JP2022149930A - Transfer sheet and method for manufacturing decorative material using the same - Google Patents

Abstract

To provide a transfer sheet which easily copes with variety of demands of customers, and can impart visibility and texture of excellent matting effects, and a method for manufacturing a decorative material using the same.SOLUTION: A transfer sheet has a transfer layer on a releasable support, wherein the releasable support has a release layer on the support, the release layer is composed of a cured product of a resin composition containing 0.5 pts.mass or more and 6.0 pts.mass or less of a wrinkle formation stabilizer with respect to 100 pts.mass of a resin, a surface on the side of the transfer layer of the release layer has an uneven shape composed of irregular wrinkles, and a 60° gloss value of the release layer is 5.0 or less.SELECTED DRAWING: None

Description

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

Conventionally, for example, interior members of buildings such as walls, ceilings and floors; In addition to fixtures and fixtures such as malls, general furniture such as wardrobes, shelves, and desks, kitchen furniture such as dining tables and sinks, various types of furniture and components used around water such as kitchens, toilets, bathrooms, and washstands, or BACKGROUND ART So-called decorative materials and decorative sheets are used as articles for decorating and protecting surfaces such as surface decorative boards for cabinets of home electric appliances and OA equipment, interior and exterior members of vehicles, and the like. In recent years, as customers have become increasingly oriented toward high-end products, there has been a demand for products such as decorative materials and decorative sheets that have a high-class feel.

As a method for imparting a sense of luxury, a method of imparting an uneven shape (also referred to as an “uneven pattern”) to the surface of an article to enhance the texture is generally employed. Specifically, "shaping processing using a shaping sheet", "embossing using an embossing plate or the like", and "using a transfer sheet having a layer having a concavo-convex shape to create a concavo-convex shape on an adherend. A transfer method for transferring a layer having a layer to give an uneven shape to the surface of an article, thereby expressing a matte effect, and the like.

For example, Patent Literature 1 discloses that a substrate sheet has a layer having an uneven shape made of an ionizing radiation curable resin on its surface, and a cross-linking density is imparted so that the uneven shape does not crack when peeled off. A pattern-imparting sheet that reproduces a desired pattern shape and a polyester decorative board using the pattern-forming sheet have been proposed.
Further, Patent Document 2 proposes a decorative sheet having a printed layer and a transparent resin layer in this order on a base material and having an embossed pattern on the outermost surface of the transparent resin layer.
Further, Patent Document 3 proposes a transfer sheet in which a transfer layer is provided on a base sheet and the transfer layer contains a predetermined resin.

JP-A-2-235744 JP 2011-073207 A JP-A-2004-167828

As mentioned above, customers are increasingly demanding high-end products, and as a result, they are demanding higher quality products. However, the uneven shape of the imprinting film described in Patent Document 1 can be obtained by forming a predetermined pattern with a liquid-repellent resin and then applying a two-liquid curable resin composition containing an inorganic filler. It is formed by repelling only the two-liquid curable resin composition on the pattern due to the liquid-repellent effect of the liquid resin. Therefore, since there is a limit to the formation of fine uneven shapes, it has not been possible to impart an excellent matting effect, and there have been cases where desired requirements cannot be met.
In addition, in the case of the method of forming an uneven shape on the outermost surface by applying embossing as in Patent Document 2, the preparation of the embossing plate is not easy because it takes a lot of time and effort. will need to be produced. Therefore, it cannot be said that it is a method that can sufficiently respond to the diversity of customer demands.
In addition, in the shaping process of Patent Document 1 and the embossing process of Patent Document 2, the manufacturing process may be restricted, and depending on the material of the article to be provided with the uneven shape, it may be difficult to provide the uneven shape.

