JP2022154615A - Transfer sheet, manufacturing method of decorative material using the same, and decorative material - Google Patents

Abstract

To provide a transfer sheet capable of imparting visibility and texture of an excellent matt effect while imparting a soft touch feeling (soft tactile feeling), a manufacturing method of a decorative material having visibility and texture of an excellent matt effect, while having a soft touch feeling, and the decorative material.SOLUTION: A transfer sheet has a surface shape in which Spc (arithmetic average curvature of projection peaks) stipulated by JIS B0601:2013 is larger than 4000 mm-1 and Rsm (average length of curve elements) stipulated by JIS B0601:2013 is less than 30 μm, at least in part of a surface thereof. Also, a manufacturing method of a decorative material using the same and a decorative material are provided.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; exterior members such as outer walls, eaves, roofs, fences and fences; , malls and other fixtures or fixtures, general furniture such as chests, shelves, desks, kitchen furniture such as dining tables and sinks, or surface decorative panels such as cabinets for home appliances and OA equipment, interior or exterior parts for vehicles A so-called decorative material or decorative sheet is used as an article for decorating and protecting the surface of such as. As such a decorative material, for example, a material having a surface layer having a desired function is used.

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 used. and a method of forming an uneven shape on the outermost surface by embossing as described in Patent Document 2, and the like.
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. Furthermore, in the case of embossing, depending on the type of substrate to be embossed, the embossing conditions, and the combination of uneven shapes on the embossing plate, the matte uneven shape on the embossing plate may not be faithfully formed on the substrate. Therefore, in some cases, sufficient matting could not be imparted.

By the way, customer demands are diversified, and not only the above-mentioned visual matte effect, but also tactile expression is required. For example, when using a matting agent such as that of Patent Document 1, by increasing the amount used, the outline of the matting agent appears on the surface of the decorative sheet, resulting in a slightly rough surface feel, In other words, "roughness"
A tactile sensation that makes you feel may appear. 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 either 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 conventional decorative sheets and decorative materials are capable of achieving both excellent matting effect and tactile feel. In the present invention, attention is paid to the "soft touch feeling" (soft touch) among the tactile sensations.

The present invention provides a transfer sheet capable of imparting excellent visibility and texture of a matte effect and imparting a soft touch feeling (soft touch), a transfer sheet having excellent visibility and texture of a matte effect and a soft touch. An object of the present invention is to provide a method for manufacturing a decorative material having a touch feeling and the decorative material.

In order to solve the above problems, the present invention provides the following [1] to [14].
[1] A transfer sheet having a transfer layer on a release support,
At least part of the surface of the transfer layer on the release support side has an Spc (arithmetic mean curvature of the apex of the protrusions) specified in JIS B0601:2013 greater than 4000 mm ⁻¹ and specified in JIS B0601:2013. A transfer sheet having a surface topography such that the measured Rsm (average length of curvilinear elements) is less than 30 μm.
[2] The transfer sheet according to [1], wherein Rz (maximum height), which is a contour curve crest and height parameter defined in JIS B0601:2013, of the surface shape is 12.5 μm or less.
[3] In [1] or [2], wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve defined in JIS B0601:2013, of the surface shape is 2.0 μm or less. Transfer sheet as described.

[4] The transfer sheet according to any one of [1] to [3], wherein the surface of the transfer layer forming the surface shape has an uneven shape composed of irregular wrinkles.
[5] According to [4], the 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. transfer sheet.
[6] The transfer sheet according to any one of [1] to [5], wherein the transfer layer has a release layer and an adhesive layer in this order from the release support side.

[7] The transfer sheet of [6], which has one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer.
[8] The transfer sheet of [6] or [7], wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation-curable resin.
[9] The transfer sheet of any one of [6] to [8], wherein the release layer contains an ultraviolet absorber or a light stabilizer.

[10] The transfer sheet of any one of [6] to [9], wherein the release layer does not substantially contain particles.
[11] The transfer sheet of any one of [1] to [10], wherein the release support has a release layer on the support.
[12] The transfer sheet of [11], wherein the release layer contains a cured product of a resin composition containing an ionizing radiation-curable resin.

[13] 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 12 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.
[14] A decorative material having a transfer layer on an adherend,
At least a part of the surface of the transfer layer opposite to the adherend has an Spc (arithmetic mean curvature of the apex of the projection) defined in JIS B0601:2013 greater than 4000 mm ^-1 and JIS B0601:2013 Rsm (average length of curvilinear element) defined in 1. is less than 30 μm, and has a surface shape.

According to the present invention, a transfer sheet that can impart excellent visibility and texture of a matte effect and can impart a soft touch feeling (soft touch), has excellent visibility and texture of a matte effect, Moreover, it is possible to provide a method for producing a cosmetic material having a soft touch feeling and the cosmetic material.

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 schematic plan view showing an embodiment of a transfer sheet of the present invention. FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG. 2 is an optical microscope image of the surface of the decorative material obtained in Example 1. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Example 2. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Example 3. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 1. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 2. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 3. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 4. FIG. 4 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 5. 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 "greater than", "less than" and "to" regarding the description of the numerical range 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 coated with the Spc specified in JIS B0601:2013. (Arithmetic Mean Curvature of Projection Vertex) is greater than 4000 mm ⁻¹ and Rsm (mean length of curvilinear element) is less than 30 μm.

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 an Spc (arithmetic mean curvature of the apex of the protrusions) of 4000 mm ⁻ It has a surface profile with Rsm (average length of curvilinear element) greater than ¹ and less than 30 μm.

[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. , It is not limited to completely the same, and may vary slightly depending on the heat and pressure conditions during transfer, but the visibility and texture of the matte effect, Spc is greater than 4000 mm ^-1 , and Rsm is less than 30 μm , the "soft touch feeling" is maintained.

The surface profile of the transfer layer is required to have Spc (arithmetic mean curvature of peaks of protrusions) greater than 4000 mm ⁻¹ and Rsm (average length of curvilinear elements) less than 30 μm. By having such a surface shape of the transfer layer, 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"). can be imparted to the adherend, and a tactile sensation (touch), particularly a “soft touch” (soft touch) can be imparted to the adherend. "Soft-touch feeling" is a sensual expression, but "soft-touch feeling" in the present specification generally includes all tactile sensations that feel "soft". Specifically, it means a tactile sensation that is felt when touching a non-moisture smooth surface with the pad of a finger, unlike the cold or rough tactile sensation that tends to occur in conventional resin decorative sheets. Examples of materials that have a “soft touch feeling” include high-quality paper (not coated paper with a coated surface), Oxford cloth using fine threads of about 60 to 120 counts (fine count to extra fine count), etc. Cloth, baby skin, silk, tencel (lyocell) and other natural fiber fabrics, promix, rayon, cupra and other synthetic fibers, regenerated fiber and other chemical fiber fabrics, or peach fabrics made from these chemical fibers Examples thereof include skin-processed (thinly raised fabric having a touch similar to that of the skin of peach fruit).

