JP2022154695A - Transfer sheet, and method for manufacturing decorative material and decorative material using the same - Google Patents

Abstract

To provide a transfer sheet which has excellent visibility and texture of matting effects, and excellent moist touch feeling.SOLUTION: A transfer sheet has a transfer layer on a releasable support, and has a surface shape of Ssk (skewness) of less than 0.00 which is defined in ISO 25178-2:2012, on at least a part of the surface on the releasable support side of the transfer layer.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a transfer sheet, a method for producing a decorative material using the transfer sheet, and a decorative material.

Conventionally, for example, interior members of buildings such as walls, ceilings and floors; In addition to fixtures and fixtures such as malls, general furniture such as wardrobes, shelves, and desks, kitchen furniture such as dining tables and sinks, various types of furniture and components used around water such as kitchens, toilets, bathrooms, and washstands, or BACKGROUND ART So-called decorative materials and decorative sheets are used as articles for decorating and protecting surfaces such as surface decorative boards for cabinets of home electric appliances and OA equipment, interior and exterior members of vehicles, and the like. As such decorative materials and decorative sheets, for example, those having a surface layer having a desired function are used. performance is required.

For decorative materials used for these purposes, a method of improving the texture by using a matte effect is widely used in order to improve the design of the materials. As a decorative material using a matte effect, for example, in Patent Document 1, a base sheet has a pattern layer and a concealing layer on one side, and has a gloss adjusting layer (mat layer, gloss layer) on the other side. A cosmetic sheet has been proposed. In the decorative sheet of Patent Document 1, the design effect of enhancing the pattern layer and the concealing layer is obtained due to the difference in gloss between the matte layer and the gloss layer of the gloss adjusting layer. For the layer, a matte ink is used in which a total of 50 parts by weight of matting agent, ie, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, is added to 100 parts by weight of resin.

Patent Document 2 proposes a decorative material having a printed layer and a transparent resin layer in this order on a substrate, and an embossed pattern on the outermost surface of the transparent resin layer.

JP-A-2000-062081 JP 2011-073207 A

As a technique for improving the texture by a matting effect, a matting agent (also referred to as a "matting agent") is used as in Patent Document 1, and the light diffusion effect itself is obtained. and a method of forming an uneven shape (also referred to as an uneven pattern) on the outermost surface by applying embossing as described in Patent Document 2.
However, when a matting agent is used as in Patent Document 1, it is necessary to increase the amount of the matting agent to achieve a better matting effect. It falls off from the coating film and damages the coating film, resulting in a decrease in scratch resistance, and the loss of the matting agent causes a change in gloss, making the scratches more noticeable, or contamination in the minute gaps at the interface between the matting agent and the resin. The surface properties tend to deteriorate due to the penetration of substances and the adsorption of contaminants to the matting agent itself, which lowers the stain resistance. On the other hand, if the amount used is reduced in order to suppress deterioration of the surface properties, the matting effect tends to be reduced, and the surface properties and the matting effect are in a dichotomy relationship. Therefore, there is a limit to the matte effect using matting agents.
In addition, when embossing is used as in Patent Document 2, preparation of embossing plates takes a lot of time and effort and is not easy. Therefore, it cannot be said that it is a method that can sufficiently respond to the diversity of customer demands. Moreover, in the embossing of Patent Document 2, the manufacturing process may be restricted, or it may be difficult to impart the uneven shape depending on the material of the article to be imparted with the uneven shape.

By the way, customer demands are diversified, and not only the above-mentioned visual matte effect but also tactile expression is required. For example, in the case of using a matting agent such as that of Patent Document 1, by increasing the amount of the matting agent used, the outline of the matting agent appears on the surface of the decorative sheet, resulting in a slightly rough touch. May occur. Moreover, when embossing is used as in Patent Document 2, a tactile sensation may be developed due to the uneven shape of the surface formed by the embossing plate. However, in any case, attention is not paid to the expression of the tactile sensation, and it cannot be said that the tactile sensation is sufficiently expressed. In other words, it cannot be said that the conventional decorative sheet can achieve both excellent matting effect and tactile feel. In the present invention, attention is paid to the "moist" tactile sensation among the tactile sensations.
Furthermore, as an embodiment for imparting a design to the surface of an article such as a decorative sheet, it is often the case that both an uneven shape and a decoration layer such as a pattern layer are imparted. In that case, in the inventions disclosed in Patent Documents 1 and 2, two different processes are required: a printing process for forming a pattern layer on the base material and an embossing process for shaping the concave-convex shape. Therefore, there is also the problem that the process time becomes long and the manufacturing cost becomes high.

An object of the present invention is to provide a transfer sheet that has excellent matte effect visibility and texture, as well as an excellent moist touch, a method for producing a decorative material using the same, and a decorative material. is.

In order to solve the above problems, the present invention provides the following [1] to [3].
[1] A transfer sheet having a transfer layer on a release support,
A transfer sheet, wherein at least a portion of the surface of the transfer layer on the release support side has a surface shape with an Ssk (skewness) of less than 0.00 as defined in ISO25178-2:2012.
[2] A method for producing a decorative material, comprising the following steps (1) and (2).
(1) A step of obtaining a laminate in which the transfer layer of the transfer sheet described in [1] and an adherend are in close contact with each other.
(2) A step of peeling off the release support from the laminate to obtain a decorative material having a transfer layer on the adherend.
[3] A decorative material having a transfer layer on an adherend,
A decorative material, wherein at least a part of the surface of the transfer layer opposite to the adherend has a surface shape with an Ssk (skewness) of less than 0.00 as defined in ISO25178-2:2012.

ADVANTAGE OF THE INVENTION According to this invention, the transfer sheet which has the visibility and feel of a material of the excellent matte effect, and is excellent in the moist touch can be provided. In addition, according to the present invention, it is possible to easily produce a decorative material that has excellent matte effect visibility and texture, as well as excellent moist touch.

FIG. 2 is a schematic diagram for explaining the surface shape of the transfer sheet of the present invention; FIG. 2 is a schematic diagram for explaining the surface shape of the transfer sheet of the present invention; 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 layer of the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram in planar view which shows one Embodiment of the transfer layer of this invention. 1 is a cross-sectional view showing an embodiment of the decorative material of the present invention; FIG. 4 is an optical microscope image of the release layer side surface of the decorative materials of Examples 1 and 3. FIG. 4 is an optical microscope image of the release layer side surface of the decorative material of Comparative Example 1. FIG. 4 is an optical microscope image of the release layer side surface of the decorative material of Comparative Example 2. FIG.

[Transfer sheet]
Hereinafter, embodiments of the present invention (hereinafter sometimes referred to as "present embodiments") will be described. In this specification, the numerical values related to "more than", "less than", and "to" regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are numerical values that can be used for the upper and lower limits of the numerical range. is.

The transfer sheet of the present embodiment has a transfer layer on a release support, and at least part of the surface of the transfer layer on the release support side is defined in ISO25178-2:2012. , Ssk (skewness) of less than 0.00.

FIG. 3 is a cross-sectional view showing one embodiment of the transfer sheet 100 of the present invention. A transfer sheet 100 in FIG. 3 has a transfer layer 20 on a release support 10 . Further, in FIG. 3, the release support 10 has a release layer 12 on the support 11 . In FIG. 3, the transfer layer 20 has a release layer 21, a primer layer 22, a decorative layer 23 and an adhesive layer 24 in this order from the side closer to the releasable support 10. As shown in FIG.
In the transfer sheet of FIG. 3, the release layer 21 is positioned on the release support 10 side of the transfer layer 20 . Therefore, in the transfer sheet of FIG. 3, at least part of the surface of the release layer 21, which is the surface of the transfer layer 20 on the release support 10 side, has a surface shape with an Ssk (skewness) of less than 0.00. have.

[About surface shape]
The surface shape of the transfer sheet of the present embodiment on at least a part of the surface of the transfer layer on the release support side (hereinafter also simply referred to as "surface shape of transfer layer" or "surface shape") will be described.
The surface shape of the transfer layer is reflected as the surface shape of the decorative material obtained by transferring the transfer layer to the adherend. As described above, the surface shape of the transfer layer is reflected as the surface shape of the decorative material obtained by transferring the transfer layer to the adherend. However, the surface shape of the transfer layer and the surface shape of the decorative material are different. , is not limited to being completely the same, and may vary slightly depending on the conditions of heat and pressure during transfer.
The surface shape must have Ssk (skewness) of less than 0.00 as defined in ISO25178-2:2012. By having such a surface shape, the transfer sheet of the present embodiment has excellent visibility and texture of the matte effect (hereinafter these are sometimes collectively referred to as "matte effect"). In addition to imparting it to the body, it can impart a particularly “moist” tactile sensation to the adherend. A “moist” tactile sensation is a sensual expression, but “moist” in the present specification generally includes all tactile sensations that give a “moist” feel. Specifically, it means the tactile sensation felt when touching a damp smooth surface with the pad of a finger. Materials having a "moist" feel include, for example, natural fiber fabrics such as silk and Tencel (Lyocell), synthetic fibers such as Promix, rayon and cupra, chemical fiber fabrics such as regenerated fibers, or Fabrics of these chemical fibers processed with peach skin (thinly raised to have a texture similar to that of the skin of peach fruit), and the like.

Ssk (skewness) is one of the three-dimensional surface texture parameters defined by the ISO, and is an index indicating the degree of deviation of height distribution from the average surface. When Ssk is 0, the surface shape is symmetrical (normal distribution) with respect to the average plane. , are measured values from which it can be grasped that the vicinity of the top of the convex portion tends to be sharp and thin. On the other hand, when Ssk is less than 0, the surface shape is biased to the upper side, that is, to the higher side with respect to the average plane (average level plane (horizontal line in FIGS. 1 and 2)), and the vicinity of the top of the convex portion is dull. It is a measured value that can be grasped that there is a tendency to become thicker. The shape tendency of the surface shape indicated by Ssk (skewness) will be described with reference to FIG. FIG. 1 is a schematic diagram of when Ssk (skewness) is less than 0 (1-1) and when it exceeds 0 (1-2). The fact that the Ssk (skewness) of the surface shape in this embodiment is less than 0.00 indicates that the surface tends to have the shape shown in (1-1). That is, since the surface shape is biased upward with respect to the average plane (average level plane (horizontal line in FIG. 1)), the surface shape imparted by the transfer sheet of the present embodiment is higher than the average plane. It can be said that there are many protrusions with a wide width (a low aspect ratio) and a shape close to a rectangle (trapezoid) in cross section, and that the protrusions are closely distributed. Due to the surface shape having such a shape, the contact area is large when touched with the pad of the finger, so that it feels stuck, which leads to the tactile sensation that you feel when you touch a moist and smooth surface. it is conceivable that. In addition, it is considered that the presence of such a convex portion results in relatively having a concave portion between the convex portions, so that a matting effect is also obtained. The details of the expression of the matte effect will be described later.
Ssk (skewness) is preferably -0.10 or less, more preferably -0.25 or less, and still more preferably -0.45 or less from the viewpoint of improving the matte effect and moist touch, and is preferable as a lower limit. is -3.00 or more, preferably -2.00 or more, more preferably -1.50 or more, and even more preferably -1.30 or more.

The measurement of Ssk (skewness) is a value measured using a shape analysis laser microscope for a rectangle (1024 μm×768 μm) at an arbitrary portion of the surface shape of the transfer layer. The surface shape of the transfer layer can be measured after transferring the transfer layer to the adherend. Measurement conditions can be adjusted as appropriate, for example, measurement can be performed under the conditions described in Examples. In addition, Sku (kurtosis), which will be described later, and Rsm (average length of curve element), Rz (maximum height), and Ra (arithmetic mean roughness) related to contour curves can also be measured in the same manner.