The transfer sheet of Patent Document 3 can be provided with an uneven shape by transferring the transfer layer to the adherend. In the transfer sheet of Patent Document 3, a base sheet into which a delustering agent is kneaded or a sandblasted base sheet is used as a base sheet which is a releasable support. The uneven shape imparted by the transfer sheet of Patent Document 3 is a shape reflecting the surface shape of the base sheet, which is the release support. However, Patent Document 3 does not consider at all about improving the texture by the surface shape of the base sheet, which is the release support.
Furthermore, in many cases, both an uneven shape and a decorative layer such as a pattern layer are provided as a decorative form for imparting a designed appearance to the surface of an article such as a decorative sheet. In that case, in the inventions described in Patent Documents 1 and 3, two different processes, a printing process for forming a pattern layer on the base material and an embossing process for shaping the uneven shape, are required. . Therefore, there is also the problem that the process time is long and the manufacturing cost is high.

SUMMARY OF THE INVENTION An object of the present invention is to provide a transfer sheet that can easily respond to the variety of customer demands and imparts excellent visibility and texture with a matte effect, and a method for producing a decorative material using the transfer sheet. be.

In order to solve the above problems, the present invention provides the following [1] and [2].
[1] A transfer sheet having a transfer layer on a release support,
The release support has a release layer on the support,
The release layer is composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a wrinkle-forming stabilizer with respect to 100 parts by mass of the resin, and the transfer layer of the release layer A transfer sheet, wherein the side surface has an uneven shape composed of irregular wrinkles, and the release layer has a 60° gloss value of 5.0 or less.
[2] A method for producing a decorative material, comprising the following steps (1) and (2).
(1) A step of obtaining a laminate in which the transfer layer side of the transfer sheet according to any one of claims 1 to 11 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.

ADVANTAGE OF THE INVENTION According to this invention, it is easy to correspond to the diversity of a customer's demand, and can provide the transfer sheet which gives the visibility and texture of the excellent matte effect, and the manufacturing method of a decorative material using the same.

1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention; FIG. 1 is a plan view showing an embodiment of the release layer side surface of a release support constituting the transfer sheet of the present invention. FIG. 1 is a cross-sectional view showing an embodiment of a releasable support constituting the transfer sheet of the present invention; FIG. 2 is an optical microscopic image of the release layer side surface of the release support constituting the transfer sheet of Example 1. FIG. 4 is an optical microscope image of the release layer side surface of the release support constituting the transfer sheet of Example 2. FIG. 4 is an optical microscope image of the release layer side surface of the release support constituting the transfer sheet of Example 3. FIG. 4 is an optical microscope image of the release layer side surface of the release support constituting the transfer sheet of Comparative Example 1. FIG. 4 is an optical microscope image of the release layer side surface of the release support constituting the transfer sheet of Comparative Example 2. FIG.

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

[Transfer sheet]
The transfer sheet of this embodiment has a transfer layer on a release support, the release support has a release layer on the support, and the release layer has wrinkles. It is composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a stabilizer with respect to 100 parts by mass of a resin, and the surface of the release layer on the transfer layer side has irregular wrinkles. and the release layer has a 60° gloss value of 5.0 or less.

FIG. 1 is a cross-sectional view showing one embodiment of the transfer sheet of the present invention. A transfer sheet 100 in FIG. 1 has a transfer layer 20 on a release support 10 . In FIG. 1, the release support 10 has a release layer 12 on the support 11 . In FIG. 1, 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. FIG.

<Releasable support>
The release support in the transfer sheet of this embodiment has a release layer on the support. The release support is peeled off from the transfer layer after transferring the transfer layer to the adherend.

[Support]
The form (or shape) of the support is not particularly limited, but in consideration of its use as a transfer sheet, it is preferably in a planar shape such as a film, sheet or plate. Here, films, sheets, and plates are usually referred to as films, sheets, and plates in order of relatively thin thickness, but in the present specification, there is no particular significance in strictly distinguishing between these three. , film, sheet and board shall not lead to a different interpretation of the rights of the present invention. Therefore, the "sheet" in the "transfer sheet" includes not only what is generally called a sheet, but also what is generally called a film or a plate-like shape. In this specification, films, sheets and plates are sometimes collectively referred to as "sheets", "sheet-like" and the like.
When the support is a sheet, it is easy to use as a transfer sheet as described above, and a release layer provided on the support, as well as a transfer layer such as a release layer, a primer layer, a decorative layer, and an adhesive layer can be formed. manufacturing aptitude is improved.

