JP2010280203A - Decorative sheet, method for manufacturing the same, and decorative molded object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet provided with a protective layer for protecting an embossed sheet so as not to damage the surface unevenness of the embossed sheet. <P>SOLUTION: The protective layer 13 includes a binder 15 of which the hardness after curing is H or above as pencil hardness and abrasion-resistant particles 14 of which the hardness is equal to or more than that of the binder 15 and the particle size is 8 μm or above as an average particle size and less than 35% of Rz of the surface of the embossed sheet 12 and is formed by coating the embossed sheet 12 with a coating solution for the protective layer having a viscosity of 200-1,000 mPa s and a thixotropy index value of 1.0 or more and less than 1.5 by screen printing. The thickness of the protective layer 13 at the protrusions of the embossed sheet 12 is 50-110% with respect to the particle size of the abrasion-resistant particles 14, the outer shapes of the abrasion-resistant particles 14 are expressed on the surfaces of the protrusions of the embossed sheet 12 and the thickness of the protective layer 13 is 70% or less than the maximum height roughness Rz of the embossed sheet 12 in the recessed parts of the embossed sheet 12. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a decorative sheet used for decoration of various electronic devices such as mobile communication devices, AV devices, in-vehicle electrical devices, and other electric devices, a method for manufacturing the decorative sheet, and such decorative sheets. The present invention relates to a decorative molded body using.

Various electronic devices such as mobile communication devices and AV devices are equipped with exterior parts such as housings and switches. These exterior parts include display elements such as letters, symbols, numbers, and designs, metal-like hairlines, and wood grain. Patterns such as tone and carbon cloth tone are given as “decoration”. In addition, the “decoration” of these exterior parts is not only a display element and a two-dimensional pattern, but also has a three-dimensional surface that has irregularities that change not only the appearance but also the actual viewing angle and light position. A decorative sheet that gives an appearance is often used.
Since a decorative sheet using an embossed sheet with irregularities is easily rubbed, durability such as wear resistance and scratch resistance is required. For example, when the unevenness on the surface of the embossed sheet is worn, the unevenness of the unevenness is reduced and the feeling of unevenness is lowered. Further, when a decorative layer for providing display elements or patterns on the uneven surface is provided, the decorative layer is peeled off, and the uneven surface of the embossed sheet is exposed, and the appearance is deteriorated. In order to avoid such problems, the surface of the embossed sheet is covered with a protective layer to enhance the durability of the decorative sheet.

  As an example of such a decorative sheet, for example, in Japanese Patent Laid-Open No. 9-24585, colored ink is embedded in a concave portion of an embossed sheet made of a transparent olefin resin having an embossed pattern on its surface, and the surface side thereof An embossed decorative sheet is disclosed in which a resin layer (protective layer) made of urethane resin is formed with a thickness of 2 μm by a gravure printing method.

Japanese Patent Laid-Open No. 9-24585

By the way, the embossed decorative sheet of Patent Document 1 can efficiently form a resin layer by a gravure printing method, but if the thickness of the resin layer is about 2 μm, it is insufficient to increase the wear resistance.
In addition, the protective layer can be formed by applying ink to the embossed sheet by the bar coating method, but the ink accumulates in the concave portion of the concave and convex surface, and the layer thickness of the concave portion increases and the layer thickness of the convex portion decreases. However, there is a problem that it is difficult to improve the wear resistance due to the loss of unevenness. Alternatively, the protective layer can be formed by applying a paint to the embossed sheet by a coating method, but a large coating machine is required, and more coating material does not adhere to the embossed sheet, resulting in an increase in manufacturing cost. In addition, since the paint contains a lot of solvent, a solvent-resistant embossed sheet is required, and there is a problem that the material selection of the embossed sheet is limited.

  The present invention has been made against the background of the prior art as described above. That is, the objective of this invention is providing the technique which provides the protective layer which does not impair the uneven | corrugated feeling in the decorating sheet | seat which gives a three-dimensional external appearance by an unevenness | corrugation. Moreover, it is providing the technique which provides a durable protective layer, without limiting the material selection of the embossed sheet used as a base material. Furthermore, it is providing the technique which can manufacture such a decorating sheet cheaply. In addition, it is to provide a decorative molded body using such a decorative sheet.

  About the decorative sheet provided with a protective layer that protects the unevenness of the surface so as not to impair the unevenness of the surface on the embossed sheet whose maximum height roughness Rz of the uneven surface whose surface has been processed unevenly is 40 μm to 120 μm, Abrasion-resistant particles and a binder that stops the wear-resistant particles on the surface of the embossed sheet are provided. The protective layer has a pencil hardness of H or higher in terms of pencil hardness and a hardness equal to or higher than that of the binder. It contains wear-resistant particles having an average particle size of 8 μm or more and a size of 35% or less of Rz on the surface of the embossed sheet, a viscosity of 200 mPa · s to 1000 mPa · s, and a thixotropic index value of 1.0 to 1.5. The coating liquid for the protective layer which is less than is applied and formed on the surface of the embossed sheet by screen printing. The thickness of the protective layer is 50% to 110% of the particle size of the wear-resistant particles, and the outer shape of the wear-resistant particles is exposed on the surface of the protective layer. The decorative sheet is characterized in that the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet.

In the embossed convex and concave portions of the embossed sheet, a protective layer is formed in which the thickness of the protective layer is 50% to 110% of the particle size of the antiwear particles, and the outer shape of the antiwear particles is exposed on the surface of the protective layer. In addition, since the protective layer has a protective layer in which the thickness of the protective layer is 70% or less of the Rz of the embossed sheet, the concave portion can be confirmed, and the concave / convex state is maintained without impairing the concave / convex feeling. Thus, the surface of the embossed sheet can be protected.
And since the viscosity is 200 mPa · s to 1000 mPa · s and the thixotropy index value is 1.0 or more and less than 1.5, the protective layer coating solution is applied to the embossed sheet surface by screen printing to form the protective layer. In addition, it is possible to maintain the concavo-convex state without impairing the concavo-convex feeling while reliably providing a protective layer for the convex and concave portions of the embossed sheet.

Since this protective layer is composed of a binder having a hardness of H or higher in pencil hardness after curing and wear-resistant particles having a hardness equal to or higher than the hardness of the binder, it can be a protective layer having excellent wear resistance. .
In addition, since the average particle size of the wear-resistant particles is 8 μm or more and 35% or less of Rz on the surface of the embossed sheet, the embossed sheet can be held without impairing the unevenness.
And since the maximum height roughness Rz of an embossed sheet is 40 micrometers-120 micrometers, it can be set as the decorating sheet which gives the tactile sense that an unevenness | corrugation is felt, and does not impair this uneven feeling by forming the said protective layer. In addition, a decorative sheet having excellent wear resistance can be obtained.
In the embossed sheet, the concavo-convex processed convex part and concave part are the microscopic shape of the surface that makes the embossed sheet feel concave and convex, the peripheral part of the peak is a convex part, and the peripheral part of the valley bottom is a concave part. 3, as shown by region R5 in FIG. 3, the embossed sheet uneven surface is divided into three parts from the peak to the valley, or from the valley to the peak, and one third of the peak side is the convex part, One third of the part is called a recess.

  Moreover, about the decoration sheet which provided the protective layer which protects so that the unevenness | corrugation of the surface may not be impaired to the embossed sheet which has the uneven surface by which the surface was uneven | corrugated, a protective layer embossed an anti-wear particle and its anti-wear particle. And a convex part that is processed to be uneven in the embossed sheet, the thickness of the protective layer is 50% to 110% of the particle size of the wear-resistant particles located in the convex part. In addition, the outer shape of the wear-resistant particles is exposed on the surface of the protective layer, and the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions of the embossed sheet. A decorative sheet characterized by the above is provided.