In the present embodiment, the surface shape preferably has a Sku (kurtosis) of 3.00 or more as defined in ISO25178-2:2012.
Sku (kurtosis) is one of the three-dimensional surface texture parameters defined by the ISO, and is an index indicating the degree of sharpness of the height distribution from the average plane. When Sku is 3, the surface shape is symmetrical (normal distribution) with respect to the average plane, when Sku exceeds 3, the height distribution has a sharp shape, and when Sku is less than 3, the height distribution is It is a measured value that can be grasped that there is a tendency to have a collapsed shape. The shape tendency exhibited by the surface shape indicated by Sku (Kurtosis) will be described with reference to FIG. FIG. 2 is a schematic diagram of Sku (kurtosis) exceeding 3.000 (2-1) and less than 3.00 (2-2). The fact that the Sku (kurtosis) of the surface shape in this embodiment is 3.00 or more means that the surface shape has the shape shown in (2-1), the height part before and after the average height is the largest, and the average The height distribution is such that there are few parts where the height protrudes more than the height and the parts where the height drops more than the average height. It can be said that there are few of them. In the surface shape that satisfies the above Ssk (skewness), if Sku (kurtosis) is 3.00 or more, tip-shaped projections and tip-shaped projections on the convex region that has a low aspect ratio shape with a wide width to height Since a small number of recesses with sharp bottoms are scattered, the contact area when touched with the pad of the finger does not spread over the entire surface like a simple flat surface (mirror surface). , and the protrusions and recesses that are scattered moderately divide and reduce the size, so that the degree of engagement with the pad of the finger becomes a moderate range, and the moist touch is improved. Moreover, the matting effect is also improved.

From the viewpoint of improving the matting effect and moist touch, Sku (Kurtosis) is preferably 3.05 or more, more preferably 3.10 or more, and still more preferably 3.15 or more, and the upper limit is preferably 5.5. It is 50 or less, more preferably 5.25 or less, still more preferably 5.00 or less.

The surface shape of the transfer layer of the present embodiment preferably has fine wrinkles (wrinkles) visible in a plan view shown in FIG. 5, which will be described later.
Regarding the surface shape of the transfer layer of the present embodiment, Ssk (skewness), and Sku (kurtosis), Rsm (average length of curvilinear element), Rz (maximum height), and Ra (arithmetic mean roughness), which will be described later. ) is likely to be within a specific numerical range due to having the minute wrinkles (wrinkles). In addition, the fine wrinkles (wrinkles) are Ssk (skewness) within a specific numerical range, and Sku (kurtosis), Rsm (average length of curve element), Rz (maximum height) within a specific numerical range and Ra (arithmetic mean roughness), it becomes easy to form. Thus, it can be said that Ssk (skewness) or the like and minute wrinkles (wrinkles) are inextricably linked. And, by having such a surface shape, the matte effect is improved along with the moist feel.

In this embodiment, it is preferable that Rsm (average length of curve element), which is a lateral parameter of the contour curve defined in JIS B0601:2013, be 100.00 μm or less.
Rsm (mean length of the curve element) is the lateral parameter of the profile and is the average length of the profile elements at the reference length. The smaller the numerical value of Rsm (average length of curvilinear element), the narrower the width of the protrusions, which is an index indicating that the surface shape tends to have narrower protrusions. Therefore, in a surface shape that satisfies the above Ssk (skewness), when Rsm (average length of curvilinear elements) is 100.00 μm or less, the width of the protrusions of the surface shape becomes narrower, and the width of the convex portion of the surface shape becomes narrower. By reducing the contact area when you touch it, the degree of hooking becomes appropriate, and the moist touch is improved. Moreover, the matting effect is also improved.
Rsm (average length of curvilinear elements) is preferably 90.00 μm or less, more preferably 80.00 μm or less, even more preferably 65.00 μm or less, and even more preferably, from the viewpoint of improving the matte effect and moist touch feeling. is 55.00 μm or less, and the lower limit is preferably 20.00 μm or more, more preferably 25.00 μm or more, and still more preferably 30.00 μm or more. Note that the cutoff value for the measurement of Rsm (average length of curvilinear element) in this specification is 0.8 mm.

In the present embodiment, the surface shape preferably has a lateral parameter Rz (maximum height) of the contour curve defined in JIS B0601:2013 of 3.00 μm or more.
Rz (maximum height) is one of the peak and height parameters of the contour curve, and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve at the reference length. The larger the numerical value of Rz (maximum height) is, the larger (higher) the shape of the protrusions are when viewed from the valley, which is an index indicating that there tends to be many such protrusions. Therefore, in the surface shape that satisfies the above Ssk (skewness), if Rz (maximum height) is 3.00 μm or more, the protrusions that are large (high) in shape as viewed from the valley when touched with the pad of a finger Since the resistance to each touch increases, the moist touch is improved. Moreover, the matting effect is also improved.
Rz (maximum height) is preferably 3.50 μm or more, more preferably 4.00 μm or more, still more preferably 4.50 μm or more, and still more preferably 4.50 μm or more, from the viewpoint of improving the matte effect and moist touch. It is 80 µm or more, and the upper limit is preferably 15.00 µm or less, more preferably 13.50 µm or less, even more preferably 11.00 µm or less, and even more preferably 10.00 µm or less. Note that the cutoff value for the measurement of Rz (maximum height) in this specification is 0.8 mm.

In the present embodiment, the surface profile preferably has Ra (arithmetic mean roughness) of 2.00 μm or less, which is a lateral parameter of the contour curve defined in JIS B0601:2013.
Ra (arithmetic mean roughness) is one of the parameters in the height direction of the profile curve, and is the average value of the difference in height from the average plane in the profile curve at the reference length. The smaller the numerical value of Ra (arithmetic mean roughness), the smaller the projections in the surface shape and the smaller the recesses formed accordingly, which is an index indicating that the surface tends to have a smoother and more uniform shape. Therefore, in the surface shape that satisfies the above Ssk (skewness), when Ra (arithmetic mean roughness) is 2.00 μm or less, the shape of the convex portions of the surface shape is more uniform and gentle. Therefore, the eccentric touch is suppressed, and especially the moist touch is improved. Moreover, the matting effect is also improved.
Ra (arithmetic mean roughness) is preferably 1.95 μm or less, more preferably 1.90 μm or less, still more preferably 1.80 μm or less, from the viewpoint of improving the matte effect and moist touch, and is preferable as a lower limit. is 0.10 μm or more, more preferably 0.40 μm or more, and still more preferably 0.60 μm or more. In addition, in measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

The surface shape of the transfer layer of the present embodiment preferably has wrinkles. By stabilizing the formation of wrinkles on the surface of the transfer layer, the matte effect is stably exhibited by the light diffusion effect caused by the shape of the wrinkles, and the layer also exhibits a moist feel. FIG. 5 is a schematic plan view showing one embodiment of the transfer layer of the transfer sheet of the present embodiment, and schematically illustrates an image of the surface of the decorative material on the transfer layer side obtained in the example. FIG. 5 shows that wrinkles are formed on the surface of the transfer layer of this embodiment. Here, “planar view” means viewing the surface of the transfer layer from the positive direction of the Z-axis in the XYZ coordinate system shown in FIGS.

Wrinkles appearing on at least one surface of the transfer layer have a surface shape having Ssk (skewness) within the above specific numerical range (preferably, Sku (kurtosis) within the above specific numerical range, Rsm (average length of curvilinear element), Rz (maximum height), and surface shape having Ra (arithmetic mean roughness)) are not particularly limited. In this way, the expression of wrinkles makes it easier to satisfy the above-mentioned surface shape, so that the appearance of wrinkles stably produces a matting effect and also expresses a moist touch.
Regarding wrinkles, at least one surface of the transfer layer may have an uneven shape composed of irregular wrinkles, from the viewpoint of expressing the surface shape, improving the matting effect, and improving the moist touch. Preferably, the irregular wrinkles are preferably composed of a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions, and the protrusions are filamentous. It is preferable to have projections. In the present specification, the term "protrusion of filament" (hereinafter also referred to as "filament projection") means that the ratio of the length and width of the protrusion (length/width) is 3 or more, preferably It means 5 or more, more preferably 10 or more, and the method for determining the length and width will be described later.
In the present embodiment, the more preferable irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and recesses formed by being surrounded by the plurality of filamentary protrusions. .

Examples of aspects related to these wrinkles include the aspect shown in FIG. 5 . FIG. 5 shows that the surface of the transfer layer has irregular wrinkles in plan view, and that the irregular wrinkles are formed by a plurality of curved filamentary projections, and a plurality of protrusions 3; It is configured by including a recess 2 formed by being surrounded by a plurality of protrusions (plurality of protrusions 3), and at least a part of the plurality of curved protrusions 3 is a meandering linear protrusion. It is also shown that a meandering recess 2 is formed by a portion and surrounded by the meandering filar projection. The transfer layer constituting the transfer sheet of the present embodiment stably exhibits a matting effect and also exhibits a moist feel due to the wrinkles shown in FIG.

Here, “curved” means having one or more portions in which the extending direction of the continuous filamentary projections 3 is reversed from one side to the other side in plan view. As an example of the portion where the extending direction is reversed from one side to the other side, for example, when the width of the planar view shape of the protrusion 3 of the filament is ignored (when the width is considered to be 0), a continuous curve Examples of approximation include a form having an inflection point. In addition, when approximating with a straight line when ignoring the width of the planar view shape of the protrusion 3 of the filament, a form having a portion approximated by two sides sandwiching one vertex of a V-shaped broken line or triangle etc.
In addition, the term "meandering" refers to a portion where the extending direction of the continuous linear projections 3 is reversed from one side to the other side (hereinafter also referred to as a "reversed portion") at least two times. There are at least two portions where the extension direction of the filament projections 3 is alternately reversed at two locations adjacent to each other when the filament projections 3 are advanced in their extending direction. means to have For example, when approximating with a continuous curve when ignoring the width of the projection 3 of the filaments in plan view, there is a form having a portion approximated by the Roman letter "S". Further, when the linear projections 3 are approximated by a straight line when the width of the projection 3 of the filament in plan view is ignored, there is a form having a portion approximated by the Roman letter "W".

In this specification, the term "irregular" means a shape having a certain rule, or a shape that is arranged according to a certain rule, which cannot be said to be patterned. A typical example of a non-irregular shape (regular shape) is a so-called "lenticular lens" in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to the longitudinal direction. , which are arranged in a specific direction with a certain periodicity. Therefore, the irregular wrinkles in the present embodiment are defined by the fact that the shape of one protrusion itself is irregular rather than a shape formed according to a certain rule such as periodicity, and that the shape of a plurality of protrusions formed by a plurality of protrusions is irregular. It includes that the shape of the protrusions is not formed and arranged according to a certain rule but is irregular, and that the shape of the recesses surrounded by such a plurality of protrusions is also irregular. be.
In the transfer layer constituting the transfer sheet of the present embodiment, the shape of one protrusion (one protrusion) itself, the shape and arrangement of each of a plurality of protrusions (plurality of protrusions), and the plurality of protrusions If any of the shapes of the enclosed recesses is irregular, a matte effect and a moist feel can be obtained by having irregular wrinkles, but it is preferable that both are irregular. The transfer sheet of the present embodiment has irregular wrinkles on the surface of the transfer layer, so that the visibility and texture of the matte effect are improved, the excellent matte effect is stably exhibited, and the texture is moist. It expresses a tactile sensation.

As described above, the transfer layer has wrinkles, that is, unevenness on at least one surface thereof. The median value of the height distribution in the uneven shape is used as a reference for the protrusions and recesses in the uneven shape, and a region having a height exceeding the median value is defined as a protrusion, and a region having a height equal to or less than the median value is defined as a recess. For example, using the density difference (i.e., lightness difference) of an image having a density corresponding to the height of the surface of the transfer layer of this embodiment, the darkest part of the density distribution image is set to gradation 255, and the density distribution image is With the lightest part as gradation 0 (the median density value corresponding to the median height value is 127), gradations 0 to 255 are defined as concave portions, and gradations 128 to 255 as convex portions. It suffices to classify them by binarizing them. The image may be photographed after transferring the transfer layer to the adherend.