As the support, those commonly used as supports (substrates) of articles such as decorative materials and decorative sheets can be employed without limitation. A support (substrate) made of metal or the like is typical, and a support made of a fibrous material or a resin is preferable. Among them, a resin support is preferable because it facilitates the formation of a release layer and has good peeling workability after transfer. Hereinafter, a support made of resin is also referred to as a plastic sheet.
The support may be a single layer, or may be a laminate of two or more layers comprising the above materials. When the support is a laminate of two or more layers, it is preferable to laminate two or more layers of different materials so that the properties of the materials of each layer complement each other.

When a multi-layered support is employed, a laminate obtained by laminating each layer constituting a plurality of layers, for example, a layer composed of material A and a layer composed of material B, is referred to as "A/B". When notating;
(1) Resin/metallic material (2) Resin/fibrous material (3) Resin 1/resin 2 (for example, when having multiple layers composed of different resins such as “olefin resin/acrylic resin”)
etc. are preferably mentioned.
Further, when the support has a plurality of layers, an adhesive layer, a pressure-sensitive adhesive layer, a primer layer (both an anchor layer and an easy-adhesion layer) may be provided between each layer of the plurality of layers as a layer for improving the adhesiveness of each adjacent layer. ) may be further included.

Examples of supports for fibrous materials include kraft paper, titanium paper, linter paper, sulfuric acid paper, paraffin paper, glassine paper, parchment paper, backing paper for wallpaper, thin paper, fine paper, Japanese paper, cardboard, base paper for gypsum board, and the like. paper supports. For the paper support, acrylic resin, styrene-butadiene rubber, melamine resin, acrylic resin, styrene-butadiene rubber, and It may be one to which various resins such as urethane resin are added (impregnated with resin after paper making, or filled during paper making). Examples of such paper supports include inter-paper reinforced paper and resin-impregnated paper. In addition, as a support in which a resin layer is laminated on a fibrous material layer, various resin layers such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer are laminated on the surface of wallpaper backing paper that is widely used in the field of building materials. The wallpaper original fabric etc. which carried out are also mentioned.

Examples of nonwoven or woven fabric supports include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon; organic fibers made of various synthetic resins such as polyester resins, acrylic resins, polyethylene, and polypropylene; Base materials such as non-woven fabrics or woven fabrics composed of various fibers such as protein-based or cellulose-based natural fibers such as silk, cotton and hemp, glass fibers and carbon fibers, and composites thereof.

Examples of resin supports include substrates composed of various resins such as synthetic resins and natural resins. A thermoplastic resin and a curable resin can be used as the synthetic resin.
Examples of thermoplastic resins include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin thermoplastic elastomers, and ionomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester thermoplastic elastomer; polymethyl (meth) acrylate, polybutyl ( acrylic resins such as meth)acrylate and methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyamide resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane and celluloid; polystyrene , acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene resin (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, A resin support made of a thermoplastic resin such as a polyimide resin may be used.
Examples of the curable resin include ionizing radiation curable resins capable of constituting the above matte layer and other thermosetting resins.
Natural resins include natural rubber, pine resin, amber, and the like.

Examples of the metallic material support include aluminum or various aluminum alloys, iron or various iron alloys such as carbon steel, and supports such as tin, copper and nickel. The support made of a metal-based material can be in the form of a film or sheet called a metal foil having a thickness of about 10 μm to 100 μm.

The support may or may not be colored. Further, 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).

Additives may be added to the support, if necessary. Additives, mainly in the case of resins, include, for example, inorganics such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. etc. The amount of the additive compounded is not particularly limited as long as it does not impair the surface characteristics, processing characteristics, etc., and can be appropriately set according to the required characteristics.

From the viewpoint of preventing deterioration of the transfer sheet of the present embodiment, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the above additives. Examples of the ultraviolet absorber and light stabilizer include those exemplified as those that can be contained in the release layer described later.
These ultraviolet absorbers, weathering agents such as light stabilizers, and other various additives can be used alone or in combination.

The thickness of the support is not particularly limited. That is, the support in the present 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.