  About the decorative sheet provided with a protective layer that protects the surface of the embossed surface so that the unevenness of the surface is not damaged on the embossed sheet whose surface has been processed to be uneven, the protective layer has anti-wear particles and anti-wear particles on the surface of the embossed sheet. A convex portion that is processed to be uneven in the embossed sheet, and the thickness of the protective layer is 50% to 110% of the particle size of the wear-resistant particles located in the convex portion, and is protected. The outer shape of the abrasion-resistant particles is exposed on the surface of the layer, and the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions of the embossed sheet. The concave portion can be confirmed, and the surface of the embossed sheet can be protected while maintaining the concave-convex state without impairing the sense of irregularity.

The embossed sheet has a maximum height roughness Rz of 40 μm to 120 μm of the uneven surface subjected to the uneven processing, and the wear-resistant particles have an average particle size of 8 μm or more and 35% or less of Rz on the surface of the embossed sheet. It can be set as the decoration sheet which is a magnitude | size.
Since the maximum height roughness Rz of the concavo-convex surface of the embossed sheet is 40 μm to 120 μm, it can be a decorative sheet that gives a tactile sensation in which concavo-convex is felt, and this concavo-convex feeling is not impaired by forming the protective layer. In addition, a decorative sheet having excellent wear resistance can be obtained.
Since the average particle size of the binder is 8 μm or more and 35% or less of Rz on the surface of the embossed sheet, the embossed sheet can be held without impairing the unevenness.

The binder is an organic polymer material having a pencil hardness of H or higher, and the wear-resistant particles can have a hardness equal to or higher than that of the binder.
Since the hardness of the binder is H or higher in terms of pencil hardness and the hardness of the abrasion-resistant particles is equal to or higher than the hardness of the binder, a protective layer having excellent wear resistance can be formed.

The mixing ratio of the antiwear particles in the protective layer to the binder can be 10 vol% to 50 vol%.
Since the mixing ratio of the abrasion-resistant particles to the binder in the protective layer is 10 vol% to 50 vol%, sufficient durability can be exhibited by the abrasion-resistant particles, and the abrasion-resistant particles are not caused to flow into the recesses due to excessive binder, The uneven state can be maintained without impairing the unevenness.

The decoration is such that the wear-resistant particles are distributed along the surface of the embossed sheet, and the embossed sheet is arranged so as not to overlap on the convex part of the embossed sheet, thereby forming a micro uneven surface along the outer shape of the wear-resistant particles on the surface of the protective layer. It can be a sheet.
The anti-abrasion particles are distributed along the surface of the embossed sheet, and the embossed sheet is arranged so that it does not overlap, and the surface of the protective layer is formed with a micro uneven surface along the outer shape of the anti-wear particles. The wear-resistant particles of the protective layer can be arranged also on the part, and the wear resistance of the decorative sheet can be improved. Furthermore, since the anti-wear particles are arranged without overlapping the convex portion, the protective layer can be formed so as to follow the outer shape of the convex portion on the uneven surface.

  The protective layer can be a matte transparent resin layer. Since the protective layer is a matte transparent resin layer, a matte surface can be formed even with a protective layer provided in a thin layer so as not to impair the unevenness of the embossed sheet. Moreover, even if it is a case where a decoration layer is provided in the back surface of a protective layer by setting it as a transparent resin layer, the decoration layer can fully be visually recognized.

  Part of the anti-wear particles disposed on the convex portion of the embossed sheet can be exposed from the binder. If a protective layer in which the wear-resistant particles are exposed from the binder is provided in the convex portion, the wear-resistant particles having higher wear resistance than the binder appear on the surface, whereby a protective layer having excellent wear resistance can be obtained. That is, rubbing against the binder can be eliminated as much as possible to make it difficult to wear the binder. Further, the wear-resistant particles arranged on the convex portions of the embossed sheet can expose the outer shape of the wear-resistant particles on the surface of the protective layer while forming a thin film of the binder on the surface. If a binder film is formed on the surface of the wear-resistant particles, the wear-resistant particles can be made more difficult to fall off.

Unlike the uneven surface on the surface of the embossed sheet, a decorative sheet having a textured surface corresponding to the particle size of the abrasion-resistant particles can be obtained.
Unlike the uneven surface on the surface of the embossed sheet, a textured surface corresponding to the particle size of the abrasion-resistant particles is provided, so that the abrasion-resistant particles in the protective layer easily stop on the textured surface, and the abrasion-resistant particles on the convex portions of the embossed sheet. Can be easily provided.

A decorative layer can be provided between the embossed sheet and the protective layer. Since the decorative layer is provided between the embossed sheet and the protective layer, the decorative layer can be easily visually recognized as compared with the case where the decorative layer is provided on the back surface of the embossed sheet. In addition, it is possible to obtain a surface having an excellent design that gives a more realistic texture such as wood tone and fiber tone.
In addition, the decorative layer provided on the uneven surface of such an embossed sheet has insufficient wear resistance because it is difficult to increase the layer thickness, but the protective layer of the present invention covers the decorative layer, so that the decorative layer Can be made difficult to peel off.

  Further, the present invention provides a decorative sheet in which an embossed sheet having a concavo-convex surface having a concavo-convex surface with a maximum height roughness Rz of 40 μm to 120 μm is provided with a protective layer for protecting the surface so as not to damage the concavo-convex surface. Regarding the manufacturing method, a binder having a hardness after curing of H or higher in pencil hardness, a hardness equal to or higher than that of the binder, an average particle size of 8 μm or more, and a size of 35% or less of Rz on the surface of the embossed sheet The embossed sheet is prepared by preparing a coating solution for a protective layer containing an antiwear particle having a thickness, adjusted with a solvent, having a viscosity of 200 mPa · s to 1000 mPa · s, and a thixotropic index value of 1.0 to less than 1.5. The protective layer is formed on the surface of the embossed sheet by applying the coating liquid for the protective layer by screen printing. The outer shape of the abrasion-resistant particles is exposed on the surface of the protective layer, and the thickness of the protective layer in the embossed recesses of the embossed sheet is 50% to 110%. A method for producing a decorative sheet, characterized by producing a decorative sheet having a thickness of 70% or less of the maximum height roughness Rz.

Since the protective layer was formed by screen-printing the protective layer coating liquid with a viscosity of 200 mPa · s to 1000 mPa · s adjusted with a solvent and a thixotropic index value of 1.0 or more and less than 1.5, uneven processing on the embossed sheet The protective layer in which the outer shape of the abrasion-resistant particles is exposed can be laminated even on the projected portion, and the concave portion can be prevented from damaging the embossed sheet surface without filling the concave portion more than necessary.
In addition, since the protective layer is formed from a coating liquid for protective layer having a binder whose hardness after curing is H or higher in pencil hardness and an anti-abrasion particle having a hardness equal to or higher than the hardness of the binder, it has excellent wear resistance. It can be a protective layer.

In the embossed convex and concave portions of the embossed sheet, a protective layer is formed in which the thickness of the protective layer is 50% to 110% of the particle size of the antiwear particles, and the outer shape of the antiwear particles is exposed on the surface of the protective layer. In the recess, since the protective layer is formed with a protective layer having a thickness of 70% or less of Rz of the embossed sheet, the recess can be confirmed, and the uneven state is maintained without impairing the uneven feeling. The surface of the embossed sheet can be protected.
In addition, since the average particle size of the wear-resistant particles is 8 μm or more and 35% or less of Rz on the surface of the embossed sheet, the embossed sheet can be held without impairing the unevenness.