(Spc (arithmetic mean curvature of protrusion vertex))
Spc (arithmetic mean curvature of protrusion apex) is one of the three-dimensional surface texture parameters defined in JIS B0601:2013, and is a portion classified as a mountain (convex portion) in the feature image included in the reference area. is the average curvature (average sharpness) of the tip of the peak, which is obtained from the arithmetic average value of the curvature radii of the peaks (protrusion apexes) of . Therefore, Spc is the reciprocal (mm ⁻¹ ) of the radius (mm).

The larger the value of Spc, the greater the curvature of the tip (1a in FIG. 1) of the peak (projection) (the reciprocal of the radius of curvature is smaller and the shape of the tip is sharper). On the other hand, the smaller the value of Spc, the smaller the curvature of the projection vertex (1b in FIG. 1) (the reciprocal of the radius of curvature is large, and the shape of the tip is dull). In other words, the smaller the Spc, the rounder the protrusions become, and the closer they are to a flat surface, the higher the luster. Therefore, in order to suppress gloss by focusing only on the Spc value, a surface shape with a large Spc (a surface shape with sharp apexes of protrusions) will increase light scattering on the surface and reduce gloss.

A surface shape with a small Spc has a rounded apex of the protrusions, so that the touch is soft. On the other hand, when the value of Spc is increased, the roundness of the protrusions is lost, and although the soft touch feeling is impaired, the matte effect is improved. Thus, if Spc is small, ie, 4000 mm ⁻¹ or less (curvature radius is 0.25 mm or more), the desired matte effect cannot be obtained, but if Spc is increased, ie, greater than 4000 mm ⁻¹ (curvature radius is less than 0.25 μm), the soft touch feeling is reduced, so it can be said that the matting effect and the soft touch feeling are in a trade-off relationship. In the present invention, in addition to Spc, by setting Rsm, which will be described later, within a specific range, it is possible to achieve both a matte effect and a soft touch feeling.

Spc is preferably 4100 mm ⁻¹ or more, more preferably 4150 mm ⁻¹ or more, from the viewpoint of improving matte effect and soft touch feeling in relation to Rsm (average length of curvilinear element) described later. It is preferably 4200 mm ⁻¹ or more, and the upper limit is preferably 7000 mm ⁻¹ or less, preferably 6500 mm ⁻¹ or less, more preferably 6000 mm ⁻¹ or less, and even more preferably 5700 mm ⁻¹ or less. The cut-off value is 0.8 mm for the measurement of Spc in this specification.

The measurement of Spc is a measurement 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, and the measurement conditions can be adjusted as appropriate. It can be measured under the conditions described in the examples. Rsm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness), which will be described later, can also be measured in the same manner.

(Rsm (average length of curvilinear element))
Rsm (average length of curve element) is a lateral parameter of the contour curve among the three-dimensional surface texture parameters defined in JIS B0601:2013, and is the average length of the contour curve element at the reference length. is. The smaller the Rsm, the more convex portions (2a and 2b in FIG. 2) included in the reference length. Therefore, in a surface shape with a small Rsm, since the apexes of the protrusions are densely present, for example, when the surface is stroked with a finger, the area in contact with the finger becomes large, resulting in a good soft touch feeling. Thus, if Rsm is large, ie, 30 μm or more, desired soft touch feeling cannot be obtained, but if Rsm is small, ie, less than 30 μm, good soft touch feeling can be obtained.

In the matte article of the present embodiment, the density of protrusions increases by reducing Rsm. The soft touch feeling is improved by increasing the Spc to improve the matte effect and further decreasing the Rsm. More specifically, the relationship between Spc and Rsm is as follows.
As described above, by increasing the Spc, a matte effect can be obtained, but a soft touch feeling cannot be obtained because the tactile sensation is rough. In the present invention, by increasing the Spc and further decreasing the Rsm, it has become possible to achieve both a matte effect and a soft touch feeling at a high level. By increasing the Spc, the surface shape has sharp projections, but as the Rsm is decreased, the projections are densely packed, so that the contact portion with the pad of the finger becomes even. , the soft touch feeling is improved. In this way, it is considered that the soft touch feeling is improved while the excellent matting effect is obtained, and it has become possible to achieve both the matting effect and the soft touch feeling at a high level.

In relation to the above Spc, from the viewpoint of improving the matte effect and the soft touch feeling, Rsm is preferably 29.5 μm or less, more preferably 29.0 μm or less, still more preferably 28.8 μm or less. is preferably 10.0 μm or more, more preferably 12.0 μm or more, and still more preferably 13.5 μm or more. By setting the lower limit to the above range, the planar shape exhibits a matte effect, and the production is not excessively difficult, which is preferable. Note that the cutoff value for the measurement of Rsm in this specification is 0.8 mm.

(wrinkles)
The surface shape of the transfer layer of the present embodiment preferably has fine wrinkles (wrinkles) visible in a plan view shown in FIG. 4, which will be described later. The wrinkles preferably have an irregular uneven shape. Regarding the surface shape of the transfer layer of the present embodiment, Spc (arithmetic mean curvature of apex of protrusion) and Rsm (average length of curvilinear element), preferably 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), while the minute wrinkles (wrinkles) are within a specific numerical range Spc (arithmetic mean curvature of the apex of the protrusion) and Having Rsm (average length of curvilinear element), and preferably Rz (maximum height) and Ra (arithmetic mean roughness) within certain numerical ranges facilitates formation. Thus, it can be said that Spc (arithmetic mean curvature of vertices of projections) and Rsm (mean length of curvilinear element), etc., and minute wrinkles (wrinkles) are inextricably linked. By having such a surface shape, the soft touch feeling (soft touch) and the matting effect are improved.
(Rz (maximum height))

In the present embodiment, as the surface shape of the transfer layer, Rz (maximum height), which is a lateral parameter of the profile defined in JIS B0601:2013, is preferably 12.50 μm or less.
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 convex portion is when viewed from the valley (concave portion). Therefore, in the surface shape that satisfies Spc (the arithmetic mean curvature of the apex of the protrusion) and Rsm (the average length of the curvilinear element), if the Rz (maximum height) is 12.50 μm or less, the height of the protrusion The variation in thickness is also reduced, and the soft touch feeling is improved.

Rz (maximum height) is preferably 12.0 μm or less, more preferably 11.5 μm or less, and still more preferably 10.0 μm or less, from the viewpoint of improving the matte effect and soft touch feeling, and the lower limit is It is preferably 3.25 μm or more, more preferably 3.50 μm or more, and still more preferably 4.00 μm or more. Note that the cutoff value for the measurement of Rz (maximum height) in this specification is 0.8 mm.

(Ra (arithmetic mean roughness))
In the present embodiment, the surface shape of the transfer layer preferably has Ra (arithmetic mean roughness) of 2.00 μm or less, which is a lateral parameter of the profile 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 height difference between the convex portions in the surface shape of the transfer layer and the concave portions formed accordingly, and the smoother and more uniform the shape tends to be. It is an index that shows Therefore, in the surface shape of the transfer layer that satisfies Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of curvilinear element), if Ra (arithmetic mean roughness) is 2.00 μm or less, Since the surface shape of the transfer layer has a more uniform and gentle shape of the protrusions, the extravagant touch is suppressed, and especially the soft touch feeling is improved. Moreover, the matting effect is also improved.
Ra (arithmetic mean roughness) is preferably 1.90 μm or less, more preferably 1.70 μm or less, and even more preferably 1.50 μm or less, from the viewpoint of improving matte effect and soft touch feeling, 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.