Irregular wrinkles are preferably formed on at least a part of the surface of the transfer layer of the present embodiment, and more preferably irregular wrinkles are formed over the entire surface. The place where the wrinkles are formed is not particularly limited as long as it is the surface of the transfer layer. Effectiveness and moist touch are expressed.
Also, as shown in FIG. 5, it has a plurality of protrusions formed by a plurality of irregular but uniform protrusions and recesses surrounded by the protrusions. is preferred. Therefore, a shape in which the width of a single convex portion (projection) changes drastically is unlikely to result in the above-described surface shape, and is not a preferable aspect for obtaining the visibility and texture of the matte effect, and the texture is moist. It cannot be said that this is a preferable mode for obtaining a smooth tactile sensation. Concerning the shapes of protrusions (protrusions) and recesses that form irregular wrinkles, specific aspects that can be advantageous in stably improving the matting effect and improving the moist touch will be described below. . When the wrinkles have the following shape, the surface shape described above is likely to be exhibited, and the matting effect and moist touch are improved.

Regarding the shape of the wrinkles formed on at least one surface of the transfer layer, the height of the projections (the height of the protrusions) is preferably 0.5 µm or more, more preferably 1 µm or more, and still more preferably 2 µm or more. , and the upper limit is about 10 μm or less. The width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm. It is below. When the height and width of the protrusions are within the above ranges, the surface shape described above is likely to be exhibited, and in relation to the recesses, the matting effect is stably improved and the moist touch is improved.
Here, the above dimensions of the projections are arbitrary 10 projections (projections) at arbitrary 10 locations (100 μm square area × 10 locations) on the transfer sheet of the present embodiment, that is, the average of a total of 100 projections value. In addition, as shown in FIG. 5, the width of one protrusion (projection) is not the same, but wide and narrow, so the width of one protrusion (projection) is ) shall be the average value of the widths of any five locations. The same applies to the height of the projection (protrusion).

The depth of the concave portion is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. is. When the depth and width of the concave portions are within the above ranges, the surface shape described above is likely to be exhibited, and in relation to the convex portions, the matting effect is stably improved and the moist touch is improved.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The distance from the top of the projection to the bottom of the recess (height difference between the projection and the recess) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 2 μm or more. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the above surface shape is likely to be exhibited, the matting effect is stably improved, and the moist touch is improved.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and further preferably 60% or less. is. When the occupancy ratio of the convex portions is within the above range, the surface shape described above is likely to be exhibited, and in relation to the occupancy ratio of the concave portions surrounded by the convex portions, the matting effect is stably improved and the touch is moist. improves.
Here, the occupancy rate of the convex portion is the average value of the occupancy rate of the convex portion at arbitrary 10 locations (100 μm square area×10 locations) on the transfer sheet of the present embodiment.

Although the convex portion and the concave portion may have portions with substantially the same direction and substantially the same width, the length thereof is preferably short from the viewpoint of improving the matting effect and improving the moist feel. Specifically, the length of continuous protrusions and recesses having approximately the same direction and approximately the same width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, and the lower limit is preferably 5 μm or more. It is more preferably 10 μm or more, still more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, so that the matting effect is stably improved and the moist touch is improved.
Here, 80% or more of any 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) in arbitrary 10 locations (100 μm square area × 10 locations) of the transfer sheet of the present embodiment and more preferably 85% or more, still more preferably 90% or more, and still more preferably 95% or more. In addition, the “substantially” of “substantially the same” in this specification means that they are substantially the same, without branching, meaning a difference within ± 3 ° in the case of direction, and ± 5 in the case of width Means difference within %.

In addition, the number of protrusions (protrusions) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and further. Preferably it is 70 or less. When the number of protrusions is within the above range, the matting effect is stably improved, and the moist touch is improved.
The number of convex portions is the average value of the number of convex portions at 10 locations (100 μm square area×10 locations) on the transfer sheet of the present embodiment.

FIG. 4 is a cross-sectional view showing one embodiment of the transfer layer 20 that constitutes the transfer sheet of this embodiment, and is a cross section taken along a plane parallel to the thickness direction (the Z direction in the figure) of the transfer layer. It is a diagram.
The shape of the recess may be, for example, an acute-angled shape as shown in FIG. 4A, a semicircular or semielliptical shape as shown in FIG. 4B, or a combination thereof. Alternatively, a shape such as 2c in FIG. 4, in which one convex part has a concave part, may be used.
On the other hand, as for the shape of the projections, as shown in 3a and 3b in FIG. 4, although the widths are wide and narrow, they exhibit a semicircular or semielliptical shape.

Regarding the surface shape of the transfer layer, Ssk (skewness), Sku (kurtosis), Rsm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness) satisfy preferred ranges. Therefore, it is preferable to design the surface shape of the release support. This is because the surface shape of the transfer layer is a shape that reflects the surface shape of the release support.
Among the above parameters, the value of Ssk (skewness) reverses the sign of the value of the release support and the value of the transfer layer. For example, when the Ssk (skewness) of the release support is -1.06, the Ssk (skewness) of the transfer layer is 1.06. Of the above parameters, except for Ssk (skewness), the values of the release support and the values of the transfer layer are basically the same. It is preferable to adjust the surface shape of the release support in consideration of the above points.

The surface shape 1 of the article has a complementary surface shape to said shape 1 after being inverted once. When the complementary surface shape is inverted, it returns to the same surface shape as the surface shape 1. do.). That is, the surface profile of the article returns to its original surface profile after being flipped twice. For this reason, it is preferable to first prepare a matte layer as a base, and then use the surface shape of the releasable support by reversing the surface shape of the matte layer. The release support having a surface shape that is the reverse of the surface shape of the basic matte layer includes, for example, the following (1-1) to (1-2), (2-1) to (2-3), It can be produced by steps (3-1) to (3-2).

(1-1) A basic matte layer 1 that satisfies parameters such as Ssk is produced.
(1-2) The matte layer 1 is pressed against the surface of the releasable support, and a shape obtained by reversing the surface shape of the matte layer 1 is formed on the surface of the releasable support. If a laminate having a release layer on the support is used as the release support, and the release layer is left in an uncured state when the matte layer 1 is pressed against the surface of the release layer, The surface of the release layer (=the surface of the releasable support) can be formed with a shape obtained by inverting the surface shape of the matte layer 1 .

(2-1) A basic matte layer 1 that satisfies parameters such as Ssk is produced.
(2-2) A mold 1 having the same surface shape as that of the matte layer 1 is prepared. The mold 1 having the same surface shape as the matte layer 1 can be obtained, for example, by producing a mold 2 in which the surface shape of the matte layer 1 is reversed, and further by producing a mold in which the surface shape of the mold 2 is reversed. can be done. A mold obtained by reversing the surface shape of mold 2 is mold 1 . The mold 1 and the mold 2 can be manufactured by a general-purpose mold manufacturing method such as electroforming.
(2-3) The mold 1 is pressed against the surface of the releasable support, and a shape obtained by inverting the surface shape of the mold 1 (=the surface shape of the matte layer 1) is applied to the surface of the releasable support. mold. If a laminate having a release layer on the support is used as the release support, and the release layer is left in an uncured state when the mold 1 is pressed against the surface of the release layer, the release layer can be removed. The surface of the layer (=the surface of the releasable support) can be molded with a shape obtained by inverting the surface shape of the mold 1 (=the surface shape of the matte layer 1).

(3-1) A surface shape that satisfies parameters such as Ssk is designed by simulation, and a mold 3 is produced by reproducing the designed surface shape by laser microfabrication.
(3-2) The mold 3 is pressed against the surface of the releasable support, and a shape obtained by inverting the surface shape of the mold 3 (=surface shape satisfying parameters such as Ssk) is formed on the surface of the releasable support. to mold. If a laminate having a release layer on the support is used as the release support, and the release layer is left in an uncured state when the mold 3 is pressed against the surface of the release layer, the release layer can be removed. A shape obtained by inverting the surface shape of the mold 3 (=surface shape satisfying parameters such as Ssk and Sku) can be formed on the surface of the layer (=surface of the releasable support).

Also, as described above, the surface shape 1 of the article becomes a surface shape complementary to the shape 1 when inverted once. Therefore, the release support of the present embodiment can also be produced by the following steps (4-1) to (4-3).
(4-1) A matte layer 2 having a reversed surface shape that satisfies parameters such as Ssk is produced.
(4-2) A mold 4 having a surface shape that is the reverse of the surface shape of the matte layer 2 is produced. The surface shape of the mold 4 is a surface shape that satisfies parameters such as Ssk. The mold 4 can be manufactured by a general-purpose mold manufacturing method such as electrocasting.
(4-3) The mold 4 is pressed against the surface of the releasable support, and the surface shape of the mold 4 (=surface shape obtained by inverting the surface shape of the matte layer 2=Ssk, etc.) is applied to the surface of the releasable support. A surface shape that satisfies the parameters of ) is formed by inverting the shape. If a laminate having a release layer on the support is used as the release support, and the release layer is left in an uncured state when the mold 4 is pressed against the surface of the release layer, the release layer can be removed. On the surface of the layer (=surface of the releasable support), a shape obtained by reversing the surface shape of the mold 4 (=surface shape obtained by reversing the surface shape of the matte layer 2=surface shape satisfying parameters such as Ssk) is formed. It can be shaped.

Furthermore, it is also possible to directly form a desired transfer layer surface shape inverted on the release layer surface of the release support by the following steps (5-1) to (5-2). can.
(5-1) In preparing a release support, a layer of an uncured UV-curable resin composition for forming a release layer is formed on the support by an appropriate coating method.
(5-2) The layer of the uncured ultraviolet-curable resin composition is irradiated with short-wave ultraviolet rays from an excimer lamp or the like to cure the resin composition to form a release layer and on the surface Forms a fine wrinkled structure. At that time, by adjusting the composition of the resin composition and/or the irradiation conditions of the short wavelength ultraviolet rays, it is possible to form on the surface of the release layer a shape that is the reverse of the desired surface shape to be formed on the surface of the transfer layer. can.

[Basic matte layer]
The basic matte layer is
(1) forming a fine wrinkle structure on the surface of the matte layer;
is preferred.
Furthermore, the basic matte layer is
(2) Composition formulation of the resin composition for forming the matte layer, particularly the types of polymerizable monomers and polymerizable oligomers, the number of functional groups, the molecular weight, the presence or absence of a wrinkle-forming stabilizer, and the wrinkles when using a wrinkle-forming stabilizer optimizing the particle size and content of the forming agent;
(3) optimizing the irradiation conditions of the resin composition for matting formation, particularly the wavelength of light with a wavelength of 100 nm or more and 380 nm or less that can cause curing shrinkage of the surface portion of the matte layer, the integrated light amount, the ultraviolet power density, etc.
(4) In addition to the above, the type and thickness of the base material forming the matte layer, the thickness of the matte layer, etc. are optimized.
is preferred.
By optimizing these, Ssk (skewness) and the like for the basic surface shape of the matte layer (= the surface shape of the transfer layer in the present embodiment) are set within the above-mentioned specific numerical range, preferably Sku ( kurtosis), Rsm (average length of curvilinear element), Rz (maximum height), and Ra (arithmetic mean roughness) are easily set within predetermined numerical ranges.

The base material for forming the base matte layer may be used without any particular limitation, and may be appropriately selected according to desired properties and the like. From the viewpoint of improving the matte effect and moist touch, a base material composed of a resin or a fibrous material is preferable, and a base material composed of a resin is more preferable. Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable, olefin resins, vinyl chloride resins, and polyester resins are more preferable, polyethylene and polypropylene are preferable as olefin resins, and polyvinyl chloride is preferable as vinyl chloride resins. Polyethylene terephthalate is preferred as the polyester resin. As the resin used for the substrate, polyester resins are preferable among these, and polyethylene terephthalate is particularly preferable. Moreover, among fibrous materials, paper is preferable. By using a base material composed of these materials, it is particularly easy to obtain the surface shape described above, and it is easy to improve the moist touch.

The base matte layer is preferably a layer composed of a cured product of a resin composition, preferably a cured product of a curable resin composition containing a cured resin.

As the resin composition for forming the matte layer, a resin composition containing a resin and a wrinkle-forming stabilizer (hereinafter referred to as may be referred to as a "resin composition for forming a matte layer"). That is, the matte layer is preferably a layer containing a resin and a wrinkle stabilizer.