And since the maximum height roughness Rz of an embossed sheet is 40 micrometers-120 micrometers, it can be set as the decorating sheet which gives the tactile sense that an unevenness | corrugation is felt, and does not impair this uneven feeling by forming the said protective layer. In addition, a decorative sheet having excellent wear resistance can be obtained.
Since the protective layer is applied and formed by the screen printing method, a large-scale apparatus is not required, the adhesion efficiency of the protective layer coating liquid is high, and the protective layer can be formed at low cost. Further, since the protective layer is applied and formed by the screen printing method, the amount of the solvent of the protective layer coating liquid can be reduced as compared with the coating method. Therefore, deformation and deterioration of the embossed sheet due to the solvent can be made difficult to occur, and the material options for the embossed sheet can be expanded.

  Moreover, about the manufacturing method of the decorating sheet which provided the protective layer which protects so that the unevenness | corrugation of the surface might be damaged to the embossed sheet | seat which the uneven | corrugated surface by which the surface was uneven | corrugated was made to contain a binder and an abrasion-resistant particle, A protective layer coating solution having a viscosity of 200 mPa · s to 1000 mPa · s and a thixotropy index value of 1.0 or more and less than 1.5 is prepared, and the coating for the protective layer is applied to the surface of the embossed sheet by screen printing. Provided is a method for producing a decorative sheet, which comprises applying a liquid to form a protective layer and producing a decorative sheet.

  Prepare a protective layer coating solution having a viscosity of 200 mPa · s to 1000 mPa · s and a thixotropic index value of 1.0 to less than 1.5, and apply the protective layer coating solution by screen printing on the surface of the embossed sheet Since the protective layer is formed, the protective layer in which the outer shape of the wear-resistant particles is exposed can be laminated even on the convex and concave portions of the embossed sheet, and the surface of the embossed sheet does not fill the concave portion more than necessary in the concave portion. It is possible not to impair the unevenness.

  Furthermore, the manufacturing method of the decorating sheet which provided the protective layer which protects so that the unevenness | corrugation of the surface might not be impaired to the embossed sheet whose maximum height roughness Rz of the uneven | corrugated surface by which the surface was uneven | corrugated was 40 micrometers-120 micrometers A coating liquid for a protective layer containing a binder and an abrasion-resistant particle having an average particle size of 8 μm or more and a size of 35% or less of Rz on the surface of the embossed sheet is prepared, and screen printing is performed on the surface of the embossed sheet. The protective layer is formed by applying the protective layer coating liquid, and the thickness of the protective layer is 50% to 110% with respect to the particle size of the wear-resistant particles in the convex and concave portions of the embossed sheet. In addition, the outer shape of the wear-resistant particles is exposed on the surface of the protective layer, and the thickness of the protective layer is the maximum height roughness Rz of the embossed sheet in the concave and convex portions in the embossed sheet. To produce a decorative sheet is 0% or less of the thickness to provide a method for manufacturing a decorative sheet according to claim.

In the embossed surface of the embossed sheet, a protective layer having a thickness of 50% to 110% of the particle size of the antiwear particles and the outer shape of the antiwear particles is formed on the surface. Since the protective layer having a thickness of 70% or less of Rz is formed, the concave portion can be confirmed, and the surface of the embossed sheet can be protected while maintaining the concave / convex state without impairing the concave / convex feeling.
In addition, since the average particle size of the wear-resistant particles is 8 μm or more and 35% or less of Rz on the surface of the embossed sheet, the embossed sheet can be held without impairing the unevenness.
And since the maximum height roughness Rz of an embossed sheet is 40 micrometers-120 micrometers, it can be set as a decorating sheet which gives a three-dimensional appearance, and without impairing this uneven feeling by forming the said protective layer. A decorative sheet having excellent wear resistance can be obtained.

  And the decoration molded object which has these decoration sheets on the surface is provided. The decorative molded body having the decorative sheet on its surface can protect the surface of the embossed sheet while maintaining the concavo-convex state without impairing the concavo-convex feeling of the embossed sheet, and is a decorative molded body with a high design that has an excellent concavo-convex feeling. It can be.

  According to the decorative sheet of the present invention, its production method, and decorative molded body, a protective layer can be provided so as not to impair the uneven surface of the embossed sheet, and the decorative sheet and decorative material excellent in wear resistance can be provided. A decorative molded body can be obtained.

The top view which shows the decorating sheet of 1st Embodiment. The longitudinal cross-sectional view which shows the decorating sheet of 1st Embodiment, and its partial expanded sectional view. The longitudinal cross-sectional view which shows the emboss sheet used for the decorating sheet of 1st Embodiment, and its partial expanded sectional view. The longitudinal cross-sectional view which shows the decorating sheet of 2nd Embodiment. The perspective view and partial expanded sectional view of a mobile telephone to which the decorative molded body of the third embodiment is applied. The longitudinal cross-sectional view which shows the conventional decoration molded object.

  Embodiments of the present invention will be described with reference to the drawings. In addition, about the structure which is common in each embodiment, the same code | symbol is attached | subjected and duplication description is abbreviate | omitted.

First Embodiment (FIGS. 1 to 3) :
The decorating sheet 11 of this embodiment is shown in FIGS. FIG. 1 is a plan view of the decorative sheet 11, and FIG. 2 is a cross-sectional view of the decorative sheet 11. The decorative sheet 11 of the present embodiment is provided with a protective layer 13 that imparts wear resistance to the surface of the embossed sheet 12 that has been subjected to uneven processing. FIG. 3 shows a cross-sectional view of the embossed sheet 12.

Embossed sheet : The embossed sheet 12 is a resin film that serves as a base for the decorative sheet 11, and as shown in FIG. 3, the surface is subjected to uneven processing, and the unevenness is expressed as carbon, denim or wood grain. The uneven surface 16 is formed. That is, the concavo-convex surface 16 of the embossed sheet 12 affects the outer shape and tactile sensation of the decorative sheet 11 and gives the decorative sheet 11 a desired texture.

The maximum height roughness Rz (also referred to as “Rz”) of the uneven surface 16 in the embossed sheet 12 is preferably 40 μm to 120 μm. If Rz of the concavo-convex surface 16 is less than 40 μm, it is difficult to form the protective layer 13 having sufficient wear resistance without filling the concave portion 16a of the concavo-convex surface 16. When Rz exceeds 120 μm, the step between the convex part and the concave part becomes large, and it becomes difficult to apply the protective layer in the concave part when the protective layer is formed by a printing method such as screen printing.
Furthermore, the surface of the concavo-convex surface 16 is preferably a fine concavo-convex textured surface 17 as shown in a partially enlarged view R4 in FIG. The textured surface 17 is completely different from the aforementioned irregular surface 16 serving as a reference for Rz. If the irregular surface 16 is a large “undulation” irregularity step, the textured surface 17 will have its “undulation”. This corresponds to a fine uneven step on the surface.

  As the material of the embossed sheet 12, a thermoplastic resin having a solvent resistance that does not cause a solvent crack when the protective layer coating liquid for forming the protective layer 13 is applied can be used. Examples thereof include acrylonitrile / butadiene / styrene copolymer (ABS) resin, polypropylene resin, polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin, and polycarbonate resin.

Protective layer : The protective layer 13 is a layer that covers the surface of the embossed sheet 12 and protects the uneven surface 16 thereof. The protective layer 13 includes anti-wear particles 14 and a binder 15, and the outer shape of the anti-wear particles 14 appears on the surface of the protective layer 13 as shown in FIG. 2, along the outer shape of the anti-wear particles 14. The minute uneven surface 13a is formed. And in the convex part 16b of the embossed sheet 12, the abrasion-resistant particle | grains 14 are arrange | positioned without overlapping.