(Surface shape of transfer layer)
The surface shape of the transfer layer of the present embodiment preferably has wrinkles. By stably forming wrinkles on the surface of the transfer layer as described above, the matte effect is stably exhibited by the light diffusion effect caused by the shape of the wrinkles, and the layer also exhibits a soft touch feeling. FIG. 4 is a schematic plan view showing one embodiment of the transfer sheet of the present embodiment, and schematically illustrates an image on the transfer layer side surface of the decorative material obtained in the example. FIG. 4 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 are caused by the surface shape, that is, the surface shape having Spc and Rsm within the above specific numerical ranges, preferably other Rz and Ra within the above specific numerical ranges. There is no particular limitation as long as it exhibits wrinkles, so that it has the surface shape described above, so that it stably exhibits a matte effect and also exhibits a soft touch feeling.
Regarding wrinkles, at least one surface of the transfer layer should have an uneven shape composed of irregular wrinkles from the viewpoint of expressing the surface shape, improving the matting effect, and improving the textured soft touch feeling. Preferably, the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions. It is preferable to have a protrusion of In the present specification, the "striated protrusion" (hereinafter also referred to as "striated protrusion") means that the ratio of the length to the 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 a recess formed by being surrounded by the plurality of filamentary protrusions. .

Examples of aspects relating to these wrinkles include the aspect shown in FIG. 4 . FIG. 4 shows that the surface of the transfer layer has irregular wrinkles in a plan view, and that the irregular wrinkles are a plurality of protrusions 2 formed by a plurality of curved linear projections, and a concave portion 3 formed by being surrounded by a plurality of protrusions (plurality of protrusions 2), and at least a portion of the plurality of curved protrusions 2 are each meandering linear protrusions. It is also shown that a meandering recess 3 is formed, formed by a portion and surrounded by the meandering filament projection. The transfer layer that constitutes the transfer sheet of the present embodiment stably exhibits a matting effect by stabilizing the formation of wrinkles shown in FIG. 4, and also exhibits a soft touch feeling.

Here, “curved” means having one or more portions in which the extending direction of the continuous filamentary projections 2 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 2 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 the width of the planar view shape of the filamentary protrusion 2 is ignored, a form having a portion approximated by two sides sandwiching one vertex of a V-shaped broken line or triangle etc.

Further, the term "meandering" refers to a portion in which the extending direction of the continuous linear projections 2 is reversed from one side to the other side (hereinafter also referred to as "reversed portion") at least two times. It has at least two points, and when the protrusion 2 of the filament is advanced in its extending direction, there are portions where the extending direction of the protrusion 2 of the filament is alternately reversed in the two adjacent places. means to have For example, when the width of the projection 2 of the filaments in plan view is ignored and approximated by a continuous curve, there is a form having a portion approximated by the Roman letter "S". In addition, when the linear projections 2 are approximated by a straight line when the width of the projection 2 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 ( lenticular lens)”, which are arranged with a certain periodicity in a specific direction. 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 soft touch feeling can be obtained by having irregular wrinkles, but both are preferably irregular. The transfer sheet of the present embodiment has irregular wrinkles on the surface of the transfer layer, thereby improving the visibility and texture of the matting effect, stably exhibiting an extremely excellent matting effect, and providing a soft texture. It expresses a feeling of touch.

As described above, the transfer layer has wrinkles, that is, unevenness on at least one surface thereof. For the projections and recesses in the uneven shape, for example, the difference in brightness of the image on the surface of the transfer layer of the present embodiment is used, and the darkest part of the density distribution image is set to gradation 255, and the lightest part of the density distribution image is graduated. For the gradation 0 to 255, the gradation 0 to 127 can be divided into concave portions, and the gradation 128 to 255 into convex portions by binarization processing. 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 location where wrinkles are formed is not particularly limited as long as it is the surface of the transfer layer. A matte effect and a soft touch feeling are exhibited by the formation of .
For example, in the case of having a decorative layer, which will be described later, and irregular wrinkles are formed in part, if the wrinkles are formed in a place corresponding to the pattern of the decorative layer (for example, on the pattern), the pattern will be more prominent than the surroundings. Since it is visually recognized as a matted portion, it is possible to improve the design.

Also, as shown in FIG. 4, it has a plurality of protrusions formed by a plurality of protrusions that are irregular but uniform to some extent, and recesses surrounded by the protrusions. is preferred. Therefore, a shape in which the width of one protrusion (protrusion) changes extremely is unlikely to be the surface shape described above, and is not a preferable aspect for obtaining the visibility and texture of the matte effect. It cannot be said that this is a preferable mode for obtaining a touch feeling. 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 soft touch feeling will be described below. . When the wrinkles have the following shape, it becomes easier to exhibit the surface shape described above, and the matte effect and the soft touch feeling 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 projections are within the above ranges, the surface shape is likely to be exhibited, and in relation to the depressions, the matting effect is stably improved and the soft touch feeling is improved.
Here, the 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 100 projections in total. value. In addition, as shown in FIG. 3, since the width of one protrusion (projection) is not the same but varies, 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 is easily exhibited, and in relation to the convex portions, the matting effect is stably improved and the soft touch feeling 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 still 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 surface shape is likely to be exhibited, the matting effect is stably improved, and the soft touch feeling 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 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 soft touch feeling is obtained. improves.
Here, the occupancy ratio of the projections is the average value of the occupancy ratios of the projections 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 of 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 soft touch feeling. 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 matte effect is stably improved and the soft touch feeling 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 soft touch feeling is improved.
The number of protrusions is the average number of protrusions at 10 locations (100 μm square area×10 locations) on the transfer sheet of the present embodiment.

FIG. 5 is a cross-sectional view showing an embodiment of the transfer layer 20 that constitutes the transfer sheet of the present embodiment, and is a cross section taken along a plane parallel to the thickness direction (the Z direction in FIG. 5) of the transfer layer. It is a diagram.
The shape of the concave portion may be, for example, an acute-angled one as shown in FIG. 5A, a semicircular or semielliptical shape as shown in FIG. 5B, or a combination thereof. Alternatively, a shape such as 3c in FIG. 5, in which one convex part has a concave part, may be used.
On the other hand, as for the shape of the convex portion, as shown in 2c and 2d of FIG.

(Formation of surface shape of transfer layer)
The surface shape of the transfer layer is preferably formed based on the surface shape of the basic matte layer described later. By forming the basic matte layer first and then forming the surface of the transfer layer, the desired surface profile can be formed without containing wrinkle stabilizers and the like. That is, the transfer layer does not need to contain a wrinkle-forming stabilizer or the like necessary for forming the basic matte layer described later. In addition, unlike the basic matte layer, there are more options for the resin constituting the transfer layer. By preparing the basic matte layer in this manner, the transfer layer can be made to have a resin composition that improves the weather resistance by adding an ultraviolet absorber, a radical scavenger, and the like, which is preferable.