(wrinkle-forming stabilizer)
The wrinkle-forming stabilizer stabilizes the formation of wrinkles on at least one surface of the matte layer, thereby uniformly expressing the visibility of the matte effect over the entire surface of the matte layer and reducing partial gloss unevenness. Visibility of a stable matte effect (hereinafter simply referred to as "visibility of a stable matte effect" and similar expressions may be used) and uniformity of the surface condition (" It also has a function of imparting texture. The wrinkles formed in the matte layer greatly contribute to the development of a moist feel.
Therefore, the so-called "matting agent" in the prior art and the "wrinkle-forming stabilizer" in the present embodiment have the same matting mechanism ( function), the structure for expressing mattness, and the relationship between the amount used and the degree of surface luster (gloss value). It also differs from the "matting agent" in that it develops a moist feel by forming wrinkles.

Matting agents that have been used for matte expression in the prior art such as the above-mentioned Patent Document 1 express the visibility of the matting effect themselves due to the light diffusion effect caused by the physical shape. is. Specifically, what is generally called a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and the light reflection and refraction properties corresponding to the contour shape of the particles The visibility of the matte effect is expressed by the light diffusion effect of the interface. On the other hand, the wrinkle-forming stabilizer of the present embodiment does not express the visibility of the matting effect by light diffusion due to reflection and refraction of light rays by the particles themselves. By stabilizing the formation of wrinkles on the surface, the light diffusion effect at the refractive index difference interface between the surface and air stably imparts the visibility of the matting effect and texture to the matte layer. Therefore, the wrinkle-forming stabilizer used in the present embodiment is different from the matting agent that itself expresses the visibility of the matting effect (even if the constituent substances and the average particle size of both are the same. ,) The matting mechanism (action) of the two, the structure for expressing the matting, etc. are different.
Furthermore, the "wrinkle-forming stabilizer" and the "matting agent" also differ in the relationship between the content and surface luster (gloss value). 60° gloss value G _60° ^AW (C) of the surface when the same substance A is used as a wrinkle-forming initiator AW (W: wrinkles) and this is contained in a specific amount C to form wrinkles on the surface is clearly lower than the ₆₀ ° gloss value G of the surface when wrinkles are not formed on the surface even when the same substance A is used as a simple matting agent ^AM and this is contained in the specific amount C (C). do. That is, the following relational expression holds.
G _60° ^AW (C) < G _60° ^AM (C)

The matting layer may contain agents conventionally used as matting agents, but preferably does not contain matting agents. As described above, the matte layer of the present embodiment provides extremely excellent visibility and texture of the matte effect even without substantially containing a matting agent that has been used to obtain the visibility of the matte effect in the past. It can be said that it has Here, "does not contain a matting agent" means not containing a matting agent at all, and even if it does contain a matting agent, it does not have the visibility of the matting effect based on the action and effect of the matting agent itself. Specifically, it means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, more preferably 3.0 parts by mass or less per 100 parts by mass of the resin. .
As used herein, the term “matting agent” refers to a layer in which the matting agent can be specifically contained, i.e., the thickness of the matting layer, from the viewpoint of forming convex portions by the effect of cueing as described above. and 30 μm, whichever is smaller.

In the present embodiment, the wrinkle-forming stabilizer is not a delustering agent, especially if it has an average particle diameter of 100% or less of the matte layer thickness or 30 μm or less, whichever is smaller. Can be used without restrictions.
From the viewpoint of improving the matte effect and moist touch, the average particle size of the wrinkle-forming stabilizer having an upper limit of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, depends on the average particle size. It is preferred to use at least one of two distinct wrinkle stabilizers. Specifically, the two types of wrinkle-forming stabilizers have an average particle size of 1 μm or more and a wrinkle-forming stabilizer 1 whose upper limit is the smaller of 100% or less of the thickness of the matte layer and 30 μm or less. and wrinkle stabilizer 2 having an average particle size of less than 1 μm. In this embodiment, if at least one of the two wrinkle-forming stabilizers is used, the formation of wrinkles is stabilized, an excellent matting effect is stably obtained, and a moist touch is also obtained. In this embodiment, the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 can be used alone, or the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 can be used in combination to improve the matting effect and moist touch. It is more preferable to use the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 together from the viewpoint of improving the wrinkle-forming properties.

As the wrinkle-forming stabilizer, for example, organic particles and inorganic particles can be used.
Organic substances constituting organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin and polyester-based resin. etc.
Inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, and the like. Among these, silica is preferred because of its excellent transparency.

The shape of the wrinkle-forming stabilizer is not particularly limited, and examples thereof include spherical, polyhedral, scaly, and irregular shapes.

The upper limit of the average particle size of the wrinkle-forming stabilizer 1 is 1 μm or more and 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. From the viewpoint of stably improving the matting effect and improving the moist feel, the average particle size of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and still more preferably 1.5 μm or more. 8 μm or more, and the upper limit is preferably 90% or less of the thickness of the matte layer, more preferably 80% or less of the thickness of the matte layer, and still more preferably It is 70% or less of the thickness of the matte layer, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less. and the upper limit of the absolute value, whichever is smaller. For example, the upper limit may be 90% or less of the matte layer thickness or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the matte layer thickness may be the upper limit. can also The thickness of the matte layer will be described later.

Moreover, the average particle size of the wrinkle-forming stabilizer 2 is less than 1 μm. From the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the moist touch, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more. It is preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle-forming stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

From the viewpoint of stabilizing the formation of wrinkles by the wrinkle-forming stabilizer, stably improving the matting effect, and improving the moist touch, the wrinkle-forming stabilizer (wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 When used together, the total content of these) is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, and still more preferably 100 parts by mass of the resin forming the matte layer is 1.0 parts by mass or more, more preferably 1.2 parts by mass or more, and the upper limit is not particularly limited from the viewpoint of stable improvement of matting effect and improvement of moist touch, but for example From the viewpoint of improving the productivity of the decorative material due to the applicability of the resin composition for forming the matte layer, and efficiently improving the visibility and texture of the matte effect, it is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 7.5 parts by mass or less, and particularly preferably 6.0 parts by mass or less.

When the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 are used in combination, the content of each of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is not particularly limited as long as the total content is within the above range. However, the content of the wrinkle-forming stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1.0 parts by mass or more with respect to 100 parts by mass of the resin. , the upper limit is preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, still more preferably 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or less. Further, the blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 0.05 to 0.95 as the blending amount of the wrinkle-forming stabilizer 1 when the total amount of these is 100 parts by mass. parts by mass, more preferably 0.10 to 0.90 parts by mass, still more preferably 0.20 to 0.80 parts by mass, and even more preferably 0.30 to 0.70 parts by mass.

As the wrinkle-forming stabilizer, organic particles and inorganic particles can be used as described above. Matting agents such as spherical alumina and calcium carbonate are used in the matte layer of the decorative sheet described in 1 above. In order for matting agents such as spherical alumina and calcium carbonate to express the visibility of the matting effect themselves due to the light diffusion effect resulting from their physical shape, as described in Patent Document 1, It is necessary to use 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate in a total amount of about 50 parts by weight per 100 parts by weight of resin. However, in the present embodiment, even if the content is small as described above, that is, the content necessary for expressing the visibility of the matte effect itself due to the light diffusion effect caused by the physical shape Even if the content is smaller than the amount, a very excellent matting effect is obtained compared to the effect obtained by the matting agent, and a moist touch is also obtained. Therefore, although the matting layer of the present embodiment does not substantially contain a matting agent, wrinkles are stably formed on the surface, so that it is superior to the case where a matting agent is used. It can be said that the visibility of the matte effect is stably obtained, and at the same time, a texture is obtained, and a moist touch is also obtained.

(resin)
As the resin for forming the matte layer, a resin composition for forming a matte layer containing a predetermined amount of the wrinkle-forming stabilizer is formed and cured to form a cured product and a resin constituting the matte layer. good. Such resins include ionizing radiation-curable resins. As described above, when the matte layer itself is used as the pattern-transferring sheet (1-2 above), the mold may be produced based on the matte layer (2-2 above). Therefore, the resin forming the matte layer is preferably a resin that easily exhibits surface properties such as processability and scratch resistance, and the ionizing radiation curable resin is a preferred resin from these points of view. Since the matte layer of the present embodiment contains an extremely small amount of the wrinkle-forming stabilizer contained in the matte layer, the performance of the resin forming the matte layer is more directly exhibited as a surface property. becomes.

The ionizing radiation-curable resin is a resin having an ionizing radiation-curable functional group, and the ionizing radiation-curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation. A functional group having an ethylenic double bond such as an allyl group is preferred. In addition, in this specification, a (meth)acryloyl group shows an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth)acrylate indicates acrylate or methacrylate.
In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing and/or cross-linking molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used, In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

Examples of ionizing radiation-curable resins include electron beam-curable resins and UV-curable resins, which stabilize the formation of wrinkles by the wrinkle-forming stabilizer, stably improve the matting effect, and provide a moist touch. From the viewpoint of improvement, an ultraviolet curable resin is preferable.
Specifically, the ionizing radiation-curable resin can be appropriately selected and used from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. Here, "(meth)acrylate" means "acrylate or methacrylate".
Polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.

From the viewpoint of stabilizing the formation of wrinkles and stably improving the matte effect, the viewpoint of improving moist touch, and the viewpoint of improving surface properties such as post-processing properties, scratch resistance and weather resistance, polyfunctional The number of functional groups of the (meth)acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, still more preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less. Moreover, when it is the said number of functional groups, said surface shape is especially easy to obtain, and it becomes easy to improve the moist touch.
These polyfunctional (meth)acrylates may be used alone or in combination.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , aminoplast resins modified with aminoplast resins having many reactive groups in small molecules (meth)acrylate oligomers, novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination.
Urethane ( meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers, Polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

The number of functional groups of these polymerizable oligomers stabilizes the formation of wrinkles, stably improves the matting effect, improves the moist touch, and further improves the processing characteristics, scratch resistance, and weather resistance of the surface. From the viewpoint of improving properties, the number is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, and even more preferably 4 or less.
From the same point of view, the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and more preferably 3,500 or more and 6,000. More preferred are: Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the present embodiment, as the resin for forming the matte layer, the polymerizable oligomer alone, the polymerizable monomer alone, or a combination of the polymerizable oligomer and the polymerizable monomer can be used. It is preferable to use the polymerizable monomer alone, or to use the polymerizable oligomer and the polymerizable monomer in combination. The polymerizable oligomer is preferably a polyfunctional urethane (meth)acrylate oligomer, more preferably a polyfunctional urethane acrylate oligomer, and the polymerizable monomer is preferably a polyfunctional polymerizable monomer, such as a polyfunctional (meth)acrylate. Monomers are more preferred, and multifunctional acrylate monomers are even more preferred. It can stabilize the formation of wrinkles, stably improve the matting effect, improve the moist touch, and further improve surface properties such as processing properties, scratch resistance, and weather resistance.
When used in combination, from the same point of view, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and further It is preferably 55 parts by mass or more, more preferably 60 parts by mass or more, and the upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less.

(resin composition)
The matte layer is preferably composed of a cured product of a resin composition containing a predetermined amount of the wrinkle-forming stabilizer, and the resin composition preferably contains the resin and the wrinkle-forming stabilizer in a predetermined amount. Quantity. The resin composition used in the present embodiment may contain other components in addition to the wrinkle-forming stabilizer and resin described above, depending on desired performance and the like.
The resin composition for forming the matte layer may contain a monofunctional (meth)acrylate for the purpose of reducing its viscosity, for example. These monofunctional (meth)acrylates may be used alone or in combination.

Moreover, when the resin is an ultraviolet-curable resin that is cured by ultraviolet rays, it preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. By containing these additives, the resin can be cured even with ultraviolet light (without using ionizing radiation), and practical surface properties can be obtained.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones 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.