The thickness of the protective layer 13 is 50% to 110% of the particle size of the wear-resistant particles 14 in the concavo-convex convex portion 16b of the embossed sheet 12, and the concavo-convex processed in the embossed sheet 12 is performed. In the recessed part 16a, it is the thickness of 70% or less of Rz of the embossed sheet 12. Moreover, in the convex part 16b, the layer thickness of the part which has only the binder 15 without the abrasion-resistant particle | grains 14 is 50%-90% of the particle size of the abrasion-resistant particle | grains 14. FIG.
The laminated state of the protective layer 13 on the embossed sheet 12 will be described in more detail. The wear-resistant particles 14 constituting the protective layer 13 are arranged so as not to overlap the convex portions 16b of the irregular surface 16. Thus, the thickness of the protective layer 13 in the convex portion 16b is about one of the wear-resistant particles 14. That is, since the thickness of the protective layer 13 at the convex portion 16b is 50% to 110% of the particle size of the wear-resistant particles 14, the portion smaller than 100% does not have the wear-resistant particles 14 but only the binder 15 exists. The upper limit of 110% means that two or more particles do not overlap in the layer thickness direction even when the anti-wear particles 14 are present. 110% means that the surface of the abrasion-resistant particles 14 may be covered with the binder 15. And even in the part where the abrasion-resistant particles 14 are not present, the binder 15 is present by a thickness that is 50% to 90% of the particle diameter to hold the abrasion-resistant particles.
The region R2 in FIG. 2 shows the case where the surface of the anti-wear particles 14 is covered with the binder 15, but depending on the type of the binder 15 and the viscosity of the coating liquid for the protective layer, the anti-wear particles as shown in the region R3. The surface of 14 may be exposed.

When the layer thickness of the binder 15 is less than 50% of the particle size of the wear-resistant particles 14 at the protrusions 16b, the holding force of the wear-resistant particles 14 is small, and the wear-resistant particles 14 easily fall off the binder. On the other hand, if it exceeds 90%, it becomes difficult for the antiwear particles 14 to be exposed on the surface of the protective layer 13, and the proportion of the binder increases, so that the antiwear particles easily flow into the recess 16a as the binder flows. That is, since the layer thickness of the binder 15 portion is 50% to 90% of the particle size of the anti-wear particles 14, the protective layer can be reliably formed on the convex portions and the concave portions while keeping the holding force of the anti-wear particles 14 high.
The reason why the thickness of the protective layer 13 in the recess 16a is 70% or less of the Rz in the embossed sheet 12 is that the recess 16a is excessively filled when the thickness exceeds 70%, and the unevenness is impaired.

  In addition, the uneven surface 16 of the embossed sheet 12 has a fine uneven surface 17 as shown by a region R1 in FIG. 3 showing a partially enlarged view. The anti-wear particles 14 are preferably laminated so that they are fitted to each other. In this way, it is possible to make it difficult for the wear-resistant particles 14 disposed on the convex portions 16b to fall into the concave portions 16a, and to easily stop the wear-resistant particles 14 on the convex portions 16b.

The abrasion resistant particles 14 forming the protective layer 13 enhance the wear resistance of the protective layer 13. The size of the abrasion-resistant particles 14 is an average particle diameter of 8 μm or more and 35% or less of Rz in the embossed sheet 12.
The reason why the average particle size of the wear-resistant particles is set to 8 μm or more is that when the average particle size is smaller than 8 μm, the wear durability of the wear-resistant particles is lowered and the binder 15 in the convex portion is also thinned. Abrasion may be insufficient. On the other hand, if an attempt is made to apply a protective layer so as to have sufficient wear resistance, the wear-resistant particles are buried in the binder, which tends to flow into the recesses, making it difficult to maintain the feeling of unevenness. Further, the average particle size of the wear-resistant particles is set to 35% or less of the Rz of the embossed sheet. When the particle size exceeds 35% of the Rz, the uneven step is reduced only by overlapping several wear-resistant particles in the recess 16a. This is because the recess is filled.
That is, in general, the average particle size of additives added to adjust the viscosity and the like to make the surface matt (matte) is less than 8 μm. Since the wear-resistant particles 14 having a large average particle size are used, the viscosity of the protective layer coating liquid for forming the protective layer 13 can be kept low. In addition, when compared with the same amount of addition, the amount of addition decreases compared to the case where the wear-resistant particles having a small average particle diameter are used. Is also very effective.

The hardness of the wear-resistant particles 14 is equal to or higher than the hardness after the binder 15 is cured. Since the hardness of the binder 15 is H or higher in pencil hardness, it is at least H or higher in pencil hardness. If the pencil hardness is softer than H, the wear-resistant particles themselves are easily worn, and the wear-resistant particles 14 are deformed when the protective layer 13 is rubbed. The wear-resistant particles 14 are easily removed from the binder 15 by the stress of this deformation. This is because it is difficult to impart wear resistance to the protective layer 13. Further, since the wear-resistant particles 14 are arranged so that the outer shape is exposed on the surface of the embossed sheet at the convex portions, the wear resistance of the protective layer can be more effectively enhanced by using particularly high-hardness wear-resistant particles. Can do.
In particular, in the convex portion 16 b of the embossed sheet 12, the thickness of the binder 15 in the protective layer 13 is 50% to 90% of the particle size of the antiwear particles 14, thereby fixing the antiwear particles 14. Therefore, dropping off of the wear-resistant particles 14 deteriorates the wear resistance of the protective layer 13. Therefore, it is a point for realizing the abrasion-resistant protective layer 13 that is excellent in suppressing the abrasion-resistant particles 14 from falling off. In addition, about pencil hardness, it is the value measured according to prescription | regulation of JISK5600-5-4.
The shape of the wear-resistant particles 14 is preferably 0.5 or more in aspect ratio. When the aspect ratio is less than 0.5, the sleep direction is such that the minor axis direction is the thickness direction of the protective layer 13, and the anti-abrasion particles 14 are easily laminated.
In order to maintain the appearance of the embossed sheet 12, the material of the abrasion-resistant particles 14 is preferably an organic polymer or an inorganic material having transparency. For example, examples of the organic polymer include melamine resin and crosslinked acrylic resin, and examples of the inorganic substance include silica and glass beads. Aluminum oxide, titanium oxide, etc. are hard and have excellent wear resistance but are white, so they can be applied when obtaining a white appearance, but are difficult to apply when obtaining an appearance other than white. Inferior in terms of sex.

The binder 15 is made of a resin that fixes the wear-resistant particles 14 to the uneven surface 16 of the embossed sheet 12, and the hardness after curing is H or more in pencil hardness. If it is softer than H, the wear resistance of the protective layer 13 will be insufficient. The wear resistance of the protective layer 13 is largely attributed to the abrasion-resistant particles 14, but the binder 15 also has a hardness of the protective layer 13 by using an organic polymer having a pencil hardness of H or higher and a high surface hardness. Can be increased.
The material of the binder 15 is an organic polymer having good adhesion to the embossed sheet 12. Specific examples include thermoplastic resins, thermosetting resins, and active energy ray curable resins. Among these, thermosetting resins and active energy ray curable resins having excellent pencil hardness and mechanical properties of the coating film. Is preferred. Furthermore, a thermosetting resin is more preferable from the viewpoint of easy preparation of a protective layer coating liquid described later. For example, examples of the thermoplastic resin include acrylic resin, vinyl chloride resin, and vinyl acetate resin. Examples of the thermosetting resin include urethane resin, epoxy resin, and polyester resin. Examples include urethane acrylate, polyester acrylate, and epoxy acrylate. Among these organic polymers, urethane resins and acrylic resins that are particularly excellent in hardness and wear resistance are preferred.