Regarding the surface shape of the transfer layer, Spc (arithmetic mean curvature of apex of projection), Rsm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness) satisfy preferred ranges. For this purpose, 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 Spc is preferably adjusted for the shape of the recesses of the release support because the shape of the recesses of the release support becomes the shape of the protrusions of the transfer layer.

A method for adjusting the shape of the concave portion of the releasable support will be described.
The surface shape A of the article becomes a surface shape complementary to the shape A when inverted once. When the complementary surface profile is further inverted, it returns to the same surface profile as the surface profile A (the "same" is not limited to being exactly the same, but Spc and Rsm fall within a specific range. By this, it means the same that allows for errors in visibility, texture and soft touch feeling of the matte effect that the original surface shape has.). That is, the surface profile of the article returns to its original surface profile after being flipped twice. This two-time reversal may be used to adjust the convex shape of the surface structure of the transfer layer.
For this reason, first, a basic matte layer (hereinafter also referred to as "basic matte layer") is prepared, and then the surface shape obtained by inverting the surface shape of the basic matte layer is formed to support releasability. It is preferable to use the surface shape of the body. 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), (3 -1) ~ (3-2) can be produced by three methods.

(1-1) Prepare a basic matte layer A that satisfies parameters such as Spc and Rsm.
(1-2) The basic matte layer A is pressed against the surface of the releasable support, and a shape obtained by reversing the surface shape of the basic matte layer A is formed on the surface of the releasable support. The basic matte layer A corresponds to the basic matte layer described later. As a release support, a laminate having a release layer on the support is preferably used, and when the basic matte layer A is pressed against the surface of the release layer, the release layer is in an uncured state, After curing, the surface of the release layer (=the surface of the releasable support) can be formed into a shape obtained by reversing the surface shape of the basic matte layer A.

(2-1) Prepare a basic matte layer A that satisfies parameters such as Spc and Rsm.
(2-2) A mold A having the same surface shape as that of the basic matte layer A is prepared. The mold A having the same surface shape as the basic matte layer A can be obtained, for example, by producing a mold B in which the surface shape of the basic matte layer A is reversed, and further by producing a mold in which the surface shape of the mold B is reversed. Obtainable. A mold obtained by reversing the surface shape of mold B is mold A. The mold A and mold B can be produced by a general-purpose mold production method such as electroforming.
(2-3) The mold A is pressed against the surface of the releasable support, and a shape obtained by inverting the surface shape of the mold A (=the surface shape of the basic matte layer A) is formed on the surface of the releasable support. to mold. As the releasable support, a laminate having a release layer on the support is preferably used, and when the mold A is pressed against the surface of the release layer, the release layer is left in an uncured state and then cured. For example, the surface of the release layer (=the surface of the releasable support) can be shaped by inverting the surface shape of the mold A (=the surface shape of the basic matte layer A).

(3-1) A surface shape that satisfies parameters such as Spc and Rsm is designed by simulation, and a mold C is produced by reproducing the designed surface shape by laser microfabrication.
(3-2) The mold C was pressed against the surface of the releasable support, and the surface shape of the mold C (=surface shape satisfying parameters such as Spc and Rsm) was inverted on the surface of the releasable support. Mold the shape. As the releasable support, a laminate having a release layer on the support is preferably used, and when the mold C is pressed against the surface of the release layer, the release layer is left in an uncured state and then cured. For example, the surface of the release layer (=the surface of the releasable support) can be shaped by inverting the surface shape of the mold C (=the surface shape that satisfies parameters such as Spc and Rsm).
As the above (3-1), the surface shape formed by the mold C in the above (3-2) is designed by simulation, and a mold C' in which the designed surface shape is reproduced by laser microfabrication is produced, and the mold is released. It may also be used as a flexible support and molded into an inverted shape.

The thickness of the basic matte layer is not particularly limited as long as it is a thickness capable of stably expressing the matting effect and forming the wrinkles to the extent that a soft touch feeling can be expressed. Considering the ease of application, etc., it 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. is 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less.
In the present specification, the thickness of the basic matte layer is the average value of the 20 thicknesses measured from the image of the cross section of the transfer sheet taken using a scanning electron microscope (SEM). do. 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.

The basic matte layer is a layer exhibiting the surface shape described above over its entire surface, and since the transfer layer of the present embodiment has the surface shape on at least part of the surface, at least part of the surface of the transfer layer It may be provided on the entire surface. When the transfer layer of the present embodiment has the release layer, it may be provided on at least part of the surface of the release layer, or may be provided over the entire surface of the release layer.
If the basic matte layer is provided at a portion of the transfer layer that is visible and touched by the consumer, that is, if the surface shape is provided at a portion of the decorative material that is visible and touched by the consumer, The effects of the invention, such as matte effect and soft touch feeling, are obtained.

Further, even when the base material has the shape of a film, sheet, or plate, the basic matte layer may be provided at a place where the consumer can see and touch the decorative material. It may be provided on a part of the surface, or may be provided on the entire surface. It is preferably provided over the

(basic matte layer)
Regarding the production methods (1-1) to (1-2) and (2-1) to (2-3) above, the basic matte layer used for "preparation of the concave shape of the release support"
(1) forming a fine wrinkle structure on the surface of the basic matte layer;
is preferred.
Furthermore, the basic matte layer is
(2) The composition formulation of the resin composition for forming the basic matte layer, especially the type of polymerizable monomer and polymerizable oligomer, the number of functional groups, the molecular weight, the presence or absence of a wrinkle-forming stabilizer, and if a wrinkle-forming stabilizer is used, Optimizing the particle size and content of the wrinkle-forming agent,
(3) Optimizing the irradiation conditions of the resin composition for forming the basic matte layer, particularly the wavelength of light having a wavelength of 100 nm or more and 380 nm or less that can cause curing shrinkage of the surface portion of the basic matte layer, the integrated weight, the ultraviolet power density, etc. ,
(4) In addition to the above, the type and thickness of the base material forming the basic matte layer, the thickness of the basic matte layer, etc. are optimized.
is preferred.
By optimizing these, the surface shape of the basic matte layer (= the surface shape of the transfer layer of the present embodiment) can be changed from Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of the curvilinear element). It is within the specific numerical range, and preferably Rz (maximum height) and Ra (arithmetic mean roughness), which will be described later, are easily set within a predetermined numerical range.

The basic 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. It may be configured as a single layer or laminated.

As the resin composition forming the basic matte layer, from the viewpoint of obtaining a basic matte layer having an excellent matting effect and an excellent soft touch feeling, a resin composition containing a resin and a wrinkle-forming stabilizer ( Hereinafter, it may be referred to as "a resin composition for forming a matte layer".) is preferable. That is, the base 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 basic matte layer, so that the visibility of the matting effect is expressed uniformly over the entire surface of the basic matte layer, and partial gloss unevenness is achieved. Visibility of a stable matte effect (hereinafter simply referred to as "visibility of a stable matte effect", and equivalent expressions may be used), and uniformity of the surface condition (also referred to as “texture”). Since the wrinkles formed in the basic matte layer directly become wrinkles in the transfer layer (release layer), they greatly contribute to the development of the soft touch feeling of the transfer sheet. That is, the improvement in the visibility, texture, and soft touch feeling of the matte effect of the basic matte layer, which will be described later, is the improvement in the visibility, texture, and soft touch feeling of the matte effect that can be imparted by the transfer sheet of the present embodiment. contribute to
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 expresses a soft touch feeling by forming wrinkles.

