in a wide range of decorative molded products and clarifying the difference in texture between the two regions, 0.10 ≤ S ₂ /S ₁ ≤ 1.00 preferably 0.13≦S ₂ /S ₁ ≦0.67.

[Transfer sheet]
The transfer sheet of the present invention comprises 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 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, the first release layer, and the second release layer a protective layer formed on the
When the cutoff value λc of the surface of the first release layer is 0.8 mm, the arithmetic average 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. Ra _y11 is the arithmetic mean roughness of JIS B0601:1994, and Rz _x11 is 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. When defined, Ra _x11 , Ra _y11 , 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 )/Ra _y11 (2)′
Rz _x11 /Ra _x11 ≤ 15.0 (3)'

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

Further, as shown in FIG. 5, the transfer sheet 50 of the present invention may have an uneven layer 42 formed on the area Q′ of the base material 41 . In this case, a relaxation 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 relaxation layer 46 . Also, an anchor layer 47 , a printed layer 48 and an adhesive layer 49 may be provided on the protective layer 45 . Thus, the transfer sheet 50 includes a release sheet X having a substrate 41, an uneven layer 42, a first release layer 43, a second release layer 44, and a relaxation layer 46, a protective layer 45, and an anchor layer 47. , a printing layer 48 and a transfer layer Y having an adhesive layer 49 .
The positions of the region P' and the region Q' are not particularly limited, and the region P' may be arranged between the regions Q' or inside the region Q' as shown in FIG. Regions Q' may be located between regions P' or within regions P' as shown.
Each layer constituting the transfer sheet of the present invention will be specifically described below.

<Base material>
The substrate used in the transfer sheet of the present invention includes polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl acetate copolymers, ethylene/vinyl alcohol copolymers and other vinyl resins. polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; acrylic resins such as poly(methyl meth)acrylate and poly(ethyl meth)acrylate; styrene resins such as polystyrene; Polyamide-based resins such as nylon 66 are used. Among these, the base material is appropriately selected according to the physical properties to be emphasized. For example, polyethylene terephthalate or the like can be used from the viewpoint of heat resistance, and nylon or the like can be used from the viewpoint of conformability to the surface shape of a transferred object such as a curved shape.

The thickness of the base material is preferably in the range of 12 to 150 μm, more preferably in the range of 25 to 100 μm, from the viewpoints of moldability, shape followability, and ease of handling.
In addition, the surface of the substrate may be previously subjected to physical treatment such as corona discharge treatment, oxidation treatment, etc., or application of a paint called an anchor agent or primer, in order to increase the adhesiveness to 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 substrate.
The uneven layer preferably contains resin components such as a thermoplastic resin, a cured product of a thermosetting resin composition, a cured product of an ionizing radiation-curable resin composition, etc. as a main component. The main component means 50% by mass or more of the total solids constituting the uneven layer, 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 that is excellent in strength and instantly cured to give an accurate and precise shape is suitable. In addition, 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. More preferably, it contains 95% by mass or more, and even more preferably 100% by mass.

The uneven layer may be formed by applying a coating liquid containing particles and a binder resin, but from the viewpoint of forming an accurate and precise shape, it has a shape complementary to the region P' and the region Q'. It is preferably formed by printing using a plate. When the uneven layer has other regions, the plate preferably has a shape complementary to the other regions. When the release sheet has other layers such as a release layer on the uneven layer, a plate having a shape that takes into consideration that the unevenness is alleviated by the other layers may be used. The details of the method of forming the uneven layer using a plate will be described later.
When the uneven layer is formed by coating, the particles contained in the coating liquid are not a little likely to aggregate, and various measures are required to suppress the increase in Rz _x11 /Ra _x11 , which complicates the process. I don't like it because

A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Thermosetting resins include acrylic resins, urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. If necessary, a curing agent is added to these curable resins in the thermosetting resin composition.