  The mixing ratio of the abrasion-resistant particles 14 to the binder 15 is preferably 10 vol% to 50 vol%. Since the mixing ratio of the abrasion-resistant particles 14 with respect to the binder 15 is 10 vol% to 50 vol%, the abrasion-resistant particles 14 can be disposed on the convex portions 16 b of the embossed sheet 12, and a large amount of the abrasion-resistant particles 14 do not accumulate in the concave portions 16 a. Thus, the anti-wear particles 14 can be arranged. That is, compared with the general case where a filler is contained in the resin, the mixing amount of the binder 15 with respect to the abrasion-resistant particles 14 is blended to a small extent. By adopting such a composition, the anti-abrasive particles 14 are easily exposed on the surface by the convex portions of the embossed sheet 12.

The protective layer 13 is formed by coating and forming the anti-wear particles 14 and the binder 15 on the surface of the embossed sheet 12. The protective layer coating liquid for that purpose is prepared by blending at least the binder 15 with the antiwear particles 14 and a solvent.
The viscosity of the protective layer coating liquid is preferably 200 mPa · s to 1000 mPa · s. If the viscosity is lower than 200 mPa · s, the viscosity is too low to be in a viscosity range that is not suitable for printing, and the amount of solvent increases, so that a sufficient binder is provided in the convex portion 16b of the irregular surface 16 of the embossed sheet 12. It is difficult to obtain a layer thickness of 15.
Further, depending on the material of the embossed sheet 12, the embossed sheet 12 may be bent or deformed by a large amount of solvent. On the other hand, when the viscosity exceeds 1000 mPa · s suitable for general printing, the ratio of the binder 15 in the coating liquid for the protective layer is large, the layer thickness of the binder 15 tends to increase, and the flow of the coating liquid for the protective layer. And the binder 15 is less likely to adhere to the recess 16a. That is, by relatively reducing the ratio of the binder, it is possible to suppress the abrasion-resistant particles from flowing into the recesses along with the flow of the binder.
Furthermore, by adjusting the viscosity within the above range, the protective layer can be reliably applied to the concave portions as described above, and a certain amount of binder is provided between the individual antiwear particles by the surface tension in the convex portions. It is intended to be retained. In this way, a protective layer in which the outer shape of the abrasion-resistant particles 14 is exposed can be formed at the convex portions.
The viscosity is measured based on JIS K7117-2, and is a value at a rotational speed of 35 rpm using an E-type rotational viscosity system VISCO88BV manufactured by Borlin.

The thixotropy index value of the protective layer coating solution is preferably 1.0 or more and less than 1.5. Here, the thixotropy index value is a viscosity ratio with respect to a rotational speed different by 10 times, and is 1 for a Newtonian fluid and takes a value of 1.0 or more for a composition to which antiwear particles are added. In general, a thixotropic index value is adjusted to about 1.5 to 5 in a coating liquid for a protective layer for printing. This is to prevent the printed pattern from being disturbed by the flow of the protective layer coating liquid. However, in the protective layer coating solution, when the thixotropy index value is 1.5 or more, the flowability is suppressed, and it is difficult to attach the protective layer coating solution to the concave portion 16a of the embossed sheet 12. Therefore, the thixotropy index value is set to 1.0 or more and less than 1.5.
Regarding the thixotropy index value, referring to the description of JIS K6833-1, the ratio of the viscosity at a rotational speed of 35 rpm to the viscosity at 350 rpm was calculated to obtain a thixotropy index value.

  The coating liquid for the protective layer composed of the anti-wear particles 14 and the binder 15 has been described. However, in addition to the anti-wear particles 14, the binder 15, and the solvent, such as a coloring material that imparts a color to the protective layer 13, a viscosity modifier, and a curing agent. Various additives and the like can be included in the protective layer coating solution.

Next, a method for manufacturing the decorative sheet 11 will be illustrated.
For example, the embossed sheet 12 is formed into a sheet by extrusion molding, and the embossed sheet 12 is manufactured by providing an uneven surface 16 with an embossing roll on the surface thereof. If necessary, the embossing roll is subjected to a graining process by sandblasting or the like. The coating solution for the protective layer is prepared by blending the antiwear particles 14 and the solvent with the binder 15 and having a viscosity of 200 mPa · s to 1000 mPa · s.
And the coating liquid for protective layers is apply | coated and printed on the surface of the embossed sheet 12 by screen printing, the protective layer 13 is formed, and the decorating sheet 11 is obtained.
In addition to the screen printing method, the protective layer 13 can be formed by various methods such as spray coating. However, the cost of the equipment, the selection of materials, the adjustment of the coating liquid and the adjustment of the coating amount, the decrease in yield, etc. A screen printing method is preferred from the viewpoint of productivity.

  According to the decorative sheet 11 and the method for manufacturing the decorative sheet 11, since the minute uneven surface 13 a is formed on the surface of the protective layer 13, the friction coefficient of the protective layer 13 can be reduced. Abrasion resistance can be increased. Since the wear-resistant particles 14 of the protective layer 13 are dispersed along the uneven surface 16 of the embossed sheet 12, the fine uneven surface 13 a can be formed on the entire surface of the protective layer 13. Abrasion resistance can be increased. Since the wear-resistant particles 14 are also disposed on the convex portions 16b of the uneven surface 16 that is easily rubbed, the wear resistance of the protective layer 13 covering the convex portions 16b can be improved. Further, since the wear-resistant particles 14 are arranged without overlapping the convex portion 16b, the protective layer 13 can be formed so as to follow the outer shape of the convex portion 16b on the concave-convex surface 16, and the concave-convex surface 16 feels uneven. It can be made difficult to lose.

Second Embodiment [FIG. 4] :
A sectional view of the decorative sheet 21 of the present embodiment is shown in FIG. Unlike the decorative sheet 11 of the previous embodiment, the decorative sheet 21 of the present embodiment includes a decorative layer 28. Other components, functions, effects, and the like are the same as those of the decorative sheet 11.

  The decorative layer 28 is provided on the surface of the concavo-convex surface 16 of the embossed sheet 12, and gives the decorative sheet 21 a variety of textures by giving display elements such as letters, symbols, and numbers, and patterns such as coloring and design patterns. Is a layer.

As a material for the decorative layer 28, a resin that is a decorative composition having good adhesion to the embossed sheet 12 can be used. Examples of the resin include acrylic resin, vinyl chloride resin, vinyl acetate resin, and urethane. Examples thereof include resins, epoxy resins, polyester resins, urethane acrylates, polyester acrylates, and epoxy acrylates.
The decorative composition can be obtained by mixing such a resin with a coloring material such as a pigment or a dispersant and diluting with a solvent.

The decorative layer 28 can be formed to have a thickness of about 1 μm by applying a decorative composition to the surface of the embossed embossed sheet 12 by gravure coating, for example. The protective layer 13 is formed by applying a protective layer coating liquid to the surface of the decorative layer 28 by screen printing. In addition to the gravure coating, the decoration layer 28 can be formed by various printing methods such as screen printing and various coating methods such as spray coating.
As another method, after the decorative layer 28 is formed on the flat embossed sheet 12, the uneven surface 16 can be formed by embossing.
The decorative sheet 21 obtained in this way is a decorative sheet 21 having not only a feeling of unevenness but also a texture that is excellent in design with display elements and patterns. Further, since the decorative layer 28 is provided between the embossed sheet 12 and the protective layer 13, the decorative layer 28 is easier to visually recognize than the case where the decorative layer 28 is provided on the back surface of the embossed sheet 12, and the It is possible to obtain a better decorative feeling that is closer to the real thing, such as denim. Moreover, since the decoration layer 28 is covered with the protective layer 13, even if the decoration layer 28 is thin, the decoration layer 28 can be protected and hardly peeled off.