In the prior art such as Patent Document 1, the matting agent that has been used for matte expression expresses the visibility of the matting effect itself 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 release layer may contain an agent conventionally used as a matting agent, but preferably does not contain a matting agent. As described above, the release layer of the present embodiment provides extremely excellent visibility and texture of the matte effect 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.

The wrinkle-forming stabilizer is not a matting agent, and can be used without any particular limitation as long as the average particle size has an upper limit of 100% or less of the thickness of the basic matting layer or 30 μm or less, whichever is smaller. can.
From the viewpoint of improving the matte effect and soft touch feeling, the average particle diameter of the wrinkle-forming stabilizer having an upper limit of 100% or less of the thickness of the basic matte layer or 30 μm or less, whichever is smaller. It is preferred to use at least one of the two wrinkle stabilizers distinguished by: 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 a 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 soft touch feeling 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 the soft touch feeling. Wrinkle-forming stabilizer 1 is preferable, and wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 can also be used in combination.

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 basic matte layer or 30 μm or less, whichever is smaller. From the viewpoint of stably improving the matting effect and improving the soft touch feeling, 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 of the thickness of the basic matte layer is preferably 90% or less of the thickness of the basic matte layer, more preferably 80% or less of the thickness of the basic matte layer, It is more preferably 70% or less of the thickness of the basic matte layer. Any combination of the upper limit of the thickness of the erase layer and the upper limit of the absolute value may be set to the smaller one. For example, the upper limit may be 90% or less of the thickness of the basic matte layer or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the thickness of the basic matte layer. You can also The thickness of the basic 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 soft touch feeling, 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 a laser beam diffraction method.

From the viewpoint of stabilizing the formation of wrinkles by the wrinkle-forming stabilizer, stably improving the matting effect, and improving the soft touch feeling, wrinkle-forming stabilizers (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, relative to 100 parts by mass of the resin forming the basic matte layer. The amount is preferably 1.0 parts by mass or more, and more preferably 1.2 parts by mass or more. For example, from the viewpoint of improving the productivity of the decorative material due to the applicability of the resin composition for forming the basic matte layer, and the visibility and texture of the matte effect, it is preferably 25.0 parts by mass or less, more. It is 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 soft touch feeling 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 soft touch feeling is also obtained.

(resin)
As the resin for forming the basic matte layer, a resin composition for forming the basic matte layer containing a predetermined amount of the wrinkle-forming stabilizer is formed and cured to form a cured product that constitutes the basic matte layer. If it is 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 manufactured based on the basic matte layer (2-2 above). For this reason, the resin forming the matte layer is preferably a resin that easily exhibits surface properties such as processability, and the ionizing radiation-curable resin is a preferred resin from these points of view. The basic matte layer retains the matte effect and soft touch feeling, and can impart the desired shape to the transfer sheet as it is. can give.

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 cross-linked 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 usually ultraviolet rays (UV) or electron beams (EB) are 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 ultraviolet curable resins, which stabilize the formation of wrinkles by the wrinkle-forming stabilizer, stably improve the matting effect, and provide a soft touch feeling. 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 stably improving the matting effect by stabilizing the formation of wrinkles, the viewpoint of improving the soft touch feeling, and the transfer sheet steadily imparting a shape having a matting effect and a soft touch feeling, The number of functional groups of the polyfunctional (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, the said surface shape is especially easy to obtain, and it becomes easy to improve a soft touch feeling.
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 thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
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.
From the viewpoint of stably improving the matting effect by stabilizing the formation of wrinkles, improving the soft touch feeling, and steadily imparting a shape having a matting effect and a soft touch feeling to the transfer sheet, Urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth)acrylate oligomer are preferred, and urethane (meth)acrylate Oligomers and 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 matte effect, improves the soft touch feeling, and also provides a shape with a matte effect and soft touch feeling. From the viewpoint of steadily imparting to the transfer sheet, the number is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, and still 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 this embodiment, as the resin for forming the basic matte layer, the polymerizable oligomer alone, the polymerizable monomer alone, or a combination of the polymerizable oligomer and the polymerizable monomer can be used. , from the viewpoint of stably improving the matting effect by stabilizing the formation of wrinkles, from the viewpoint of improving the soft touch feeling, and from the viewpoint of steadily imparting a shape having a matting effect and a soft touch feeling to the transfer sheet. Preferably, the polymerizable monomer is used alone, or the polymerizable oligomer and the polymerizable monomer are used 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.
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 basic matte layer is preferably composed of a cured product of a resin composition containing a predetermined content of the wrinkle-forming stabilizer. It is included in the content. The resin composition may contain other components in addition to the wrinkle-forming stabilizer and resin, depending on desired performance and the like.
The resin composition for forming the basic 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.

Further, 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 basic matte layer)
The basic matte layer is formed by irradiating a layer of the resin composition for forming the basic matte layer containing the resin and the wrinkle-forming stabilizer with light having a wavelength of at least 100 nm or more and 380 nm or less. A forming step is provided.
By this forming method, for example, a basic matte layer having a surface shape as shown in FIG. 5 can be formed (the transfer layer in FIG. 5 is obtained by reversing the surface shape of the basic matte layer twice). That is, the surface topography of the transfer layer in Figure 5 is the same as the surface topography of the base matte layer (identical here means as described above). For example, the resin composition for forming the basic matte layer is applied on a substrate, a layer of the resin composition is formed on the substrate, and the wavelength light is irradiated to form the basic matte layer. can be formed to produce a laminate having a substrate and a basic matte layer.
This forming method forms a basic matte layer having a matting effect such that the 60° gloss value on the side of the basic matte layer is 20.0 or less, 10.0 or less, or even less, and has a soft touch feeling. It is suitable when

The method for forming the basic matte layer makes it possible to easily obtain the basic matte layer. Specifically, in forming the basic matte layer, the matte-forming resin composition containing a wrinkle-forming stabilizer for forming the basic matte layer is irradiated with ultraviolet light having a short wavelength of at least 100 nm or more and 380 nm or less. Thus, wrinkles can be formed on at least one surface of the basic matte layer, and the basic matte layer can be provided with a matte effect and a soft touch feeling.

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

When short-wavelength ultraviolet rays are irradiated to a coating layer in which a resin composition for forming a basic matte layer is applied to a predetermined thickness, the energy of the ultraviolet rays permeates only the surface portion, and the energy does not reach the lower layers. As a result, only the surface portion of the resin composition begins to cure, 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 basic 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 basic matting layer. However, the matting effect and the stable expression of the soft touch feeling cannot be explained only by curing only the surface portion with short wavelength ultraviolet rays. Can not. That is, in order for the basic matte layer to stably have wrinkles to exhibit a matte effect and a soft touch feeling, it is essential to contain a wrinkle-forming stabilizer. Considering that a stable matte effect and soft touch feeling due to wrinkle formation are not obtained when the wrinkle formation stabilizer is not included, the wrinkle formation stabilizer functions as a nucleus that triggers wrinkle formation. Around the core, 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 matte effect and soft touch feeling are stably exhibited.