(Method for forming matte layer)
The first method for forming the matte layer of the present embodiment comprises irradiating the layer of the resin composition for forming the matte layer containing the resin and the wrinkle stabilizer with light having a wavelength of at least 100 nm or more and 380 nm or less. It is characterized by comprising a step of forming a matte layer.
By the first formation method, for example, a matte layer having a surface shape as shown in FIG. 4 can be formed (the transfer layer in FIG. 4 is obtained by reversing the surface shape of the matte layer twice). That is, the surface shape of the transfer layer in FIG. 4 is the same as the surface shape of the matte layer). For example, the above resin composition for forming a matte layer is applied on a substrate, a layer of the resin composition is formed on the substrate, and the above wavelength light is irradiated to form a matte layer. Then, a laminate having a substrate and a matte layer can be produced.
This forming method is used when forming a matte layer having a matte effect such that the 60° gloss value on the matte layer side is 20.0 or less, 10.0 or less, or even less and has a moist touch. is suitable for

The method for forming a matte layer according to the present embodiment makes it possible to easily obtain a matte layer as a base. Specifically, in forming the matte layer, a resin composition for forming a matte layer containing a wrinkle-forming stabilizer is irradiated with ultraviolet light having a short wavelength of at least 100 nm or more and 380 nm or less. Wrinkles can be formed on at least one surface of the matte layer, and a matte effect and a moist touch can be imparted to the matte layer.

By irradiating the resin composition for forming the matte layer with such a short-wavelength ultraviolet ray, wrinkles are formed on at least one surface of the matte layer, and the matting effect and moist touch are exhibited. Although the details are unknown, it is presumed to be due to the following mechanism.

When a coating layer of a resin composition for forming a matte layer is applied to a predetermined thickness and irradiated with ultraviolet light having a short wavelength, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the lower layer. As a result, only the surface portion of the resin composition begins to harden, and it is thought that only the surface causes curing shrinkage, resulting in the formation of wrinkles. Thus, the formation of wrinkles is considered to occur when the resin composition for forming the matte layer is cured only in a certain thickness direction from the surface by irradiation with short-wave ultraviolet rays.
In addition, from the comparison of the examples and comparative examples described later, the formation of wrinkles becomes unstable when the wrinkle-forming stabilizer is not included, and the visibility and texture of the matting effect are stable over the entire surface of the matting layer. The matte effect and the stable expression of moist touch cannot be explained only by curing only the surface portion with short-wave ultraviolet rays, because the matte effect and moist touch are not sufficiently exhibited and the moist touch is not sufficiently exhibited. . That is, in order for the matte layer of the present embodiment to stably have wrinkles to exhibit a matte effect and a moist feel, it is essential to contain a wrinkle-forming stabilizer. Considering that a stable matting effect and a moist touch due to wrinkle formation were not obtained when the wrinkle-forming stabilizer was not contained, the wrinkle-forming stabilizer functions as a nucleus that triggers wrinkle formation. Around the nucleus, the resin on the surface of the resin composition gathers to form wrinkle protrusions (projections) and recesses along with the formation of the protrusions (projections), resulting in wrinkles. It is considered that the formation is stable, and the matting effect and moist touch are stably exhibited.

In the formation method of the present embodiment, the resin composition for forming the matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. By this irradiation, as described above, the energy of the ultraviolet rays penetrates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition starts to harden. Causes curing shrinkage to stabilize the formation of wrinkles, and the surface layer of the resin composition becomes a cured product and constitutes a matte layer. Then, after that, curing progresses from the near-surface portion where curing progresses slowly to the deep portion away from the depth direction, and the layer of the resin composition becomes a cured product, thereby covering the entire thickness of the resin composition. It cures, exhibits a light diffusion effect on the surface, and constitutes a matte layer having wrinkles that exhibit a moist feel. From the viewpoint of accelerating the progress of curing to the deep portion, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of 100 nm or more and 380 nm or less, as described later.

The light having a wavelength of at least 100 nm or more and 380 nm or less includes, for example, rare gases such as Ar, Kr, Xe, and Ne, halogen halides of rare gases such as F, Cl, I, and Br, or mixed gases thereof. Preferred is "excimer light," which includes light in the ultraviolet wavelength region from excited dimers, or excimers, formed by the discharge. The wavelength of the excimer light and the excimer serving as the light source include, for example, light with a wavelength of 126 nm emitted from the excimer of Ar ₂ (hereinafter abbreviated as “126 nm (Ar ₂ )”), 146 nm (Kr ₂ ), and 157 nm. Wavelength light such as (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF) can be preferably employed. As the excimer light, either spontaneous emission light or laser light with high coherence due to stimulated emission can be used, but the use of spontaneous emission light is usually sufficient. A discharge lamp that emits the light (ultraviolet rays) is also called an “excimer lamp”.
The excimer light has a single wavelength peak and is characterized by a narrow half width of the wavelength compared to ordinary ultraviolet rays (for example, ultraviolet rays emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, the formation of wrinkles is stabilized, the matting effect is stably improved, and the moist touch is also improved.

The wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, and even more preferably, from the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the moist touch. is 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, still more preferably less than 200 nm, and most preferably 172 nm (Xe ₂ ). Thus, in the present embodiment, from the viewpoint of stably improving the matting effect and improving the moist touch, it is preferable to use light with a shorter wavelength, medium wavelength ultraviolet light (wavelength: 280 to 320 nm). It can also be said that short-wavelength ultraviolet rays (wavelength: 280 nm or less) are more preferable, and short-wavelength ultraviolet rays are even more preferable. Short-wave ultraviolet rays preferably have a wavelength of less than 200 nm.

In the present embodiment, the integrated amount of light of the wavelength is preferably 1 mJ/cm ² or more, more preferably 1 mJ/cm 2 or more, from the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the moist touch. is 10 mJ/cm ² or more, more preferably 30 mJ/cm ² or more, and even more preferably 50 mJ/cm ² or more. The upper limit is not particularly limited, and from the viewpoint of productivity such as reducing the number of lamps required for irradiation of wavelength light and improving production efficiency, the upper limit is preferably 1,000 mJ/cm ² or less, more preferably 1,000 mJ/cm 2 or less. It is 500 mJ/cm ² or less, more preferably 300 mJ/cm ² or less. From the same point of view, the ultraviolet power density is preferably 0.001 W/cm or more, more preferably 0.01 W/cm or more, still more preferably 0.03 W/cm or more, and the upper limit is preferably 10 W/cm. Below, more preferably 5 W/cm or less, still more preferably 3 W/cm or less.
Further, the oxygen concentration at the time of irradiation with light of the above wavelength is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

In the matte layer forming step of the present embodiment, in addition to the irradiation with light having a wavelength of at least 100 nm or more and 380 nm or less, other treatments that contribute to curing of the resin composition for forming the matte layer may be performed.
For example, from the viewpoint of stabilizing the formation of wrinkles due to the difference in the degree of curing progress between the surface portion and the deep portion distant from the surface in the depth direction, and promoting the progress of curing to the deep portion, for example, 380 nm After pre-curing the entire resin composition for forming the matte layer by previously irradiating with light having a wavelength exceeding 385 nm or more and preferably 400 nm or less, it is possible to irradiate with light having a wavelength of 100 nm or more and 380 nm or less. Alternatively, after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed to further cure the resin composition. Pre-curing and post-curing may be appropriately determined depending on desired properties (for example, surface properties such as processability and stain resistance) required for the matte layer. Moreover, although the above wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiation such as electron beams. For example, in post-curing, an electron beam can be preferably used from the viewpoint of improving the surface properties of the matte layer.

In the formation method of the present embodiment, the matte layer is formed by applying a resin composition for forming the matte layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma coating method, or the like. The applied coating layer (uncured resin layer) can be formed by irradiating with light having a wavelength of at least 100 nm or more and 380 nm or less.

<Releasable support>
The release support is peeled off from the transfer layer after transferring the transfer layer to the adherend. The surface shape of the release support is a shape that is the reverse of the surface shape of the transfer layer.
The releasable support may have a single-layer structure or a two-layer or more structure. The release support preferably has a structure having a release layer on the support.

[Support]
The material of the support is not particularly limited, and includes paper, fiber, metal, glass, ceramics, resin, and the like. Among these, a support made of a resin is preferable because it facilitates formation of a release layer and has good peeling workability after transfer. A support made of resin is hereinafter referred to as a plastic film.

The thickness of the support is not particularly limited. That is, the support in this embodiment may be a support having a thickness on the order of micrometers or a support having a thickness on the order of millimeters or more.
The support may or may not be colored. In addition, when the support is colored, there are no particular restrictions on the mode of coloring, and it may be transparent coloring or opaque coloring (concealing coloring).

The resins that make up the plastic film include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; Resins, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester resins such as polyester thermoplastic elastomers, polymethyl acrylate, polyethyl methacrylate , acrylic resins such as polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, polyamide resins represented by nylon 6 or nylon 66, cellulose triacetate, cellophane, celluloid Cellulose resins such as polystyrene, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers (ABS) and other styrene resins, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resins, polyarylate resins, polyimide resins, and the like. Among these resins, polyester resins are preferred, and among polyester resins, polyethylene terephthalate is preferred.

Although the thickness of the plastic film is not particularly limited, it is preferably 10 μm or more and 200 μm or less, more preferably 15 μm or more and 150 μm or less, and more preferably 20 μm or more and 125 μm or less in order to improve the handleability of the transfer sheet. More preferred.

In order to enhance adhesion to the release layer, the support may be subjected to a physical surface treatment such as an oxidation method or a roughening method, or a surface treatment such as a chemical surface treatment on one or both sides thereof, or may be subjected to a surface treatment such as a chemical surface treatment. An agent layer may be formed.

[Release layer]
The release layer is a layer provided as necessary in order to improve the releasability between the release support and the transfer layer.
The release layer is preferably provided over the entire surface of the support in order to improve the releasability from the transfer layer.
The release layer preferably contains a resin, and more preferably contains a resin and a release agent.

(resin)
The release layer preferably contains a resin as a main component. The main component means that the total solid content constituting the release layer is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and more Preferably, it is 95% by mass or more.

In order to improve durability, the release layer preferably contains a cured product of a resin composition containing a curable resin as the resin.
The proportion of the cured product of the resin composition containing the curable resin is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the total amount of the resin contained in the release layer. , more preferably 95% by mass or more, more preferably 100% by mass.

The cured product of a resin composition containing a curable resin includes a cured product of a resin composition containing a thermosetting resin and a cured product of a resin composition containing an ionizing radiation-curable resin.
A cured product of a resin composition containing an ionizing radiation-curable resin is preferable because it tends to have better scratch resistance.

A resin composition containing a thermosetting resin 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, urethane acrylic resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. These can be used individually or in combination of multiple types. Moreover, the resin composition containing a thermosetting resin may be one to which a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent is added.

Examples of the ionizing radiation-curable resin for the release layer include those exemplified as the ionizing radiation-curable resin for the matte layer.

(Release agent)
Examples of the release agent include fluorine-based release agents, silicone-based release agents, and the like, and silicone-based release agents are preferable from the viewpoint of obtaining high releasability at a lower cost.

Examples of the silicone-based release agent include those having a polysiloxane structure as a basic structure. Among them, modified silicone oil in which an organic group is introduced into at least one of the side chain and terminal thereof is preferred, and an organic group is present at both terminals. Incorporated modified silicone oils are more preferred. As the organic group, reactive functional groups such as (meth)acrylic group, amino group, epoxy group, mercapto group, carbinol group, phenol group, carboxyl group, etc., and polyether group are used from the viewpoint of obtaining a design with a higher texture. , an aralkyl group, a fluoroalkyl group, an alkyl group, a fatty acid amide group, a non-reactive functional group such as a phenyl group, and the like. Among them, a reactive functional group is preferable, and a (meth)acryl group is particularly preferable, that is, a (meth)acryl-modified silicone oil is particularly preferable. Moreover, these organic groups may have a substituent such as a nitrogen atom, a sulfur atom, a hydroxyl group, an alkyl group, or the like.

The content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and still more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the resin forming the release layer. Department. When the content of the release agent is within the above range, the effect of addition of the release agent can be efficiently obtained.

The surface shape of the release layer is a reverse shape of the surface shape of the transfer layer. Therefore, it is preferable that the release layer has a predetermined thickness. The thickness of the release layer is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm. Below, more preferably 150 μm or less, still more preferably 100 μm or less.
In this specification, the thickness of the release layer is the average value of the 20 thicknesses measured from the image taken with a scanning electron microscope (SEM) for the cross section of the transfer sheet. . The acceleration voltage of the SEM is set to 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[Other layers]
The release support constituting the transfer sheet of the present embodiment may have a layer other than the support and the release layer. Examples of layers other than the support and release layer include an antistatic layer and an easy-adhesion layer.