The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as an "ionizing radiation-curable compound"). Examples of ionizing radiation-curable functional groups include ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, epoxy groups, and oxetanyl groups.
A compound having an ethylenically unsaturated bond group is preferable as the ionizing radiation-curable resin. From the viewpoint of suppressing damage to the uneven layer in the process of manufacturing the transfer sheet, the ionizing radiation-curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups. Polyfunctional (meth)acrylate compounds having two or more saturated bond groups are more preferred. Both monomers and oligomers can be used as polyfunctional (meth)acrylate compounds.
Ionizing radiation means an electromagnetic wave or a charged particle beam that has an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Among polyfunctional (meth)acrylate compounds, bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, 1,6-hexane. diol diacrylate and the like.
Trifunctional or higher (meth)acrylate monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di Examples include pentaerythritol tetra(meth)acrylate and isocyanuric acid-modified tri(meth)acrylate.
Further, the (meth)acrylate-based monomer may have a partially modified molecular skeleton, and may be modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. can also be used.

Examples of polyfunctional (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.
Urethane (meth)acrylates are obtained, for example, by reacting polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates.
Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting tri- or more functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid, bifunctional (Meth)acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with polybasic acid and (meth)acrylic acid, and bifunctional or higher aromatic epoxy resins, It is a (meth)acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.
The ionizing radiation-curable resins may be used singly or in combination of two or more.

When the ionizing radiation-curable resin is an ultraviolet-curable resin, the uneven layer-forming coating liquid 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-acyloxime ester, thioxanthone, and the like.
In addition, the photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. One or more selected types can be mentioned.

The thickness of the uneven layer after drying (hereinafter referred to as thickness _T1 of the uneven layer) is not particularly limited, but is preferably 1 to 15 μm, more preferably 2 to 12 μm. The thickness _T1 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 preferred that the uneven layer does not substantially contain particles. Specifically, the content of the particles in the uneven layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, 0% by mass is even more preferable.

<First release layer>
The first release layer is a layer provided to easily separate the transfer layer from the substrate and the uneven layer and to improve the contrast of the decorative molded product, and is formed on the above-described region P'. . Therefore, the surface shape of the first release layer is a shape following the uneven shape of the uneven layer, that is, an 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 product obtained using the transfer sheet of the present invention is the above formulas (1) to ( 3) can be easily satisfied.
It should be noted that the unevenness of the high-frequency component tends to make peeling more difficult. Therefore, by satisfying the above formula (2)′, other layers (base material, uneven layer, etc.) can be easily peeled off 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 ratio [T ₁ /T ₂ ] of the thickness T ₁ of the uneven layer and the thickness T ₂ of the first release layer after drying (hereinafter referred to as the thickness T ₂ of the first release layer) is preferably 0. .2-200, more preferably 1.0-100, still more preferably 2.0-50, still more preferably 3.0-10.
By setting the ratio to 0.2 or more, it is possible to leave the unevenness of the low-frequency component and to easily provide the anti-glare property due to the unevenness of the low-frequency component. Further, by setting the ratio to 200 or less, the unevenness of the high frequency component can be reduced and the contrast of the decorative molded product can be improved. Further, by setting the ratio to 200 or less, unevenness of extreme height (depth) is reduced, and glare can be easily suppressed.
The thickness _T1 of the uneven layer and the thickness _T2 of the first release layer are obtained by measuring the thickness at 20 points from a cross-sectional image taken using a scanning transmission electron microscope (STEM), for example, and measuring the thickness at 20 points. It can be calculated from the average value of the values. The acceleration voltage of STEM is preferably 10 kV to 30 kV. The magnification of the STEM is preferably 1,000 to 7,000 times when the film thickness to be measured is on the micron order, and is preferably 50,000 to 300,000 times when the film thickness to be measured is on the order of nanometers.

The first release layer is not particularly limited as long as it has a low adhesive strength with the protective layer and can be easily peeled off the transfer layer from the base material. melamine-based resins.), 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 nitrocellulose, the heat A copolymer of monomers forming a plastic resin, or a resin composition obtained by modifying these resins with (meth)acrylic acid or urethane can be used alone or in combination.
In the present invention, it is particularly preferable to form using 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 an ionizing radiation-curable resin having an ester group in the side chain, and may be acrylic (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, epoxy (meth)acrylate, or the like 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 a 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 and an isocyanate can be used, and it is particularly preferable to use a resin obtained by reacting an acrylic polyol and an isocyanate.