Third Embodiment (FIG. 5) :
The present embodiment relates to a decorative molded body 31 in which the decorative sheets 11 and 21 shown in the previous embodiment are provided on the surface of the molded body.
The decorative molded body 31 shown here is obtained by fixing the decorative sheets 11 and 21 to a resin molded body that becomes the casing 32 of the mobile phone 30 via an adhesive layer 33 made of an adhesive. FIG. 5 shows a perspective view of the mobile phone 30 and a partially enlarged cross-sectional view of the decorative molded body 31 that forms the surface of the mobile phone 30.
According to the decorative molded body 31, it is possible to obtain a molded body excellent in design.

  The decorative sheets 11 and 21 including the embossed sheet 12 and the protective layer 13 and the decorative molded body 31 in which these decorative sheets 11 and 21 are fixed to the surface of the molded body are illustrated, but the embossed sheet is provided on the surface of the molded body. An uneven surface similar to the 12 uneven surface 16 may be directly formed, and a protective layer 13 may be formed on the surface to provide a “decorated molded body” including the molded body and the protective layer 13.

  Next, the present invention will be described in more detail based on experimental examples.

1. Decorative sheet manufacturing :

Sample 1 :
A carbon-like embossed sheet (12) made of ABS resin was prepared. When the cross section of the embossed sheet (12) was observed with an electron microscope, the thickness was 350 μm and the maximum height roughness Rz of the uneven surface (16) was 40 μm. On the surface of the concavo-convex surface (16) of the embossed sheet (12), a decorative layer (28) having a thickness of about 1 μm was formed with a decorative composition made of a black metallic urethane resin.
Next, a protective layer coating solution for forming the protective layer (13) was prepared. The resin component used as the binder (15) is urethane ink (SG429R manufactured by Seiko Advance, the pencil hardness after curing is 2H), and the abrasion-resistant particles (14) are silica abrasion-resistant particles having a pencil hardness exceeding 2H (Fuji Siricia 476 manufactured by Silysia Chemical, average particle size = 14 μm) was used, respectively, and the anti-wear particles (14) were blended at 21 vol% with respect to the resin component. At this time, the solvent was increased from that for normal printing and the viscosity of the protective layer coating solution was adjusted to 500 mPa · s. The viscosity was measured using an E-type rotational viscosity system VISCO88BV manufactured by Borlin, and the value when the rotational speed was 35 rpm was taken as the viscosity value. Further, the ratio between the viscosity at a rotational speed of 35 rpm and the viscosity at 350 rpm was calculated to obtain a thixotropy index value. The viscosity was measured based on JIS K7117-2, and the thixotropy index value was introduced based on the description of JIS K6833-1.
This protective layer coating solution was printed on the surface of the decorative layer (28) by screen printing to obtain a decorative sheet (21). The printing plate used was 270 mesh made of nylon and the emulsion thickness was 12 μm. The obtained decorative sheet (21) was designated as Sample 1.
In addition, the mixing | blending capacity | capacitance ratio of the abrasion-resistant particle | grain was computed as follows. First, the blending volume of the binder is calculated from the blending weight part × solid content ratio / specific gravity, while the blending volume of the anti-wear particles is calculated from blending weight part × volume per unit weight (apparent volume for porous). The total amount of the obtained binder and anti-abrasion particles was set to 100, and the respective ratios were converted to vol%.

Sample 2 :
Another decorative sheet (21) was produced in the same manner as Sample 1 except that Rz of the uneven surface (16) of the embossed sheet (12) was set to 70 μm.
Sample 3 :
Another decorative sheet (21) was produced in the same manner as Sample 1, except that the Rz of the uneven surface (16) of the embossed sheet (12) was set to 90 μm.
Sample 4 :
Another decorative sheet (21) was produced as Sample 4 in the same manner as Sample 1, except that the uneven surface (16) of the embossed sheet (12) was 120 μm.

Sample 5 :
Similar to Sample 1, except that the Rz of the uneven surface (16) in the embossed sheet (12) was changed to 50 μm, and the wear-resistant particles (14) were changed to silica wear-resistant particles having an average particle diameter of 11 μm (Silicia 780 manufactured by Fuji Silysia Chemical). Another decorative sheet (21) was produced as Sample 5.
Sample 6 :
Another decorative sheet (21) was produced as Sample 6 in the same manner as Sample 1, except that the wear-resistant particles (14) were changed to silica wear-resistant particles having an average particle diameter of 8 μm (Silicia 450 manufactured by Fuji Silysia Chemical). .
Sample 7 :
Sample 7 differs from Sample 1 in that the abrasion-resistant particles (14) are made of acrylic resin beads (transparent crosslinked acrylic beads GR400 manufactured by Negami Kogyo Co., Ltd., pencil hardness 2H, average particle size = 14 μm). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 7.

Sample 8 :
Sample 8 is different from Sample 1 in that Rz of the uneven surface (16) in the embossed sheet (12) is set to 60 μm. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 8 was obtained.
Sample 9 :
Sample 9 is different from Sample 1 in that Rz on the uneven surface of the embossed sheet is set to 10 μm. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated Sample 9.
Sample 10 :
Sample 10 is different from Sample 1 in that Rz on the uneven surface of the embossed sheet is set to 170 μm. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 10.

Sample 11 :
The sample 11 is different from the sample 1 in that the protective layer does not include anti-wear particles. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 11 was obtained.
Sample 12 :
The sample 12 is different from the sample 1 in that the protective layer does not include anti-wear particles. Furthermore, the layer thickness of the binder was made thinner than that of Sample 11. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated Sample 12.
Sample 13 :
Sample 13 is different from Sample 1 in that the wear-resistant particles are soft urethane resin beads (Negami Kogyo's crosslinked urethane beads C400, pencil hardness B, average particle size = 14 μm). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated Sample 13.

Sample 14 :
Sample 14 differs from Sample 1 in that the wear-resistant particles are soft urethane resin beads (Negami Kogyo's crosslinked urethane beads C800, pencil hardness B, average particle size = 6 μm). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 14.
Sample 15 :
Sample 15 differs from Sample 1 in that the wear-resistant particles are silica wear-resistant particles having an average particle size of 2.7 μm (Silicia 530 manufactured by Fuji Silysia Chemical). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 15.
Sample 16 :
Sample 16 differs from Sample 1 in that the wear-resistant particles are silica wear-resistant particles having an average particle size of 2.7 μm (Silicia 530 manufactured by Fuji Silysia Chemical). Further, the layer thickness of the binder was made thinner than that of Sample 15. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 16.

Sample 17 :
Sample 17 differs from Sample 1 in that the wear-resistant particles are silica wear-resistant particles having an average particle size of 0.016 μm (Aerosil RY200S manufactured by Nippon Aerosil). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and designated as Sample 17.
Sample 18 :
Sample 18 is different from Sample 1 in that the viscosity of the coating liquid for the protective layer was adjusted to 1100 mPa · s. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 18 was obtained.
Sample 19 :
Sample 19 is different from Sample 1 in that the wear-resistant particles are acrylic resin beads (Toughtic AR650MZ manufactured by Toyobo, pencil hardness 2H, average particle size = 60 μm). Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 19 was obtained.