<Transfer layer>
A transfer layer is a layer that is transferred to an adherend.
The transfer layer preferably has at least a release layer. Further, the transfer layer more preferably has a release layer and an adhesive layer in this order from the release support side. Further, the transfer layer more preferably has one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. When a primer layer and a decorative layer are provided between the release layer and the adhesive layer, the primer layer is preferably positioned closer to the release layer than the decorative layer.

Also, the transfer layer may further have other functional layers. Other functional layers include an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an antifogging layer, a transparent conductive layer, and the like.

[Release layer]
The release layer is a layer positioned on the outermost surface of the transfer layer when transferred to an adherend. For this reason, the release layer preferably has good scratch resistance, weather resistance, stain resistance, and the like.

The release layer preferably contains resin as a main component. The main component means that the total solid content of the release layer is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

In order to improve scratch resistance, the release layer preferably contains a cured product of a resin composition containing a curable resin as the resin.
The ratio of the cured product of the resin composition containing the curable resin to the total amount of the resin contained in the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more, More preferably 95% by mass or more, more preferably 100% by mass.

The cured product of a resin composition containing a curable resin includes a cured product of a resin composition containing a thermosetting resin and a cured product of a resin composition containing an ionizing radiation-curable resin.
A cured product of a resin composition containing a thermosetting resin is preferable because it is easy to improve weather resistance because there is no restriction on the use of an ultraviolet absorber.
A cured product of a resin composition containing an ionizing radiation-curable resin is preferable because it tends to have better scratch resistance. Among them, a cured product of a resin composition containing an electron beam curable resin is preferable because it is easy to improve weather resistance because it does not limit the use of an ultraviolet absorber while improving scratch resistance.

Examples of the resin composition containing the thermosetting resin for the release layer include those exemplified as the resin composition containing the thermosetting resin for the release layer.
Examples of the resin composition containing the ionizing radiation-curable resin for the release layer include those exemplified as the resin composition containing the ionizing radiation-curable resin for the matte layer. Resins are preferred.

The release layer may contain particles such as matting agents and wrinkle stabilizers, but is preferably substantially free of such particles. By substantially not containing particles in the release layer, it is possible to suppress deterioration in scratch resistance, weather resistance, stain resistance, and the like of the release layer caused by detachment of particles.
That the release layer does not substantially contain particles means that the content of particles is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.1% by mass or less, based on the total solid content constituting the release layer. It is 0.01% by mass or less, more preferably 0% by mass.

The release layer preferably contains an ultraviolet absorber or a light stabilizer, and more preferably contains an ultraviolet absorber and a light stabilizer, in order to improve weather resistance. General-purpose compounds can be used as the ultraviolet absorber and light stabilizer. Among UV absorbers, hydroxyphenyltriazine compounds are preferred. Among light stabilizers, hindered amine compounds are preferred.

The content of the ultraviolet absorber in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the resin of the release layer. 1 part by mass or more and 7 parts by mass or less is more preferable.
The content of the light stabilizer in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the resin of the release layer. 1 part by mass or more and 7 parts by mass or less is more preferable.

The thickness of the release layer is preferably 1.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and 3 μm or more and 15 μm or less, in order to improve the handleability of the transfer sheet and the scratch resistance and weather resistance of the release layer. is more preferred.

[Adhesive layer]
The release layer is a layer that is formed as necessary in order to facilitate the transfer of the transfer layer to the adherend. For example, when a separately prepared adhesive is used between the adherend and the transfer sheet when transferring the transfer layer of the transfer sheet to the adherend, the transfer layer does not have an adhesive layer. may Further, when the transfer layer and the adherend can be brought into close contact without using an adhesive, the transfer layer does not have to have an adhesive layer.
When the transfer layer has an adhesive layer, it is preferable to form the adhesive layer at the farthest position from the release support among the layers constituting the transfer layer. The adhesive layer can also function as a decorative layer, which will be described later.

The adhesive layer includes a pressure-sensitive adhesive layer, a curable adhesive layer, and a heat-sensitive adhesive layer. Among these, a heat-sensitive adhesive layer is preferable in order to improve the handleability of the transfer sheet and the adhesion between the transfer layer and the adherend. A heat-sensitive adhesive layer is sometimes called a heat seal layer.

When the adhesive layer is a pressure-sensitive adhesive layer, the adhesive layer preferably contains an adhesive.
As the adhesive, acrylic, urethane, silicone, rubber, or other adhesives can be appropriately selected and used.

When the adhesive layer is a curable adhesive layer, the adhesive layer preferably contains a thermosetting adhesive.
The thermosetting adhesive preferably contains a composition having the property of cross-linking due to a chemical reaction caused by heat. Adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like can be exemplified. The urethane-based resin constituting the two-liquid curing urethane-based adhesive is a polyurethane containing polyol (polyhydric alcohol) as a main agent and isocyanate as a cross-linking agent (curing agent).

When the adhesive layer is a heat-sensitive adhesive layer, the adhesive layer preferably contains a thermoplastic resin.
Thermoplastic resins include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, epoxy resins, etc. and these can be used singly or in combination. Among these, acrylic resins having good weather resistance are preferred.

The weight average molecular weight of the thermoplastic resin is preferably 10,000 or more and 200,000 or less, preferably 50,000 or more and 150,000 or less, and more preferably 80,000 or more and 120,000 or less. When the weight-average molecular weight of the thermoplastic resin is within the above range, the coating aptitude is improved and the adhesive layer can be easily formed in a favorable state. Furthermore, when the weight average molecular weight of the thermoplastic resin is within the above range, the adhesion between the adhesive layer and the adherend can be easily improved.

The thickness of the adhesive layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and even more preferably 3 μm or more and 7 μm or less. When the thickness of the adhesive layer is within the above range, the adhesion between the adhesive layer and the adherend can be easily improved, and the transfer sheet can be easily handled.

The adhesive layer can contain a colorant, if desired.
By including a coloring agent in the adhesive layer, the design of the transfer layer can be enhanced by the adhesive layer alone or by combining the adhesive layer with a decorative layer described later.

The coloring agent is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, nickel azo complex, phthalocyanine blue, azomethine azo black, and other organic pigments or dyes; metal pigments, such as scaly foil pieces of aluminum and brass; scaly foils, such as titanium dioxide-coated mica and basic lead carbonate Pearl luster (pearl) pigments such as flakes;

The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 20 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the adhesive layer. Part or less is more preferable.
When the content of the colorant is 5 parts by mass or more, the design of the transfer layer can be easily improved. Further, when the content of the coloring agent is 90 parts by mass or less, it is possible to easily suppress the decrease in the adhesive strength of the adhesive layer.

[Primer layer]
In order to improve the adhesion between the layers constituting the transfer layer, the transfer layer is subjected to surface treatment such as the physical surface treatment or chemical surface treatment described above on the surface of each layer, or a primer layer is provided between each layer. may be formed. Both the surface treatment and the formation of the primer layer may be carried out. A primer layer can be formed, for example, between the release layer and the adhesive layer. When the primer layer and the decorative layer are provided between the release layer and the adhesive layer, it is preferable that the primer layer is positioned closer to the release layer than the decorative layer.
By forming the primer layer between the release layer and the adhesive layer, the interlayer adhesion of the transfer layer is improved, and the weather resistance and durability of the transfer layer can be improved.

The primer layer is mainly composed of a binder resin, and may contain additives such as ultraviolet absorbers and light stabilizers, if necessary.

Binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and polycarbonate-based urethane-acrylic copolymers (carbonate bonds in the polymer main chain). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the ends and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Resins such as coalescent resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred, and these can be used alone or in combination.
Further, the binder resin may be one obtained by adding a curing agent such as an isocyanate curing agent or an epoxy curing agent to these resins and curing by crosslinking.
Among these, polycarbonate-based urethane-acrylic copolymers are preferred.

A polycarbonate-based urethane-acrylic copolymer can be obtained, for example, by the following steps (1) and (2). Polycarbonate-based urethane-acrylic copolymers are preferable in that they have good flexibility, easily follow curing shrinkage of the release layer, and have good weather resistance.
(1) A polycarbonate-based polyurethane polymer is obtained by reacting a polycarbonate diol and (di)isocyanate.
(2) The polycarbonate-based polyurethane polymer and an acrylic monomer are radically polymerized to obtain a polycarbonate-based urethane-acrylic copolymer.

Examples of (di)isocyanates include aromatics such as 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalenediisocyanate, n-isocyanatephenylsulfonyl isocyanate, o- or p-isocyanatephenylsulfonyl isocyanate. group isocyanates; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; alicyclic isocyanates;

Examples of acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid -n- (Meth)acrylic acid alkyl esters such as butyl and isobutyl (meth)acrylate.

The mass ratio of the acrylic component to the urethane component in the polycarbonate-based urethane-acrylic copolymer is preferably in the range of 95:5 to 30:70, preferably 93:7 to 50:50. and more preferably 90:10 to 60:40. By setting the mass ratio of the acrylic component to the urethane component within the above range, the primer layer does not become an excessively hard coating film, and sufficient workability can be obtained. Further, by setting the mass ratio of the acrylic component to the urethane component within the above range, when the release layer is made of a urethane acrylic resin such as a urethane (meth)acrylate oligomer, the adhesion between the release layer and the release layer is improved.

The primer layer preferably contains an antiblocking agent. Anti-blocking agents include inorganic particles and organic particles such as silica, alumina, aluminum hydroxide, barium sulfate, talc, and calcium carbonate. Among these, inorganic particles are preferred, and among inorganic particles, silica is preferred.

The average particle size of the antiblocking agent is preferably about 0.1 to 10 μm, more preferably 0.5 to 8 μm, still more preferably 0.5 to 5 μm. The particle size of the antiblocking agent is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.
The content of the antiblocking agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 3 to 20 parts by mass, and particularly preferably 5 parts by mass with respect to 100 parts by mass of the binder resin. ~15 parts by mass.

The thickness of the primer layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

[Decoration layer]
The transfer layer may have a decorative layer to enhance the design. The decorative layer is preferably formed between the release layer and the adhesive layer.

The decoration layer may be formed on the entire surface of the transfer sheet, or may be formed only on a part thereof.

Examples of the decorative layer include a colored layer formed by solidly applying ink; a pattern layer formed by printing a pattern with ink; a metal thin film; and the like.
Patterns (patterns) expressed by the decorative layer include wood grain patterns such as annual rings and duct grooves on the surface of the wood plate; stone grain patterns on the surface of stone plates such as marble and granite; texture patterns on the surface of fabric; leather grain patterns on the surface of leather; tiling pattern including joint groove; brickwork pattern including joint groove; grain pattern; satin pattern; abstract patterns such as geometric patterns, letters, figures, polka dots and floral patterns; and the like.

As the ink used for the colored layer and pattern layer, a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. are appropriately mixed with the binder resin. used.
The binder resin for the colored layer and pattern layer is not particularly limited, and examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and vinyl chloride-acetic acid. Resins such as vinyl copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins and cellulose acetate resins can be used. Moreover, various types of resins can be used, such as a one-component curing type resin and a two-component curing type resin accompanied by a curing agent such as an isocyanate compound.

The coloring agent is not particularly limited, and the coloring agents exemplified for the adhesive layer can be suitably used.
The content of the coloring agent is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass, based on 100 parts by mass of the resin constituting the decorative layer. More preferred are:

The colored layer and pattern layer may contain additives such as ultraviolet absorbers, light stabilizers and colorants.
The thickness of the colored layer and the pattern layer may be appropriately selected according to the desired pattern. In order to improve the design, the thickness is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and 2 μm or more and 5 μm. More preferred are: When it is necessary to conceal the color and appearance of the adherend, the thickness of the colored layer and pattern layer should be 1.5 μm or more, depending on the type and content of the colorant contained. preferable.

Examples of metal thin films include thin films of simple metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt; thin films of alloys containing two or more of the above metal elements; Examples of alloys include brass, bronze, stainless steel, and the like.
The film thickness of the metal thin film can be about 0.1 μm or more and 1 μm or less.