The first release layer may further contain a release agent. Examples of release agents include waxes such as synthetic waxes and natural waxes. Polyolefin waxes such as polyethylene wax and polypropylene wax are preferable as the synthetic wax. The first release layer can improve releasability by containing a release agent.

The first release layer preferably does not contain a filler with an average particle size of 0.5 μm or more, and more preferably does not contain a filler with an average particle size of 0.2 μm or more. Since the first release layer does not contain a filler having an average particle size of 0.5 μm or more, it is possible to reduce the high-frequency component of the unevenness on the first release layer. Therefore, the decorative molded product obtained 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 on the surface (unevenness of the surface of the first release layer By forming the shape), the contrast of the uneven shape portion is improved, and the design can be enhanced. In addition, it is possible to suppress the glare of the concave-convex portion.

A filler of less than 0.5 μm may be added to the first release layer in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing unevenness of high-frequency components, 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 with respect to 100 parts by mass of the resin component. .

The first release layer is prepared by preparing a first release layer coating solution containing a resin constituting the first release layer and an appropriate solvent, etc., and applying this onto the uneven shape of the uneven layer by a gravure printing method. , a screen printing method, a slit reverse method, or a reverse coating method using a gravure plate.

The thickness _T2 of the first release layer is preferably 0.05-10 μm, more preferably 0.1-5 μm.

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

In the present invention, the surface of the region Q' of the second release layer may be substantially smooth with no irregularities, or may have irregularities like the region P'.
In the present invention, when the arithmetic mean 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 Ra _x11 and It is preferable that the Ra _x22 satisfies the following formula (4)'.
Ra _x22 < Ra _x11 (4)'

When Ra _x11 and Ra _x22 satisfy the formula (4)', the region P' and the region Q' can be clearly distinguished from each other, and the design of the decorative molded product can be improved.
Further, by satisfying the formula (4) 'and satisfying the above formula (3) ', the difference between the peel strength of the region P 'and the peel strength of the region Q 'is suppressed from increasing, and the release sheet is It is possible to easily suppress the generation of a streaky pattern when peeling.

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, from the viewpoint of improving designability. is more preferable, and 0.050 μm or more is even more preferable.

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

The second release layer is not particularly limited as long as it has a low adhesion to the protective layer and can be easily peeled off the transfer layer from the base material. The resin composition 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 with an average particle size of 0.5 μm or more, and more preferably does not contain a filler with an average particle size of 0.2 μm or more. Since the second release layer does not contain a filler having an average particle size of 0.5 μm or more, the smoothness of the surface of the second release layer is improved, thereby forming a protective layer provided on the second release layer. surface smoothness can be improved. As a result, when the transfer layer including the protective layer is transferred to the transferred body (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 mold release A texture different from the texture formed by layers can be expressed.

The second release layer may contain a filler of less than 0.5 µm in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing unevenness of high-frequency components, 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 with respect to 100 parts by mass of the resin component. .

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

Thickness T ₃ (hereinafter referred to as the second The thickness T ₃ of the second release layer) is preferably 0.05-10 μm, more preferably 0.1-5 μm. On the other hand, the thickness _T3 of the second release layer in the case of having the uneven layer on the region Q′ of the substrate and not having the relaxation layer is preferably 0.05 to 10 μm, more preferably 0.1 to 10 μm. 5 μm.