In the method for forming the basic matte layer, the resin composition for forming the basic 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 the basic 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 basic matte layer having wrinkles that exhibit a soft touch feeling. 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 soft touch feeling is also improved.

From the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the soft touch feeling, 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. is 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, even 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 soft touch feeling, 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.

From the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the soft touch feeling, the integrated light amount of the wavelength light is preferably 1 mJ/cm ² or more, more preferably 10 mJ/cm ² . Above, more preferably 30 mJ/cm ² or more, still 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.
In addition, the oxygen concentration at the time of irradiation with the above-mentioned wavelength light 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 basic matte layer forming step, in addition to 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 basic 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 resin composition for forming the basic matte layer by irradiating in advance with light having a wavelength exceeding 385 nm or more, preferably with light having a wavelength of about 385 nm or more and 400 nm or less, irradiating with light having a wavelength of 100 nm or more and 380 nm or less. Alternatively, post-curing may be performed to further cure the resin composition after irradiation with light having a wavelength of 100 nm or more and 380 nm or less. 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 basic matte layer. Moreover, although the 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 basic matte layer.

In the method for forming the basic matte layer, the basic matte layer is formed by coating a resin composition for forming the basic matte layer with a known method such as gravure printing, bar coating, roll coating, reverse roll coating, comma coating and the like. The coating layer (uncured resin layer) applied by the method of (1) 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 releasable support is a shape that is the reverse of the surface shape that the transfer sheet of the present embodiment can impart to an adherend, that is, the shape that is the reverse of the surface shape of the transfer layer. Further, the surface shape of the release support is preferably formed by the basic matte layer as described above.
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 the formation of a release layer and has good peeling workability after transfer. A support made of resin is hereinafter referred to as a plastic sheet. Films, sheets, and plates are referred to in order of relatively thin thickness. The difference does not cause any difference in the interpretation of the rights of the present invention.
In the case of a substrate made of a fibrous material such as paper, when a liquid resin composition for forming a matte layer is applied, the liquid composition permeates into the substrate, thereby increasing the number of fibers on the surface of the substrate. The effect of the uneven shape appears on the surface of the matte layer, and the desired Spc and Rsm values may not be obtained. In such a case, it is preferable to form a known permeation-preventing resin layer on the surface of the substrate of fibrous material on which the matting layer is formed by a method such as coating. As such a permeation-preventing resin layer-forming resin, for example, a two-liquid curable urethane resin can be used.

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 30 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 necessary in order to improve the releasability between the release support and the transfer layer, and to exhibit a function as a "mold" for imparting a surface shape to the transfer layer (release layer). It is a layer provided according to
The release layer is preferably provided over the entire surface of the support in order to improve the releasability from the transfer layer and to give the entire surface of the transfer layer (release layer) a shape.
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 that constitutes 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, and is a layer capable of imparting a surface shape to the adherend. Therefore, the release layer preferably has good surface properties such as scratch resistance, weather resistance, and stain resistance.

The release layer preferably contains 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 90% by mass or more, still more preferably 95% by mass or more, and more preferably is 100% by mass or more.

The release layer is a cured product of a resin composition containing a curable resin as the resin, in order to obtain surface properties such as scratch resistance, to easily retain the surface shape, and to easily impart a desired surface shape. and preferably urethane acrylic resins such as urethane (meth)acrylate oligomers.
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. be.

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 in that surface properties such as scratch resistance can be obtained, the surface shape can be easily maintained, and a desired surface shape can be easily imparted. 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 there is no restriction on 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.
It is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
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.

The release layer may contain particles such as matting agents and wrinkle stabilizers, but is preferably substantially free of said particles. By substantially not containing particles in the release layer, it is possible to suppress deterioration in the abrasion resistance, weather resistance, stain resistance, etc. of the release layer caused by falling off of the particles. In addition, even if no matting agent is contained, a sufficient matting effect can be obtained depending on the surface shape, so a matting agent is not particularly required.
The fact 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 adhesive 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, an acrylic, urethane, silicone, rubber, or other adhesive 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. Examples include adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like. 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 may contain a coloring agent as needed.
By including a coloring agent in the adhesive layer, the adhesive layer alone or in combination with the adhesive layer and a decorative layer described later enhances the design of the transfer layer and improves the concealability of the transfer layer for attachment. It can hide the color and appearance of the surface of the material.

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 may be subjected to physical surface treatments such as the oxidation method and roughening method described above, chemical surface treatments, etc., if necessary. A primer layer may be provided between these layers as an easy adhesion layer, or these surface treatments and a primer layer may be combined. It may have a primer layer. The 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 and the urethane component within the above range, the primer layer does not become an excessively hard coating film, and sufficient processability is obtained, and when the primer layer is formed on the release layer, This is preferable because it improves the adhesion between the release layer and the primer layer.

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.
The patterns (patterns) expressed by the decorative layer include wood grain patterns such as annual rings and conduit 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; Tile patterns including joint grooves; brickwork patterns including joint grooves; grain patterns; satin patterns; 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. 0.5 μm or more and 5 μm or less is more preferable. In particular, 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. is preferred.

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 separator is provided so as to be in contact with the adhesive layer 24 when the transfer sheet of this embodiment has the layer structure shown in FIG. 3, for example. Then, when the transfer sheet is used, the separator is peeled off, and the exposed adhesive layer and the adherend are brought into contact with each other to be laminated.

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 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 matt finish, the 60° gloss value 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 this embodiment, when forming the basic matte layer, by using a combination of two types of wrinkle-forming stabilizers having a predetermined average particle size and reducing the content thereof to a small amount as described above, Not only is it possible to stably obtain excellent matte effect visibility and texture, but also a rough and soft touch feeling 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. In addition, a cosmetic material exhibiting a color tone other than black or other dark colors can also 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.

[Manufacturing method of transfer sheet]
The transfer sheet of this embodiment can be manufactured, for example, as follows. The manufacturing method described below assumes the manufacture of a transfer sheet having the layer structure shown in FIG.
It can be produced through a releasing support forming step, a release layer forming step, a primer layer forming step, a decorative layer forming step, and an adhesive layer forming step.
The step of forming the release support is as described in the method for forming the surface shape of the transfer layer. It is applied, the surface shape of the basic matte layer is formed on the applied surface, and it is cured by irradiation with ultraviolet rays or the like. Needless to say, when the release support does not have a release layer and is only a support, the support may be provided with the above-mentioned surface shape. The conditions for curing the release layer may be appropriately selected according to the type of the resin composition of the release layer, and the release layer may be cured by irradiation with heat, ultraviolet rays, electron beams, or other ionizing radiation.

Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but usually the uncured resin layer can be cured at an acceleration voltage of about 70 to 300 kV. preferable. The irradiation dose is preferably an amount that saturates the crosslink density of the ionizing radiation curable resin, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

The electron beam source is not particularly limited, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type are used. be able to.
When ultraviolet rays are used as the ionizing radiation, radiation containing ultraviolet rays having a wavelength of 190 to 380 nm is emitted. There are no particular restrictions on the ultraviolet light source, and for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, carbon arc lamps and the like are used.