The release layer, the primer layer, the adhesive layer and the decorative layer described above can be obtained, for example, by applying a coating liquid containing the composition forming each layer by a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method or a comma coating method. It can be formed by coating on a releasing support by a known method such as the above, and drying and curing as necessary.

<Separator>
The transfer sheet may have a separator on the opposite side of the transfer layer to the release support.
When the adhesive layer is a pressure-sensitive adhesive layer, having a separator on the transfer layer makes it easier to prevent blocking when the transfer sheet is wound into a roll, and prevents the transfer sheet from accidentally sticking to other objects. You can make it easier to prevent sticking.

The material of the separator is not particularly limited as long as it can be separated from the transfer layer, and a plastic film is preferably used.
As the plastic film used as the separator, the same ones as those exemplified for the above support can be used. It is preferable that the surface of the separator that is in contact with the transfer layer is subjected to release treatment with a release agent or the like. As the release agent, known release agents such as fluorine-based release agents and silicone-based release agents can be used.
The thickness of the separator is not particularly limited, but is preferably 10 μm or more and 200 μm or less, more preferably 15 μm or more and 150 μm or less, and further preferably 20 μm or more and 100 μm or less, in order to improve the handleability of the transfer sheet. preferable.

[60° gross value]
The transfer sheet of the present embodiment can form a transfer layer on an adherend having excellent visibility of the matting effect. In the present specification, the term "matte" means that glossiness is difficult to visually recognize, and although it cannot be generalized because it varies depending on the color tone of the transfer layer, for example, the 60° gloss value is 20.0 or less, preferably 10.0. If it is about 0 or less, it is generally treated as "matte". In addition, since the transfer sheet of the present embodiment imparts a matte finish, the 60° gloss value described above is the 60° gloss value that can be imparted by the transfer sheet of the present embodiment. means the 60° gloss value of the decorative material).
If the transfer layer constituting the transfer sheet of the present embodiment has a stable matte effect and texture due to stable formation of wrinkles, the same applies to the decorative material obtained by transferring the transfer layer to the adherend. , it can be a decorative material with a high-class feeling that stably has the visibility and texture of a matte effect.
The 60° gloss value of the release support constituting the transfer sheet and the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend are somewhat differences occur, but they are basically the same.

Up to now, for example, in the case of a decorative material exhibiting a dark color such as black, excellent matting with a 60° gloss value of 20.0 or less, preferably 10.0 or less has been achieved by incorporating a matting agent into the matting layer. It is possible to give the visibility of the effect. "Dark color" means low lightness, for example, CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* L ^* value in color system measured in accordance with JIS Z8781-4:2013 (hereinafter simply "L ^* is sometimes referred to as "value") is usually about 40 or less, preferably 30 or less. However, since a large amount of the matting agent is used, streaks and unevenness occur during the formation of the matting layer, so that it is not easy to manufacture, and there is a problem that the strength of the matting layer is lowered. Further, in the case of a decorative material exhibiting a color tone other than a dark color, even if the matting layer contains a matting agent, there is a limit to the reduction of the 60° gloss value.
Such a tendency becomes more remarkable as the 60° gloss value becomes smaller. Therefore, in the conventional technology using a matting agent, it is necessary to suppress the amount of the matting agent used for manufacturing reasons, etc., and it is not possible to obtain a better visibility of the matting effect. .

In the present embodiment, two types of wrinkle-forming stabilizers having a predetermined average particle size are used in combination when forming the base matte layer, and the content thereof is reduced as described above. As a result, not only is it possible to stably obtain an extremely excellent matte effect in terms of visibility and texture, but also a moist touch is obtained. In addition, by suppressing the amount of the wrinkle-forming stabilizer to an extremely small amount, it is possible to suppress a significant increase in the viscosity of the resin composition, thereby improving the productivity of the matte layer.

The 60° gloss value of the decorative material obtained using the transfer sheet of the present embodiment varies depending on the color tone as described above, so it cannot be defined unconditionally. The 60° gloss value on the transfer layer side is 10.0 or less, and further, 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, and 2.0 or less. It is something that can be expressed. Also, a cosmetic material exhibiting a color tone other than black or dark color can have the 60° gloss value.
In this specification, the 60° gloss value on the transfer layer side is the 60° specular gloss measured in accordance with JIS K 5600-4-7: 1999, using a gloss meter or the like at arbitrary 10 points. It is the average value of the values that can be measured from the transfer layer side. When measuring the 60° gloss value, it is preferable to attach a black plate to the back surface of the measurement sample via an adhesive layer in order to suppress reflection from the back surface of the sample.

[Method for producing decorative material]
The method for manufacturing a decorative material according to the present embodiment includes the following steps (1) and (2).
(1) A step of obtaining a laminate in which the transfer layer side of the transfer sheet of the present embodiment and the adherend are in close contact with each other.
(2) A step of peeling off the release support from the laminate to obtain a decorative material having a transfer layer on the adherend.

The adherend in step (1) is not particularly limited, and an adherend made of resin, paper, nonwoven fabric, woven fabric, wood, metal, nonmetallic inorganic material, etc., can be appropriately selected.
When a resin is used as an adherend, a physical or chemical treatment such as an oxidation method or roughening method may be applied to one or both sides of the transfer sheet, if desired, in order to improve the adhesion between the transfer layer of the transfer sheet and the adherend. surface treatment can be applied.
The shape of the adherend is not particularly limited.

In step (1), the transfer layer side of the transfer sheet and the adherend can be brought into close contact with each other by, for example, the adhesive layer of the transfer layer. When the transfer layer does not have an adhesive layer, an adhesive may be interposed between the transfer layer and the adherend in step (1).

One embodiment of the step (1) is a lamination method having the following steps (a1) and (a2) in order.
(a1) The step of bringing the transfer layer side surface of the transfer sheet into contact with the adherend on the flat plate and superimposing the same.
(a2) A step of applying heat and/or pressure from the release support side of the transfer sheet to bring the adherend on the flat plate into close contact with the transfer layer of the transfer sheet.

Further, as another embodiment of the step (1), there is a method by in-mold molding, which requires the following steps (z1) to (z4) in order. In the in-mold molding, the resin to be poured in step z2 becomes the adherend.
(z1) A step of arranging the transfer sheet so that the transfer layer side faces the inside of the mold for in-mold molding.
(z2) A step of injecting a resin into the mold for in-mold molding.
(z3) A step of integrating the transfer sheet and the resin to bring the transfer layer of the transfer sheet and the resin into close contact with each other to form a resin molding.
(z4) A step of removing the resin molded body from the in-mold mold.

When the transfer sheet has a separator on the opposite side of the transfer layer to the release support, it is preferable to perform the following step (0) before the step (1).
(0) A step of peeling off the separator from the transfer sheet.

The decorative material obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. And various uses, for example, interior members of buildings such as walls, ceilings and floors, exterior members such as outer walls, eaves, roofs, fences and fences, window frames, doors, door frames, handrails, baseboards, In addition to fittings or fixtures such as rims and malls, general furniture such as chests, shelves, desks, etc., kitchen furniture such as dining tables and sinks, various types of furniture used around water such as kitchens, toilets, bathrooms, washbasins, etc. It is suitably used as various members such as members, surface decorative boards for cabinets such as home appliances and OA equipment, interior or exterior members for vehicles, signboards, soundproof walls, and the like. That is, the transfer sheet of the present embodiment is suitably used as a transfer sheet for transferring the uneven shape to these various members.
Furthermore, in addition to the above-mentioned various members, the decorative material can be used alone or in a form laminated or combined with other materials, such as packaging materials, anti-glare films for displays, whiteboards or blackboards, credit cards, cash cards. , telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, show window, etc.), artificial leather, and the like.

[Cosmetic material]
The decorative material of the present embodiment is a decorative material having a transfer layer on an adherend, wherein at least part of the surface of the transfer layer opposite to the adherend is provided with ISO25178-2:2012 It has a surface shape whose Ssk (skewness) is less than 0.00.

FIG. 6 is a cross-sectional view showing one embodiment of the decorative material 200 of the present invention. A decorative material 200 in FIG. 6 has a transfer layer 20 on an adherend 30 . 6, the transfer layer 20 has an adhesive layer 24, a decoration layer 23, a primer layer 22 and a release layer 21 in this order from the side closer to the adherend 30. As shown in FIG.
In the decorative material of FIG. 6, a release layer 21 is positioned on the surface of the transfer layer 20 opposite to the adherend 30 . Therefore, in the decorative material of FIG. 6, at least part of the surface of the release layer 21 opposite to the adherend 30 has a surface shape with an Ssk (skewness) of less than 0.00.

Examples of the adherend constituting the decorative material of the present embodiment include the adherends exemplified in the manufacturing method of the decorative material of the present embodiment. Examples of the transfer layer constituting the decorative material of the present embodiment include the transfer layer exemplified for the transfer sheet of the present embodiment.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

1. Evaluation 1-1. Measurement of Surface Shape Regarding the surface shape of the release layer side of the decorative materials obtained in Examples and Comparative Examples, Ssk (skewness), Sku (kurtosis), Rsm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness) were measured. The measurement area was a rectangular area (1024 μm×768 μm) at an arbitrary point on the surface of the decorative material. The measuring device uses a shape analysis laser microscope ("VK-X150 (control unit) / VK-X160 (measurement unit)", manufactured by Keyence Corporation), objective lens: 50 times, laser wavelength: 658 nm, measurement mode: surface Shape mode, measurement pitch: 0.13 μm, measurement quality: measured in high-speed mode.
The cutoff values for Rsm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness) were set to 0.8 mm.
The surface shape of the release layer side of the decorative material can be regarded as the surface shape of the transfer layer on the release support side.

1-2. 60° Gloss Value A sample was prepared by bonding a black plate to the back surface of the polycarbonate resin plate of the decorative material obtained in Examples and Comparative Examples via an adhesive layer. The 60° specular gloss was measured from the release layer side of the sample using a gloss meter (“Microgloss (model name)” manufactured by BYK Gardner) in accordance with K 5600-4-7:1999.

1-3. Evaluation of texture before weather resistance test The surface texture (uniformity of surface condition) of the decorative materials obtained in Examples and Comparative Examples was evaluated by 20 random adults according to the following criteria.
A: 18 or more people evaluated that the surface condition was uniform and the visibility of the matte effect was high.
B: 15 or more and 17 or less evaluated that the surface condition was uniform and the visibility of the matte effect was high.
C: 14 or less evaluated that the surface condition was uniform and the visibility of the matting effect was high.

1-4. Evaluation of texture after weather resistance test The following weather resistance test was performed on the decorative materials obtained in Examples and Comparative Examples. The surface texture (uniformity of surface condition) of the decorative material after the weather resistance test was evaluated according to the same criteria as in 1-3.
<Weather resistance test>
A weather resistance test was performed using a weather resistance test apparatus (trade name “Metal Weather” manufactured by Daipla-Wintes Co., Ltd.). In the weather resistance test, the following "ultraviolet irradiation process", "condensation process", and "water spraying process" were defined as one cycle, and the cycle was repeated until 500 hours passed.
《Ultraviolet irradiation process》
Illuminance: 60 mW/cm ² , Black panel temperature: 63° C., Chamber humidity: 50% RH, Time: 20 hours <<condensation process>>
Illuminance: 0 mW/cm ² , Black panel temperature: 30° C., Humidity in chamber: 98% RH, Time: 4 hours <<water spray process>>
Water is sprayed for 10 seconds before and after the condensation process.

1-5. Evaluation of moist touch For the cosmetic materials obtained in Examples and Comparative Examples, silk fabric was used as a touch standard for moist touch, and 20 random adults were asked to evaluate the surface touch. and evaluated according to the following criteria.
A: 18 or more people evaluated that the tactile sensation was close to the standard and that the tactile sensation was moist.
B: 15 or more and 17 or less evaluated that the tactile sensation was close to the standard and that the tactile sensation was moist.
C: 14 or less people evaluated that the tactile sensation was close to the standard and that the tactile sensation was moist.