<relaxation layer>
In the transfer sheet of the present invention, when a concavo-convex layer is formed on the region Q' of the base material, in order to make the concavo-convex shape of the concavo-convex layer smoother, In addition, it is preferable to further provide a relaxation layer.
The relaxation layer may be formed only from a resin such as polyvinyl resin, polyester resin, acrylic resin, polyvinyl acetal resin, cellulose resin, or the like. as a coloring agent. By including a colorant in the relieving layer, a marker is formed at the same time as the relieving layer is formed for alignment when a pattern is printed on the transfer layer and for alignment with the transferred body (resin molded body). can be done. In this case, the color is not limited to colors that can be perceived by humans, and includes colors that can be detected mechanically, such as infrared rays. Among them, the relaxation layer is preferably black from the viewpoint of reliable detection regardless of the type of light source of the phototube. Examples of printing methods include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing, sublimation transfer printing, and inkjet printing. In addition, by not containing a coloring agent in the second release layer and containing a coloring agent in the relaxation layer, it is possible to make it difficult to form unevenness caused by the coloring agent on the surface of the second release layer, and the second release layer It is possible to easily improve the releasability between the mold layer and the protective layer.

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

The ratio of the thickness of the uneven layer when the uneven layer is formed on the region Q 'of the base material to the total thickness of the layers constituting the release sheet present on the uneven layer [thickness of the uneven layer / on the uneven layer The total thickness of the layers constituting the existing release sheet] is preferably from 0.01 to 70, more preferably from 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 for the anchor layer, print layer, adhesive layer, etc. are as described in the section "Decorated Molded Article".

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

A known transfer method can be used for the method of manufacturing the decorated molded product. For example, (i) a method of attaching a transfer sheet to a preformed transfer target (resin molding), transferring the transfer layer of the transfer sheet, and peeling off the release sheet of the transfer sheet, (ii) ) A transfer sheet is adhered 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 the transfer layer is then applied to the resin molding. (iii) a method of integrating with a transfer sheet when injection molding a transferred body (resin molded body), and then peeling off the release sheet of the transfer sheet [ in-mold molding (injection molding simultaneous transfer decoration method)] and the like. Among them, in-mold molding (injection molding simultaneous transfer decoration method) enables decoration molding to be performed on a resin molding having a complicated surface shape such as a three-dimensional curved surface.

As one embodiment of the method for producing a decorative molded product using the transfer sheet of the present invention by in-mold molding,
(a) placing the transfer layer side of the transfer sheet toward the inside of the mold for in-mold molding;
(b) a step of injecting a resin into the mold for in-mold molding;
(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 transferred body (resin molded body);
(d) a step of peeling off the release sheet of the transfer sheet after the object to be transferred (resin molded object) is removed from the mold.
A complicated design can be expressed on the surface of the resin molded product by manufacturing the decorative molded product by such a manufacturing process.

<Manufacturing method of release sheet>
A release sheet having regions P' and Q' can be produced, for example, by the following steps (A1) to (A2).

(A1) A step of applying an uneven layer-forming coating liquid containing an ionizing radiation-curable resin composition onto 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 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 step (A1).
When the release sheet has a release layer (first release layer, second release layer), (A3) the step of forming a release layer on the uneven layer may be performed after the step (A2). .

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

The plate used in 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, a long male plate (plate having the same shape as region P' and region Q') is prepared by laser engraving, stereolithography, etc., and this is reversed and wound around the surface of the cylinder. be able to.
The surface of the plate used in step (A2) is preferably plated with nickel, chromium, or the like, more preferably hard chromium plating.