Next, the release layer-forming resin composition is applied onto the cured release layer and cured in the same manner as the release layer.

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

[Method for producing decorative material]
The manufacturing method of the decorative material of the present embodiment has the following steps (I) and (II).
(I) 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.
(II) 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 (I) 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 (I), 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 (I).

One embodiment of the step (I) 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 (I), 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 and bringing the transfer layer of the transfer sheet and the resin into close contact 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 arbitrarily decorated such as grooving and chamfering can be applied to the surface and the butt end 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, washstands, etc. It is suitably used as various members such as members, surface decorative boards for cabinets such as home appliances and OA equipment, interior and exterior members for vehicles, signboards, soundproof walls, and the like.
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, and 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. That is, the transfer sheet of the present embodiment is suitably used as a transfer sheet for transferring a transfer layer such as an uneven shape and a pattern layer to these various members.
Among the decorative materials, the resin decorative board is preferably used mainly for surface decorative boards of general furniture such as chests of drawers, shelves, and desks, fittings such as doors, various counters, 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 the Spc (arithmetic mean curvature of peaks of protrusions) is greater than 4000 mm ⁻¹ and Rsm (average length of curvilinear elements) is less than 30 μm.

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 Spc (arithmetic mean curvature of the apex of the protrusion) greater than 4000 mm ⁻¹ and Rsm (curve The average length of the elements) is less than 30 μm.

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 Spc (arithmetic mean curvature of projection apex), Rsm (average length of curvilinear element), Rz (maximum height ) and Ra (arithmetic mean roughness) were measured. The measurement area is a rectangle (1024 μm × 768 μm) at any point on the surface of the decorative material, using 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: 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 laminating a black plate via an adhesive layer on the back surface of the polycarbonate resin plate of the decorative material obtained in Examples and Comparative Examples. 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 device (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, Chamber humidity: 98% RH, Time: 4 hours <<Water spray process>>
Water is sprayed for 10 seconds before and after the condensation process.

(Evaluation of soft touch feeling)
For the decorative materials obtained in Examples and Comparative Examples, an oxford cloth using 80-count cotton thread was used as a standard of soft-touch feeling, and 20 random adults were asked to evaluate the surface feel. , was 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 soft.
B: 15 or more and 17 or less evaluated that the tactile sensation was close to the standard and that the tactile sensation was soft.
C: 14 or less people evaluated that the tactile sensation was close to the standard and that the tactile sensation was soft.

2. Preparation of Basic Matte Layer and Releasable Support [Basic Matte Layer]
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 easy-adhesion layer, the resin composition 1 for forming the basic matte layer described later is applied by a gravure method (coating amount: 18 μm (dry)), and then ultraviolet rays are applied using a UV irradiation device composed of an LED. (wavelength: 395 nm, amount of ultraviolet rays: 6 W/cm ² ), and then ultraviolet rays are irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), output density of ultraviolet rays: 1 W/cm, integrated amount of light: 10 up to 100 mJ/cm ² in a nitrogen atmosphere (oxygen concentration of 200 ppm or less)), and then further irradiated with ultraviolet rays using a high-pressure mercury lamp (ultraviolet power density: 200 W/cm), resulting in a laminate having a matte layer on the substrate ( 1) was obtained.

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, a curable resin for the following laminate (2) (for forming a release layer) is applied on the easy-adhesion layer by a gravure method to form a coating film (coating amount: 5 μm (dry)), and support. A laminate (2) having an easy-adhesion layer and an uncured release layer on the body was obtained.
Next, the surface of the obtained laminate (1) on the basic matte layer side is dry-laminated to the uncured coating film (uncured release layer) of the laminate (2), and the laminate (2′) is obtained. got
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 curable resin.
Next, the laminate (1) was peeled off from the laminate (2') to obtain a release support used in Example 1 having an easy-adhesion layer and a release layer on the support. On the surface of the release support, a shape obtained by reversing the surface shape of the basic matte layer is formed.

<Resin composition 1 for forming basic matte layer>
・60 parts by mass of polyfunctional urethane acrylate oligomer (number of functional groups: 4) ・30 parts by mass of polyfunctional acrylate monomer (bifunctional) ・10 parts by mass of monofunctional acrylate monomer ・Wrinkle-forming stabilizer (silica particles, average particle size : 5 nm) 3 parts by mass and 0.8 parts by mass of a photopolymerization initiator (benzophenone-based) <curable resin for laminate (2) (for releasing layer formation)>
・Urethane acrylate oligomer 100 parts ・Reactive acrylic-modified silicone oil 0.5 parts (used as a release agent)

3. Preparation of transfer sheet and decorative material [Example 1]
On the release layer of the release support obtained above, the resin composition 1 for forming a release layer described later is applied to form an uncured resin layer, and an electron beam (applied voltage: 175 KeV, 5 Mrad ( 50 kGy)) was irradiated to cure the uncured resin layer to form a release layer (thickness: 5 μm). Corona irradiation was then performed on the release layer.
Next, a resin composition for forming a primer layer, which will be described later, 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. Then, from the transfer sheet side, using a laminator (manufactured by Navitas Co., Ltd., roll type thermal transfer machine, product name "RT-300"), pressurize while heating under the 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 of the transfer sheet 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 oligomer): 100 parts by mass ・Ultraviolet 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]
In [Matte layer 1], the resin composition for forming the matte layer, the coating amount thereof, and the base material were changed to the coating amount and the base material shown in Table 1, and the resin composition for forming the release layer was changed to the following. A release support, a transfer sheet, and a decorative material of Example 2 were obtained in the same manner as in Example 1, except that Resin Composition 2 was used.
<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 absorber (BASF, trade name: Tinuvin479): 2. 0 parts by mass Light stabilizer (Nippon Emulsifier Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[Example 3]
A polypropylene sheet (PP, thickness: 100 μm) obtained by subjecting the substrate to corona discharge treatment by changing the coating amount of the resin composition for forming the matte layer in [matte layer 1] to that shown in Table 1. ), a resin composition for forming an easy-adhesion layer (urethane resin, coating amount: 2 μm (when dry)) is applied to one surface of the base material, and the matte layer is formed on the easy-adhesion layer. A release support, a transfer sheet, and a decorative material of Example 3 were obtained in the same manner as in Example 1, except that the resin composition for was applied.

[Example 4]
In Example 1, the substrate was changed to a PET sheet (Cosmoshine (registered trademark) A4160 (50 μm) manufactured by Toyobo Co., Ltd.), and a colored layer (thickness: 3 μm (when dry) was applied to the easy-adhesion surface of the substrate. ) in the same manner as in Example 1, except that the resin composition 1 for forming the basic matte layer is applied on the colored layer after coating the release support and the transfer sheet of Example 4. And a cosmetic material was obtained.