2. Preparation of matte layer [Matte layer 1]
A resin composition containing an acrylic resin and a urethane resin as a binder resin was applied to one side of a substrate (PET sheet subjected to corona discharge treatment, thickness: 100 μm), dried, and formed into an easy-adhesion layer (thickness: 2 μm).
On the easily adhesive layer, the following resin composition 1 for forming a matte layer is applied by a gravure method (coating amount: 5 g/m ² (dry)), and then using a UV irradiation device composed of LEDs. was irradiated with ultraviolet rays (wavelength: 395 nm, amount of ultraviolet rays: 6 W/cm ² ), and then ultraviolet rays were irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), output density of ultraviolet rays: 1 W/cm, integrated light amount : 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration of 200 ppm or less)), and then further ultraviolet irradiation using a high-pressure mercury lamp (ultraviolet power density: 200 W/cm) to form a matte layer 1 on the substrate. A laminate 1 was obtained.

<Resin composition 1 for forming matte layer>
・Multifunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass ・Bifunctional acrylate monomer: 35 parts by mass ・Wrinkle-forming stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass ・Wrinkle-forming stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass Photoinitiator (benzophenone type): 0.8 parts by mass

[Matte layer 2]
A laminate having a matte layer 2 on a substrate in the same manner as for the matte layer 1, except that the matte layer-forming resin composition 1 was changed to the matte layer-forming resin composition 2 below. got 2.

<Resin composition 2 for forming matte layer>
・Multifunctional urethane acrylate oligomer (tetrafunctional): 90 parts by mass ・Monofunctional acrylate monomer: 10 parts by mass ・Wrinkle-forming stabilizer 1 (silica particles, average particle size: 3 µm): 3.0 parts by mass ・Wrinkle-forming stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass Photoinitiator (benzophenone type): 0.8 parts by mass

[Matte layer 3]
A laminate having a matte layer 3 on a substrate in the same manner as the matte layer 1, except that the matte layer-forming resin composition 1 was changed to the matte layer-forming resin composition 3 below. got 3.

<Resin composition 3 for forming matte layer>
・Multifunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass ・Bifunctional acrylate monomer: 35 parts by mass ・Photopolymerization initiator (benzophenone type): 0.8 parts by mass

[Matte layer 4]
The resin composition 1 for forming the matte layer was changed to the following resin composition 4 for forming the matte layer, and only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3 Mrad)) was irradiated. A laminate 4 having a matte layer 4 on a substrate was obtained in the same manner as for the matte layer 1 .

<Resin composition 4 for forming matte layer>
· Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Bifunctional acrylate monomer: 35 parts by mass · Matting agent (average particle diameter: 8.0 µm): 15.0 parts by mass · Photopolymerization initiator (benzophenone-based ): 0.8 parts by mass

3. Production of releasable support, transfer sheet and decorative material [Example 1]
The laminate 1 produced above was used as a release support in Example 1. In the release support of Example 1, the matte layer 1 functions as a release layer.
Next, on the release layer of the release support (on the matte layer 1 of the release support), the following resin composition 1 for forming a release layer is applied to form an uncured resin layer, An electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) was applied to cure the uncured resin layer to form a release layer (thickness: 5 μm). Corona irradiation was then performed on the release layer.
Next, the following resin composition for forming a primer layer was applied onto the corona-irradiated release layer and dried to form a primer layer having a thickness of 2.5 μm.
Next, an acrylic resin (PMMA, weight average molecular weight: 96,000) was applied onto the primer layer and dried to form a 4 μm-thick heat-sealable adhesive layer. After forming the adhesive layer agent, the transfer sheet of Example 1 was obtained by aging at room temperature for 24 hours.

The adhesive layer of the transfer sheet of Example 1 and one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC, trade name: "Carbo Polish") as an adherend were opposed and laminated. After that, from the transfer sheet side, using a laminator (Roll type thermal transfer machine manufactured by Navitas, product number "RT-300"), the transfer sheet is heated and pressed under conditions of a lamination roll temperature of 160 ° C. and a conveying speed of 1.5 m / min. A laminate was obtained in which the transfer layer and the adherend were in close contact with each other.
Next, the release support was peeled off from the laminate to obtain a decorative material of Example 1. The decorative material of Example 1 has a transfer layer on the adherend.

<Resin composition 1 for forming release layer>
Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 100 parts by mass UV absorber (BASF, trade name: Tinuvin479): 0.5 parts by mass Light stabilizer (BASF, trade name: Tinuvin123): 0.3 parts by mass

<Resin composition for forming primer layer>
・ Polycarbonate-based urethane acrylic copolymer: 100 parts by mass (weight average molecular weight 50,000)
- Ultraviolet absorber (BASF, trade name: Tinuvin479): 20 parts by mass - Ultraviolet absorber (BASF, trade name: Tinuvin400): 15 parts by mass - Light stabilizer (BASF, trade name: Tinuvin123): 3. 5 parts by mass Antiblocking agent (silica with an average particle size of 3 μm): 10 parts by mass Solvent: Appropriate amount

[Example 2]
A resin composition containing an acrylic resin and a urethane resin as a binder resin was coated on one side of a support (PET sheet subjected to corona discharge treatment, thickness: 100 μm), dried, and formed into an easy-adhesion layer (thickness: 2 μm).
Next, on the easily adhesive layer, the following resin composition for forming a release layer was applied by a gravure method to form a coating film (coating amount: 5 g/m ² (when dry)), and the , to obtain a laminate 2′ having an easy-adhesion layer and an uncured release layer.
Next, the surface of the laminate 2 on the matte layer 2 side was dry-laminated to the uncured coating film (uncured release layer) of the laminate 2' to obtain a laminate 2''.
Next, an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) was irradiated from the PET side of the laminate 2′ constituting the laminate 2″ to cure the uncured release layer.
Next, the laminate 2 was peeled off from the laminate 2″ to obtain a releasable support used in Example 2 having an easy-adhesion layer and a release layer on the support. The surface shape of the matte layer 2 is reversed on the release layer of the flexible support.

Next, on the release layer of the release support, the resin composition 1 for forming a release layer is applied to form an uncured resin layer, and an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy) ) to cure the uncured resin layer to form a release layer (thickness: 5 μm). Corona irradiation was then performed on the release layer.
Next, the above resin composition for forming a primer layer was applied onto the corona-irradiated release layer and dried to form a primer layer having a thickness of 2.5 μm.
Next, an acrylic resin (PMMA, weight average molecular weight: 96,000) was applied onto the primer layer and dried to form a 4 μm-thick heat-sealable adhesive layer. After forming the adhesive layer agent, the transfer sheet of Example 2 was obtained by aging at room temperature for 24 hours.

The adhesive layer of the transfer sheet of Example 2 and one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC, trade name "Carbo Polish") as an adherend were opposed and laminated. After that, from the transfer sheet side, using a laminator (Roll type thermal transfer machine manufactured by Navitas, product number "RT-300"), the transfer sheet is heated and pressed under conditions of a lamination roll temperature of 160 ° C. and a conveying speed of 1.5 m / min. A laminate was obtained in which the transfer layer and the adherend were in close contact with each other.
Next, the release support was peeled off from the laminate to obtain a decorative material of Example 2. The decorative material of Example 2 has a transfer layer on the adherend.

<Resin composition for forming release layer>
・Urethane acrylate oligomer 100 parts by mass ・Reactive acrylic-modified silicone oil 0.5 parts by mass

[Example 3]
A transfer sheet and a decorative material of Example 3 were obtained in the same manner as in Example 1, except that the release layer-forming resin composition 1 was changed to the following release layer-forming resin composition 2.

<Resin composition 2 for forming release layer>
・Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 40 parts by mass ・Ionizing radiation curable resin (hexafunctional urethane acrylate oligomer): 60 parts by mass ・Ultraviolet absorbent (BASF, product name: Tinuvin479): 2 parts by mass Part Light stabilizer (Nippon Emulsifier Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[Comparative Examples 1 and 2]
The releasable supports, transfer sheets and decorative materials of Comparative Examples 1 and 2 were prepared in the same manner as in Example 2, except that the laminate 2 in obtaining the releasable supports was changed to laminates 3 and 4. Obtained. On the release layer of the release support used in Comparative Examples 1 and 2, a shape obtained by reversing the surface shape of the matte layers 3 and 4 is formed.

From the results in Table 1, the decorative material obtained using the transfer sheet of the present embodiment has a 60° gloss value of 1.5 or 1.6 on the release layer side of the decorative material, indicating a matting effect. It was confirmed that the visibility was extremely excellent and the texture was also excellent. In addition, it was confirmed that the moist texture was also excellent.
On the other hand, the decorative material obtained using the transfer sheet of Comparative Example 1 had some wrinkles on the surface as shown in FIG. 8, but the visibility of the matting effect was stably obtained. Although there were parts with the same gloss value as in Examples, there were parts with high gloss, and the surface condition was unstable (not uniform), and the texture could not be said to be excellent. there were. Moreover, the decorative materials obtained using the transfer sheets of Comparative Examples 1 and 2 lacked a moist feel, and rather had a rough feel.

7 is an optical microscope image of the release layer side of the decorative material obtained using the transfer sheets of Examples 1 and 3 (the width of the image corresponds to 272.0 μm. The width of FIGS. 8 and 9). is also the same.). According to the optical microscope images (FIG. 7) of Examples 1 and 3, it can be confirmed that the decorative material of Example has irregular wrinkles on its surface. On the other hand, according to the optical microscope image (FIG. 8) of Comparative Example 1, some wrinkles were generated on the surface, and although there were some areas with wrinkles similar to those of the example, the wrinkles were not formed. It can be seen that it is stable (not uniform) and mixed with areas without wrinkles. Further, according to the optical microscope image (FIG. 9) of Comparative Example 2, wrinkles as in Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed, indicating that the surface condition was unstable. (not uniform), and it cannot be said that the texture is excellent.

100: Transfer sheet 200: Decorative material 10: Releasable support 11: Support 12: Release layer 20: Transfer layer 21: Release layer 22: Primer layer 23: Decorative layer 24: Adhesive layer 30: Adherend 2: concave portion 3: convex portion (protruding portion)

Claims (16)

A transfer sheet having a transfer layer on a release support,
A transfer sheet, wherein at least a portion of the surface of the transfer layer on the release support side has a surface shape with an Ssk (skewness) of less than 0.00 as defined in ISO25178-2:2012. 2. The transfer sheet according to claim 1, wherein the surface profile has an Sku (kurtosis) defined in ISO25178-2:2012 of 3.00 or more. 3. The transfer sheet according to claim 1 or 2, wherein Rsm (mean length of curved element), which is a lateral parameter of the contour curve defined in JIS B0601:2013, of the surface shape is 100.00 µm or less. The surface shape according to any one of claims 1 to 3, wherein Rz (maximum height), which is a peak and height parameter of a contour curve defined in JIS B0601:2013, is 3.00 μm or more. transfer sheet. The surface shape according to any one of claims 1 to 4, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve defined in JIS B0601:2013, is 2.00 μm or less. transfer sheet. 6. The transfer sheet according to any one of claims 1 to 5, wherein the surface of the transfer layer forming the surface shape has an uneven shape composed of irregular wrinkles. 7. The transfer sheet according to claim 6, wherein the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary projections and recesses formed by being surrounded by the plurality of filamentary projections. . 8. The transfer sheet according to any one of claims 1 to 7, wherein the transfer layer has a release layer and an adhesive layer in this order from the release support side. 9. The transfer sheet according to claim 8, comprising one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. 10. The transfer sheet according to claim 8 or 9, wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation-curable resin. The transfer sheet according to any one of claims 8 to 10, wherein the release layer contains an ultraviolet absorber or a light stabilizer. The transfer sheet of any one of claims 8-11, wherein the release layer is substantially free of particles. The transfer sheet according to any one of claims 1 to 12, wherein the release support has a release layer on the support. 14. The transfer sheet according to claim 13, wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation-curable resin. A method for producing a decorative material, comprising the following steps (1) and (2).
(1) A step of obtaining a laminate in which the transfer layer of the transfer sheet according to any one of claims 1 to 14 and an adherend are in close contact with each other.
(2) A step of peeling off the release support from the laminate to obtain a decorative material having a transfer layer on the adherend. A decorative material having a transfer layer on an adherend,
A decorative material, wherein at least a part of the surface of the transfer layer opposite to the adherend has a surface shape with an Ssk (skewness) of less than 0.00 as defined in ISO25178-2:2012.

Images