Among the above-mentioned means for producing a plate, sandblasting is preferable from the viewpoint of easy control of Rz _x11 /Ra _x11 , which is an index of randomness 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 times the abrasive collides with the cylinder, the distance between the injection nozzle and the cylinder, the diameter of the injection nozzle, and the size of the injection nozzle for the workpiece. The irregular shape can be adjusted by controlling the angle, injection pressure, injection frequency, and the like. Although the number of times for averaging unevenness varies depending on the sandblasting conditions, under the sandblasting conditions of the example, it is preferable to perform sandblasting about 3 to 8 times on the same portion of the cylinder surface.
Among the control means described above, "the number of collisions of the abrasive against the cylinder" is the simplest and most effective for controlling "Rz _x11 /Ra _x11 ". That is, when the number of collisions of the abrasive against the cylinder surface is small, "Rz _x11 /Ra _x11 " tends to increase, and "(Ra _x11 -Ra _y11 )/Ra _y11 " indicating the low frequency ratio tends to decrease. Also, as the number of collisions of the abrasive against the cylinder surface increases, "Rz _x11 /Ra _x11 " tends to decrease and "(Ra _x11 -Ra _y11 )/Ra _y11 " indicating the low frequency ratio tends to increase. However, there is a limit to reducing "Rz _x11 /Ra _x11 " by increasing the number of collisions, and the decrease in "Rz _x11 /Ra _x11 " gradually saturates.
In addition, when the material of the cylinder surface is made hard, it becomes difficult for the cylinder to be deeply scraped by the abrasive, so "Rz _x11 /Ra _x11 " tends to decrease.
Further, when the particle size of the abrasive is large, unevenness tends to be averaged, and "Rz _x11 /Ra _x11 " tends to decrease. Further, when the abrasive has a spherical shape, it is difficult to form specific unevenness, and the unevenness tends to be averaged and "Rz _x11 /Ra _x11 " tends to be small.
Also, 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 similar. In other words, "Rz _x11 /Ra _x11 " tends to show substantially the same value even when the distance between the injection nozzle and the cylinder is changed.
Moreover, when the injection pressure is increased, both Ra _x11 and Rz _x11 tend to increase, and the rate of increase is about the same. In other words, "Rz _x11 /Ra _x11 " tends to show substantially the same value even when the injection pressure is varied.
From the above, in order to satisfy the formulas (1) to (3), use a large spherical abrasive as the abrasive, set the number of collisions of the abrasive against the cylinder surface to be large, and set the injection pressure 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 reduced more than the surface unevenness of the uneven layer. Therefore, when another layer is formed on the uneven layer, the plate used in the step (A2) should have a shape that takes into consideration the relief of the unevenness.
For example, when a release layer having a thickness of 0.4 μm is formed on the uneven layer, the Ra and Rz of the surface of the release layer are about 60% of those of the surface of the protective layer. When forming a mold layer, Ra and Rz on the surface of the release layer are about 50% of the surface of the uneven layer. Ra and Rz are about 40% of the uneven layer surface. The aforementioned ratio is a guideline, and may vary slightly depending on conditions such as the viscosity of the release layer coating liquid.
The reduction rates of Ra and Rz when other layers are formed on the uneven layer are approximately the same. Therefore, Rz/Ra on the uneven layer surface and Rz/Ra on other layers are approximately the same. Therefore, the value of Rz _x11 /Ra _x11 can be roughly adjusted by the shape of the mold.

A release sheet having regions P' and Q' can also be produced, for example, by the following steps (B1) to (B2).
(B1) A step of filling a plate having a shape complementary to regions P' and Q' with a coating solution for forming a concavo-convex layer.
(B2) A step of transferring the uneven layer-forming coating liquid filled in the plate onto the substrate, and drying and curing as necessary to form an uneven layer.

From the viewpoint of forming an accurate and precise shape, the above-described 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 disposed on the light emitting surface side of the display element, and the front plate is the above-described decorative molded product of the present invention. It is arranged so that the surface on the side of the protective layer faces the side opposite to the display element. In other words, the image display device of the present invention is arranged so that the resin molding side with the protective layer of the decorative molding as a reference and the light emitting side of the display element face each other.

Examples of display elements include liquid crystal display elements, EL display elements (organic EL display elements, inorganic EL display elements), plasma display elements, and the like, and LED display elements such as micro LED display elements. 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.
As the touch panel, systems such as a resistive film system, a capacitance system, an electromagnetic induction system, an infrared system, and an ultrasonic system can be used.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. In addition, this invention is not limited to the form as described in an Example.