[Comparative Example 1]
In [Matte layer 1], the base material was changed to a colored base paper for building materials (thickness: 30 μm), and one side of the base material was coated with a colored layer (thickness: 3 μm (dry)). Thereafter, the releasing support of Comparative Example 1 was prepared in the same manner as in Example 1, except that the resin composition 1 for forming the matte layer was applied onto the colored layer (coating amount: 5 μm (when dry)). , a transfer sheet and a decorative material were obtained.

[Comparative Example 2]
In Example 1, in [Matte layer 1], the coating amount of the resin composition for forming the matte layer was set to 5 μm, and ultraviolet rays using a UV irradiation device composed of LEDs were not irradiated in the same manner. , a release support, a transfer sheet and a decorative material of Comparative Example 2 were obtained.

[Comparative Example 3]
Comparative Example 3 was prepared in the same manner as in Example 1, except that the resin composition 2 for forming the basic matte layer was used instead of the resin composition 1 for forming the basic matte layer in [Matte layer 1]. A release support, a transfer sheet and a decorative material were obtained.

<Resin composition 2 for forming basic matte layer>
・60 parts by mass of polyfunctional urethane acrylate oligomer (number of functional groups: 7) ・30 parts by mass of polyfunctional acrylate monomer (bifunctional) ・10 parts by mass of monofunctional acrylate monomer ・Wrinkle-forming stabilizer (silica particles, average particle size : 5 nm) 15 parts by mass and 0.8 parts by mass of a photopolymerization initiator (benzophenone type)

[Comparative Example 4]
Comparative Example 4 was carried out in the same manner as in Example 2 except that the resin composition 2 for forming the basic matte layer was used instead of the resin composition 1 for forming the basic matte layer in [Matte layer 1]. A release support, transfer sheet and decorative material were obtained.

[Comparative Example 5]
In Comparative Example 4, the separation of Comparative Example 5 was performed in the same manner, except that instead of the resin composition 2 for forming the basic matte layer, the resin composition 3 for forming the basic matte layer containing a matting agent was used. A type support, a transfer sheet and a decorative material were obtained.

<Resin composition 3 for forming basic matte layer>
・60 parts by mass of polyfunctional urethane acrylate oligomer (number of functional groups: 4) ・30 parts by mass of polyfunctional acrylate monomer (bifunctional) ・10 parts by mass of monofunctional acrylate monomer ・Matting agent (silica particles, average particle size: 7 μm) 40 parts by mass · 3 parts by mass of a wrinkle-forming stabilizer (silica particles, average particle size: 5 nm) · 0.8 parts by mass of a photopolymerization initiator (benzophenone type)

Regarding the release supports, transfer sheets and decorative materials obtained in Examples 1 to 3 and Comparative Examples 1 to 5, Spc (arithmetic mean curvature of peaks of projections), Rsm (average length of curvilinear elements) and 60 ° Gloss values were measured, texture (uniformity of surface condition) was evaluated, and soft touch feeling was evaluated. These results are shown in Table 1.
7 to 14 are micrographs of the surfaces of the decorative materials obtained in Examples 1 to 3 and Comparative Examples 1 to 5. FIG.

From the results in Table 1, the release support, the transfer sheet, and the decorative material of the present embodiment have a 60° gloss value on the matte layer side of 1.9 to 2.2, indicating a matte effect. It was confirmed that the product has excellent visibility and excellent texture. It was also confirmed that the soft touch feeling was also excellent.
On the other hand, it was found that the transfer sheet of Comparative Example 1 having an Rsm of 30 μm or more was poor in texture and could not provide a soft touch feeling. The transfer sheets of Comparative Examples 2 to 4, which have an Rsm of 30 μm or more and an Spc of 4000 mm ⁻¹ or less, have a 60° gloss value of 3.5 to 6.5 and a texture better than that of the transfer sheet of Comparative Example 1. turned out to be even worse. It was also found that the soft touch feeling could not be obtained. Similarly to Comparative Examples 2 to 4, the matte article of Comparative Example 5 using a resin composition for forming a matte layer containing a matting agent was also inferior in 60° gloss value, texture and soft touch feeling. I found out.

Since the transfer sheet of the present embodiment can impart excellent visibility and texture with a matte effect and can impart a soft touch feeling, it can be used in various applications, such as walls, ceilings, floors, etc. Exterior materials such as exterior walls, eaves, roofs, fences, and fences, window frames, doors, door frames, handrails, baseboards, rims, malls, and other fittings or fixtures, as well as general items such as chests of drawers, shelves, desks, etc. Used as decorative members for various members such as furniture, kitchen furniture such as dining tables and sinks, surface decorative boards for cabinets such as home appliances and OA equipment, interior and exterior members for vehicles, and for the above buildings. In addition to the decorative member that can be used, the transfer sheet of the present embodiment is laminated, combined, or combined with other materials (adherend materials), such as packaging materials, antiglare films for displays, whiteboards (whiteboards) or blackboards, credits It is suitable for various cards such as cards, cash cards, telephone cards, various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), signboards, soundproof walls, artificial leather, etc.

1a: Projection apex (large Spc)
1b: Projection vertex (Spc small)
2: Convex part 2a: Convex part (Rsm small)
2b: Convex part (Large Rsm)
2c, 2d: convex portion 3: concave portion 3a to 3c: concave portion 10: release support 11: support 12: release layer 20: transfer layer 21: release layer 22: primer layer 23: decoration layer 24: adhesive Layer 30: adherend 100: transfer sheet 200: decorative material

Claims (14)

A transfer sheet having a transfer layer on a release support,
At least part of the surface of the transfer layer on the release support side has an Spc (arithmetic mean curvature of the apex of the projection) defined in JIS B0601:2013 greater than 4000 mm ⁻¹ and defined in JIS B0601:2013. A transfer sheet having a surface topography such that the measured Rsm (average length of curvilinear elements) is less than 30 μm. 2. The transfer sheet according to claim 1, wherein Rz (maximum height), which is a contour curve crest and height parameter defined in JIS B0601:2013, of said surface shape is 12.5 μm or less. 3. The transfer sheet according to claim 1, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve defined in JIS B0601:2013, of the surface shape is 2.0 μm or less. 4. The transfer sheet according to any one of claims 1 to 3, wherein the surface of said transfer layer forming said surface shape has an uneven shape composed of irregular wrinkles. 5. The transfer sheet according to claim 4, wherein the 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. . 6. The transfer sheet according to any one of claims 1 to 5, wherein the transfer layer has a release layer and an adhesive layer in this order from the release support side. 7. The transfer sheet according to claim 6, comprising one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. 8. The transfer sheet according to claim 6, 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 6 to 8, wherein the release layer contains an ultraviolet absorber or a light stabilizer. A transfer sheet according to any one of claims 6 to 9, wherein the release layer is substantially free of particles. The transfer sheet according to any one of claims 1 to 10, wherein the release support has a release layer on the support. 12. The transfer sheet according to claim 11, wherein the release layer contains 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 12 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,
At least part of the surface of the transfer layer opposite to the adherend has an Spc (arithmetic mean curvature of the apex of the projection) defined in JIS B0601:2013 greater than 4000 mm ^-1 and JIS B0601:2013 Rsm (average length of curvilinear element) defined in 1 is less than 30 μm, and has a surface shape.

Images