Sample 20 :
Sample 20 differs from Sample 1 in that the wear-resistant particles are made of acrylic resin beads (Toyobo Tufic AR650MZ, pencil hardness 2H, average particle size = 60 μm). Further, the binder was formed thicker than the sample 19. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 20 was obtained.
Sample 21 :
The sample 21 is different from the sample 1 in that no protective layer is provided. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 21 was obtained.
Sample 22 :
The sample 22 differs from the sample 1 in that the protective layer is not provided with wear-resistant particles, and a urethane-based protective layer coating liquid (Neolabasan N78100 made by Musashi Paint) having a pencil hardness of HB is used as a binder. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 22 was obtained.
Sample 23 :
Sample 23 is different from Sample 1 in that the viscosity of the protective layer coating solution was adjusted to 180 mPa · s. Other than that, another decorative sheet (21) was produced in the same manner as Sample 1, and Sample 23 was obtained.

2. Test method :
For the above samples 1 to 23, various values shown below were measured and calculated, and two items of “abrasion resistance” and “maintenance ratio of unevenness in the protective layer” were evaluated. These results are shown in Tables 1 and 2.

“Maximum height roughness (Rz) of uneven surface in embossed sheet” (in the table: Rz);
The longitudinal section of the embossed sheet was observed and measured with an electron microscope.
“Viscosity of coating liquid for protective layer” (in the table: viscosity);
The viscosity at a rotational speed of 35 rpm was measured with a Borlin E-type rotational viscometer VISCO88BV.
“Pencil hardness of abrasive particles and binder” (in the table: pencil hardness);
About anti-abrasion particle | grains, it measured according to the prescription | regulation of JISK5600-5-4 about the board piece of the same material. About the binder, it measured similarly about the coating film which printed itself on glass according to the prescription | regulation of JISK5600-5-4.

“Thickness of the binder at the convex part of the uneven surface” (in the table: thickness of the convex part);
The uneven surface of the embossed sheet was observed with an electron microscope, and the thickness of the binder in the portion where there was no anti-abrasion particle in the convex portion was measured.
“Thickness of the binder in the concave portion of the uneven surface” (in the table: thickness of the concave portion);
The uneven surface of the embossed sheet was observed with an electron microscope, and the thickness of the binder in the recess was measured. Note that, since the wear-resistant particles were almost buried in the recesses, the thickness of the binder was almost the same as the thickness of the protective layer.
“TI value of coating liquid for protective layer” (in the table: TI value);
The viscosity at a plurality of rotation speeds was measured, a correlation graph between the rotation speed and the viscosity was created, and the ratio of the viscosity values at 35 rpm and 350 rpm was calculated.

“Ratio of average particle size of wear-resistant particles to Rz of uneven surface” (in the table: ratio of particle size to Rz);
It calculated with the following formula (1).
([Average particle size of wear-resistant particles] / [Rz of uneven surface]) × 100 Formula (1)
“Ratio between the thickness of the binder at the convex portion of the uneven surface and the average particle size of the wear-resistant particles” (in the table: ratio of the convex portion thickness to the particle size);
It calculated with the following formula (2).
([Binder thickness at convex part] / [Average particle size of anti-abrasion particles]) × 100 Formula (2)
“Ratio of the binder thickness in the concave portion of the concave / convex surface to Rz of the concave / convex surface” (in the table: ratio of the concave portion thickness to Rz);
It calculated with the following formula (3).
([Binder Thickness in Recess] / [Rz of Concave Surface]) × 100 Formula (3)

“Abrasion resistance” (in the table: wear resistance);
Using a sand eraser (RADIC, 500B manufactured by Sakura Crepas Co., Ltd.), the surface of each sample was rubbed under conditions of a load of 500 g, a moving stroke of 25 mm, and a speed of 60 / min. In the table, “good” indicates that the reciprocation of the sand eraser took 100 times or more until the embossed sheet was exposed, and “insufficient” indicates that the embossed sheet was exposed by reciprocation of the sand eraser less than 100 times.
“Roughness maintenance ratio in protective layer” (in the table: unevenness maintenance ratio);
It calculated how much Rz after protective layer formation was changing with respect to Rz of the uneven surface of an embossed sheet. The same Rz value is obtained at 100%.

3. Test results :
Samples 1 to 8 were excellent in “wear resistance”, and an excellent result of “maintenance ratio of the unevenness of the protective layer” was 50% or more. On the other hand, Sample 12 to Sample 14, Sample 16, Sample 17, Sample 19, Sample 21 to Sample 23 have insufficient “wear resistance”, and Sample 9 to Sample 11, Sample 15, Sample 17 to Sample No. 19 had a feeling of unevenness. The sample 20 had completely different unevenness feeling. Details of Sample 10 to Sample 23 will be described below.

Since the Rz of Sample 9 was as small as 10 μm, the concave portion of the uneven surface was filled with the protective layer, and the “ratio of Rz of the uneven surface to the thickness of the binder in the concave portion of the uneven surface” was 220%. For this reason, the “irregularity maintenance ratio in the protective layer” was as low as 10%, and the feeling of unevenness was lost.
Since the sample 10 had a large Rz of 170 μm, it was difficult for the protective layer to adhere to the concave portion of the uneven surface, and the “binder thickness in the concave portion of the uneven surface” was as thin as 3 μm. For this reason, the protective layer could not be formed uniformly, and the unevenness was greatly changed.
In Sample 11, since the protective layer did not contain anti-wear particles, the concave portion of the uneven surface was filled with the protective layer, and the “ratio of Rz of the uneven surface to the thickness of the binder in the concave portion of the uneven surface” was 100%. For this reason, the “irregularity maintenance ratio in the protective layer” was as low as 25%, and the unevenness was lost.

Sample 12 does not contain anti-abrasion particles in the protective layer as in sample 11, and the thickness of the binder is reduced in order to maintain the uneven feeling. The “thickness” has become as thin as 2 μm. For this reason, “abrasion resistance” was insufficient.
In Sample 13, since the pencil hardness of the abrasion-resistant particles was as soft as B, the abrasion-resistant particles were easy to fall off. For this reason, “abrasion resistance” was insufficient. This is considered that when the sand eraser was in contact with the protective layer, the wear-resistant particles were deformed and the interface between the wear-resistant particles and the binder was easily peeled off.
Sample 14 was softer in pencil hardness of the abrasion-resistant particles as in Sample 13, but the average particle size of the abrasion-resistant particles was smaller than that of Sample 13. However, the wear-resistant particles easily fall off and the “abrasion resistance” is insufficient.

In Sample 15, the wear-resistant particles are as small as 2.7 μm, so that the binder flows into the concave portion of the concave and convex surface and the concave portion of the concave and convex surface is filled with the protective layer. “Ratio of Rz of the concave and convex surface and the thickness of the binder in the concave portion of the concave and convex surface Was 88%. For this reason, the “roughness maintenance ratio in the protective layer” was as low as 38%, and the unevenness feeling was lost. Even if the viscosity of the coating liquid for the protective layer is 900 mPa · s and 1000 mPa · s or less, if the thixotropy index value is as large as 1.6, the fluidity is lowered and it is difficult to form a uniform coating film.
In Sample 16, the thickness of the binder was reduced because the wear-resistant particles were as small as 2.7 μm as in Sample 15, but the “thickness of the binder on the convex portion of the uneven surface” was reduced to 2 μm. For this reason, “abrasion resistance” was insufficient.
In Sample 17, the wear-resistant particles are as small as 0.016 μm, so that the binder flows into the concave portion of the concave and convex surface and the concave portion of the concave and convex surface is filled with the protective layer. “Rz of the concave and convex surface and the thickness of the binder in the concave portion of the concave and convex surface Ratio "was 80%. For this reason, the “retention ratio of the unevenness in the protective layer” was as low as 40%, and the unevenness feeling was lost. Furthermore, “abrasion resistance” was insufficient.