1. Preparation of plate 1-1. Production of Plate A A cylinder having a metal layer made of hard copper with a thickness of 200 μm on its surface was prepared. Then, while masking the area other than the processed part, while rotating the cylinder, the surface of the unmasked part of the cylinder is repeatedly sandblasted under the following conditions until the surface unevenness approaches the average, and the area P 'is in the center. , and a plate A in which a region Q' is arranged in the peripheral portion.
[Sandblasting conditions]
・Cylinder diameter: 300mm
・Abrasive particles: glass beads with an average particle diameter of 83 μm ・Diameter of injection nozzle: 9 mm
・Angle of injection nozzle to workpiece: vertical ・Distance between injection nozzle and workpiece: 400 mm
・Injection pressure: 0.17 MPa
・Pump frequency: 90Hz

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

2. Preparation of transfer sheet [Example 1]
A coating solution for forming an uneven layer having the following formulation was applied to the surface of a polyethylene terephthalate film (substrate) having a thickness of 50 μm and treated for easy adhesion, followed by drying 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

Next, using the plate A prepared in "1" above, uncured unevenness is shaped, and at the same time, ionizing radiation is irradiated from the polyethylene terephthalate film side to cure the shaped unevenness, and the shaped unevenness is cured on the polyethylene terephthalate film. A concavo-convex layer was formed. When the thickness _T1 of the uneven layer after drying was measured by the method described in the specification, it was 5.0 μm.

Next, a release layer-forming coating liquid having the following formulation was applied to the entire surface of the uneven layer, dried, and cured to form a release layer, thereby obtaining a release sheet used in Example 1. The release sheet had a structure in which a region P' was arranged in the central portion and a region Q' was arranged in the peripheral portion. When the thickness of the first release layer on the region P' was measured by the method described in the specification, it was 0.7 µm.
<Coating liquid for forming release layer>
・Acrylic polyol 70 parts by mass ・Isocyanate 25 parts by mass ・Ethyl acetate 161 parts by mass ・Methyl isobutyl ketone 56 parts by mass

Next, on the release layer of the release sheet, a coating liquid for forming a protective layer having the following formulation is applied so that the coating amount after drying is 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 amount of light at this time was measured with an illuminometer (trade name: UVPF-A1) manufactured by Eye Graphics, it was 15 mJ/m ² .
<Coating solution for forming protective layer>
・Urethane acrylate 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 coated on the protective layer so that the coating amount after drying was 3.0 g/m ² , dried to form a coating film, and then aged at 40°C for 72 hours. and cured to form an anchor layer with a thickness of 2 μm.
<Coating liquid for forming anchor layer>
・ 100 parts by mass of acrylic polyol (solid content 25% by mass)
(toluene/ethyl acetate/methyl ethyl ketone mixed solvent)
・Xan methylene diisocyanate 10 parts by mass (solid content 75% by mass, solvent: ethyl acetate)

Next, a coating liquid for forming an adhesive layer having the following formulation was applied onto the anchor layer so that the coating amount 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 a transfer sheet of Example 1 was obtained.
<Coating solution for adhesive layer>
・ Acrylic resin 100 parts by mass (solid content 20% by mass)
(ethyl acetate/n-propyl acetate/methyl ethyl ketone mixed solvent)
・Methyl ethyl ketone 40 parts by mass

The transfer sheet is superimposed on a transparent acrylic sheet (manufactured by Kuraray Co., Ltd., trade name: Comoglass DK3, thickness 2 mm) as a transfer target (resin molded body) so that the adhesive layer side faces the transfer target. Then, the transfer sheet and the transfer sheet were adhered to each other by heating and pressing from the support side of the transfer sheet, 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. 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 the conditions shown in Table 2. Further, in the same manner as in Example 1, except that the transfer sheet of Example 1 was changed to the transfer sheet of Examples 2 to 3 and Comparative Examples 1 to 6, the addition of Examples 2 to 3 and Comparative Examples 1 to 6 was performed. A decorative molding was obtained.

[Comparative Example 7]
On a polyethylene terephthalate film (substrate) having a thickness of 50 μm, a coating liquid for forming a matte layer having the following formulation was applied so as to have a thickness of 2.5 μm after drying to form a coating film. A releasable smooth film having an opening corresponding to the region P was attached. The laminated body A in which the mat layer was pre-cured was obtained by aging at room temperature (25° C.) for 72 hours while the smooth films were bonded together. After the laminate A was aged at 40° C. for 96 hours to completely cure the mat layer, 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 area P' and a substantially smooth area Q' surrounding the area P'.
Next, a transfer sheet and a decorative molded product 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.

<Coating liquid for matte layer>
・ 40 parts by mass of acrylic polyol (solid content 50% by mass)
・ Filler 4 parts by mass (melamine-formaldehyde condensate particles, average particle size 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 liquid having the above formulation was applied to the peeled surface so that the thickness after drying was 0.5 μm. C. for 96 hours and cured to completely cure the pre-cured matte layer and form a release layer to obtain a release sheet used in Comparative Example 8.
Next, a transfer sheet and a decorative molded product of Comparative Example 8 were obtained in the same manner as in Example 1 except that the release sheet of Comparative Example 8 was used instead of the release sheet of Example 1.

3. Measurements and Evaluations The following evaluations and measurements were performed on the decorated moldings obtained in Examples and Comparative Examples. Table 1 shows the results.

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

3-1-2. Measurement with a cutoff value of 0.08 mm Using a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Co., Ltd.), the following measurement conditions were used to measure the decorative molded products prepared in Examples and Comparative Examples. The surface of the protective layer region P (the portion corresponding to the region P' of the transfer sheet) was measured for Ra _y1 according to JIS B0601:1994.
[Stylus of surface roughness detector]
Trade name SE2555N manufactured by Kosaka Laboratory (tip curvature radius: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
・Reference length (cutoff value λc of roughness curve): 0.08 mm
・ Evaluation length (reference length (cutoff value λc) × 5): 0.4 mm
・Feeding speed of stylus: 0.5mm/s
・ Spare length: (cutoff value λc) × 2
・Vertical magnification: 2000 times ・Horizontal magnification: 10 times

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

3-2. Antiglare property A sample (width 180 mm, length 100 mm) in which a black plate was pasted via a transparent adhesive to the resin molded body side surface (transparent acrylic sheet side surface) of the decorative molded products obtained in Examples and Comparative Examples ) was made. The sample was placed on a horizontal surface, a fluorescent lamp was placed 1.5 m above the sample, and the illuminance above the sample was observed from various angles in an environment of 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 border of the outline cannot be recognized.
C: The image of the fluorescent lamp is reflected like a mirror on the uneven area, and the contour of the fluorescent lamp (border of the contour) can be clearly recognized.

3-3. Glare The surface of the transparent acrylic sheet side of the decorative molded products obtained in Examples and Comparative Examples was placed on the surface of an image display device (trade name iPad (registered trademark) Air manufactured by Apple, resolution: 264 ppi), and the screen was displayed as green, and whether or not the bright spots were conspicuous was visually evaluated. The evaluation environment was a bright indoor environment equipped with a fluorescent lamp (environment where the illuminance on the decorative molded product was 800 to 1200 Lx with the image display device turned off).
Areas P and Q were visually observed from the front, and 3 points were not disturbed by minute variations in brightness, 2 points were neither of these, and 2 points were noted by fine variations in brightness. 1 point, 20 subjects evaluated and calculated the average score.
<Evaluation Criteria>
A: Average score of 2.5 or more B: Average score of 1.5 or more and less than 2.5 C: Average score of less than 1.5

3-4. Contrast A sample was prepared by laminating the transparent acrylic sheet side of the decorative moldings obtained in Examples and Comparative Examples onto the printed surface of a black acrylic resin plate on which an image was printed. In a bright room equipped with a fluorescent light (illuminance on the sample is 800 to 1200Lx), visually observe the uneven part on the area P of the sample, three points with good contrast between the printed image and the black background, Evaluations were made by 20 subjects, and an average score was calculated by assigning 2 points to a case where neither can be said, and 1 point to a case where the contrast between the printed image and the black background is poor.
<Evaluation Criteria>
AA: Average score of 2.7 or more A: Average score of 2.5 or more and less than 2.7 B: Average score of 1.5 or more and less than 2.5 C: Average score of less than 1.5