In Sample 18, the viscosity of the coating liquid for the protective layer was as high as 1100 mPa · s and the amount of the solvent was small. %. For this reason, the “irregularity maintenance ratio in the protective layer” was lowered to 48%, and the feeling of unevenness was lost.
Sample 19 had a large wear-resistant particle of 60 μm and a “ratio of Rz on the uneven surface to the average particle diameter of the wear-resistant particle” of 150%, which was extremely large with respect to the unevenness. The protective layer applied under the same conditions as Sample 1 had a “ratio of the average particle diameter of the wear-resistant particles to the thickness of the binder at the convex portions of the irregular surface” as small as 22%. For this reason, the abrasion-resistant particles dropped off, and the “abrasion resistance” was insufficient. In addition, the concave portion of the uneven surface was filled with the wear-resistant particles and the binder, and the “ratio of Rz of the uneven surface to the thickness of the binder in the concave portion of the uneven surface” increased to 75%. For this reason, the “retention ratio of the unevenness in the protective layer” was as low as 40%, and the unevenness feeling was lost.
Sample 20 used 60-μm large anti-abrasion particles as in sample 19, and the binder thickness was increased in order to suppress the anti-oating of anti-wear particles at the protrusions. The unevenness could not be maintained.

Since the sample 21 was not provided with a protective layer, the embossed sheet was worn with sand eraser, and the “wear resistance” was insufficient.
In Sample 22, the pencil hardness of the binder was as soft as HB, so that the wear-resistant particles were likely to fall off and the “abrasion resistance” was insufficient.
In sample 23, the viscosity of the coating liquid for the protective layer was as low as 180 mPa · s, so the protective layer could not be formed uniformly, and “abrasion resistance” was insufficient.

1 decorative sheet (conventional technology)
3 Protective layer (conventional technology)
11 Decorating sheet (first embodiment)
DESCRIPTION OF SYMBOLS 12 Embossed sheet 13 Protective layer 13a Micro uneven surface 14 Abrasion-resistant particle 15 Binder 16 Concavity and convexity surface 16a Concave surface 16b Convex portion 17 Textured surface 17a Fine concave portion 21 Decorating sheet (second embodiment)
28 decorative layer 30 mobile phone 31 decorative molded body (third embodiment)
32 Housing 33 Adhesive layer

Claims (13)

In the decorative sheet provided with a protective layer that protects the unevenness of the surface so as not to damage the embossed sheet whose maximum height roughness Rz of the uneven surface whose surface has been processed unevenly is 40 μm to 120 μm,
The protective layer comprises anti-wear particles and a binder that stops the anti-wear particles on the embossed sheet surface,
The protective layer has a binder whose hardness after curing is a pencil hardness of H or more, a hardness equal to or greater than that of the binder, an average particle size of 8 μm or more, and a size of 35% or less of Rz on the embossed sheet surface. A protective layer coating solution that contains anti-wear particles with a viscosity of 200 mPa · s to 1000 mPa · s and a thixotropy index value of 1.0 or more and less than 1.5 is applied to the surface of an embossed sheet by screen printing. And
The thickness of the protective layer is 50% to 110% with respect to the particle size of the anti-abrasion particles, and the outer shape of the anti-wear particles is exposed on the surface of the protective layer. ,
The decorative sheet is characterized in that the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions processed in the embossed sheet. In the decorative sheet provided with a protective layer that protects the embossed sheet having an uneven surface whose surface is unevenly processed so as not to damage the unevenness of the surface,
The protective layer comprises anti-wear particles and a binder that stops the anti-wear particles on the embossed sheet surface,
In the embossed convex portion of the embossed sheet, the thickness of the protective layer is 50% to 110% of the particle size of the antiwear particles, and the outer shape of the antiwear particles appears on the surface of the protective layer. The decorative sheet is characterized in that the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions of the embossed sheet.   The maximum height roughness Rz of the concavo-convex surface of the embossed sheet is 40 μm to 120 μm, the average particle size of the wear-resistant particles is 8 μm or more, and the size is 35% or less of Rz on the surface of the embossed sheet. Item 3. A decorative sheet according to item 2.   4. The decorative sheet according to claim 2, wherein the binder is an organic polymer material having a hardness of H or higher in pencil hardness, and the wear-resistant particles have a hardness equal to or higher than that of the binder.   The decorative sheet according to any one of claims 2 to 4, wherein the mixing ratio of the anti-wear particles in the protective layer to the binder is 10 vol% to 50 vol%.   Abrasion-resistant particles are distributed and arranged along the surface of the embossed sheet, and are arranged so as not to overlap at the convex portions of the embossed sheet, thereby forming a micro uneven surface along the outer shape of the wear-resistant particles on the surface of the protective layer. The decorative sheet according to any one of claims 1 to 5.   The decorative sheet according to any one of claims 1 to 6, wherein the protective layer is a matte transparent resin layer.   The decorative sheet according to any one of claims 1 to 7, wherein the embossed sheet has a textured surface corresponding to the particle size of the wear-resistant particles, unlike the uneven surface.   The decorative sheet according to any one of claims 1 to 8, wherein a decorative layer is provided between the embossed sheet and the protective layer. In the method for producing a decorative sheet provided with a protective layer that protects the surface of the embossed surface with unevenness on the surface so as not to damage the unevenness of the surface on the embossed sheet having a maximum height roughness Rz of 40 μm to 120 μm.
A binder whose hardness after curing is H or more in pencil hardness, an abrasion resistance having a hardness equal to or greater than the hardness of the binder, an average particle size of 8 μm or more, and a size of 35% or less of Rz on the surface of the embossed sheet Containing particles, adjusting with a solvent to prepare a protective layer coating solution having a viscosity of 200 mPa · s to 1000 mPa · s and a thixotropic index value of 1.0 or more and less than 1.5;
Applying the protective layer coating liquid on the surface of the embossed sheet by screen printing to form a protective layer,
The thickness of the protective layer is 50% to 110% with respect to the particle size of the wear-resistant particles at the uneven portions of the embossed sheet, and the outer shape of the wear-resistant particles is exposed on the surface of the protective layer. And
A method for producing a decorative sheet, comprising producing a decorative sheet in which the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions of the embossed sheet. In the embossed sheet having a concavo-convex surface whose surface is processed into a concavo-convex surface, a method for producing a decorative sheet provided with a protective layer that protects the surface so that the concavo-convexity is not impaired.
A coating solution for a protective layer containing a binder and antiwear particles, adjusted with a solvent and having a viscosity of 200 mPa · s to 1000 mPa · s and a thixotropic index value of 1.0 to less than 1.5 is prepared. A method for producing a decorative sheet, comprising: applying a protective layer on the surface by screen printing to form a protective layer, and producing a decorative sheet. In the method for producing a decorative sheet provided with a protective layer that protects the surface of the embossed surface with unevenness on the surface so as not to damage the unevenness of the surface on the embossed sheet having a maximum height roughness Rz of 40 μm to 120 μm.
A protective layer coating solution containing a binder and an anti-abrasion particle having an average particle size of 8 μm or more and 35% or less of Rz on the surface of the embossed sheet is prepared, and the surface of the embossed sheet is screen-printed by screen printing. Apply a protective layer coating solution to form a protective layer,
The thickness of the protective layer is 50% to 110% with respect to the particle size of the wear-resistant particles at the uneven portions of the embossed sheet, and the outer shape of the wear-resistant particles is exposed on the surface of the protective layer. And
A method for producing a decorative sheet, comprising producing a decorative sheet in which the thickness of the protective layer is 70% or less of the maximum height roughness Rz of the embossed sheet in the concave and convex portions of the embossed sheet.   A decorative molded body having the decorative sheet according to any one of claims 1 to 9 on a surface thereof.

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