3-5. Image Clarity The transparent acrylic sheet side of the decorative moldings obtained in Examples and Comparative Examples was placed on the surface of an image display device (trade name iPad (registered trademark) Air manufactured by Apple Inc., resolution: 264 ppi). , a moving image was displayed, and the visibility of the moving image viewed through the region P was evaluated. The evaluation environment was a bright room environment equipped with a fluorescent lamp (environment in which the illuminance on the decorative molded product was 800 to 1200 Lx when the image display device was turned off).
Twenty people were given 3 points for those who felt the action was powerful with clear images, 2 points for those who could not say either way, and 1 point for those who felt that the clarity of the image was insufficient and the action was insufficient. Subjects evaluated and the average score was calculated.
<Evaluation Criteria>
A: Average score of 2.5 or more B: Average score of 1.5 or more and less than 2.5 C: Average score of 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 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). Designability was evaluated on two points: "clear contrast between region P and region Q (clear distinction between the two regions)" and "absence of whitening". 3 points for overall good design, 2 points for neither, and 1 point for overall poor design. points were calculated.
<Evaluation Criteria>
A: Average score of 2.5 or more B: Average score of 1.5 or more and less than 2.5 C: Average score of 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 properties, contrast and image sharpness.

The decorative molded article of the present invention can be suitably used in fields such as communication equipment such as mobile phones, information equipment 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 displays of communication devices such as mobile phones and information devices inside automobiles.

10, 20, 30 Decorative molded article 40, 50, 60 Transfer sheet 1, 11, 21 Resin molding 2, 12, 22, 35, 45, 55 Protective layer 13, 23, 47, 57 Anchor layer 14, 24, 48, 58 printed layer 15, 25, 49, 59 adhesive layer 31, 41, 51 substrate 32, 42, 52 uneven layer 33, 43, 53 first release layer 34, 44, 54 second release layer 46, 56 relaxation layer P protective layer region P
Q area Q of the protective layer
P' Substrate region P'
Q' base material region Q'
X release sheet Y transfer layer

Claims (6)

A decorative molded product in which a protective layer is provided on a resin molded product,
The protective layer has a region P having unevenness and a region Q adjacent to the region P,
Ra _x1 is the arithmetic mean roughness of JIS B0601:1994 when the cutoff value λc of the surface of the region P is 0.8 mm, and JIS when the cutoff value λc of the surface of the region P is 0.08 mm When the arithmetic average roughness of B0601:1994 is defined as _Ray1 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 decorative 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 )/Ra _y1 ≦0.38 (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 satisfy the following formula (4). The decorative molded article according to claim 1, which fills.
Ra _x2 <Ra _x1 (4) a substrate having a region P′ and a region Q′ adjacent to said region P′;
a concavo-convex layer having a concavo-convex shape provided on the region P′ of the base;
a first release layer formed on the uneven shape of the uneven layer;
a second release layer provided on the region Q′ of the base;
Having the first release layer and a protective layer formed on the second release layer,
Ra _x11 is the arithmetic mean roughness of JIS B0601:1994 when the cutoff value λc of the surface of the first release layer is 0.8 mm, and the cutoff value λc of the surface of the first release layer is 0.8 mm. _Ray11 is the arithmetic average roughness of JIS B0601: 1994 when the cutoff value of the surface of the first release layer is 0.8 mm, and the ten-point average roughness of JIS B0601: 1994 when the cutoff value of the surface of the first release layer is 0.8 mm. A transfer sheet wherein Ra _x11 , Ra _y11 , and Rz _x11 satisfy the following formulas (1)′ to (3)′ when Rz _x11 is defined.
0.050 μm≦Ra _x11 <0.140 μm (1)′
0.30≦(Ra _x11 −Ra _y11 )/Ra _y11 ≦0.38 (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 , the Ra _x11 and the Ra _x22 are expressed by the following formula ( 4) The transfer sheet of claim 3, wherein 'is satisfied.
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 molding;
a step of peeling off the first release layer and the second release layer of the transfer sheet;
A method for manufacturing a decorative molded product. An image display device having a display element and a front plate disposed on the light emitting surface side of the display element, wherein the front plate is the protective layer side surface of the decorative molded product according to claim 1 or 2. is arranged so as to face the opposite side of the display element.

Images