When a plastic sheet is used as the support, its thickness 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, in order to improve the handleability of the transfer sheet. More preferably, it is 20 μm or more and 125 μm or less.

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.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. Examples of roughening methods include sandblasting and solvent treatment. These surface treatments are appropriately selected according to the type of substrate, but generally corona discharge treatment is preferred from the viewpoint of surface treatment effects, operability, and the like.

[Release layer]
The release layer in the transfer sheet of the present embodiment is a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a wrinkle-forming stabilizer with respect to 100 parts by mass of the resin (hereinafter, " It is a layer composed of a cured product of a release layer-forming resin composition. That is, in the present embodiment, the release layer is a layer containing a wrinkle-forming stabilizer in a content of 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the resin forming the release layer. be.

(wrinkle-forming stabilizer)
The wrinkle-forming stabilizer stabilizes the formation of wrinkles on the surface of the release layer, so that the visibility of the matting effect is uniformly expressed over the entire surface of the release layer of the present embodiment, and partial gloss unevenness is reduced. Reduced visibility of stable matte effect (hereinafter simply referred to as "visibility of stable matte effect" and similar expressions may be used) and a function of imparting texture. It is.
More specifically, the above-mentioned "stabilizing the formation of wrinkles" possessed by the wrinkle-forming stabilizer is the shape of "wrinkles" and their geometric characteristic values (individual protrusions in the uneven shape of wrinkles ( convex portion) length, width and ratio thereof, and also, for example, Rz (maximum height), Rsm (average length of curvilinear element), Ra (arithmetic mean roughness), Ssk (skewness), Sku (kurtosis) Statistical indicators such as, and various numerical values and indicators such as in-plane distribution (dispersion σ) converge when the "wrinkle-forming stabilizer" is used compared to when it is not used.

In the transfer sheet of the present embodiment, the surface shape of the transfer layer is a shape that reflects the surface shape of the release support (≈the surface shape of the release layer). Therefore, since the release layer of the transfer sheet of the present embodiment has a matting effect and texture, the decorative material obtained by transferring the transfer layer of the transfer sheet has a matting effect and texture (combined with It can also be called a “luxury feeling”.) That is, the so-called "matting agent" in the prior art and the "wrinkle-forming stabilizer" in the present embodiment have the same matting mechanism (function) even if the constituent substances and the average particle size are the same. ), the structure for expressing mattness, and the relationship between the amount used and the degree of surface luster (gloss value).

In the prior art, matting agents that have been used for expressing a matt appearance exhibit a matting effect per se due to a light diffusion effect resulting from their physical shape. 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 shape corresponding to the contour shape of the particles reflects and reflects light rays. The visibility of the matte effect is expressed by the light diffusion effect of the refractive interface. On the other hand, in the transfer sheet of the present embodiment, the wrinkle-forming stabilizer does not express the visibility of the matte effect by light diffusion due to reflection and refraction of light rays by the particles themselves, but rather the refractive index of the surface and air. Wrinkle formation at the difference interface By stabilizing the formation of wrinkles on the surface of the release layer due to the stabilizer, the light diffusion effect caused by the shape of the wrinkles stably on the transfer sheet along with the visibility of the matting effect. It gives texture. 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). The same substance A is used as a wrinkle-forming initiator AW (W: abbreviation for wrinkle), and when this is contained in a specific amount C to form wrinkles on the surface, the 60° gloss value G _60° ^AW ( C) is the 60 ° gloss value G of the surface when the same substance A is used as a simple matting agent AM (M: matte, abbreviation for matte), and wrinkles are not formed on the surface even when this is contained in the specific amount C Clearly lower than _60° ^AM (C). 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 transfer sheet of the present embodiment exhibits extremely excellent visibility and texture of the matting effect without substantially containing a matting agent that has been used to obtain the visibility of the matting effect. It can be said that it has Therefore, when a matting agent is included (added), it is sufficient to reinforce the matting effect due to wrinkles on the surface of the release layer. 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. .
In the present specification, the term "matting agent" specifically refers to a layer that can contain the matting agent, that is, a release layer, from the viewpoint of forming convex portions by the effect of cueing as described above. It means particles having an average particle size with a lower limit of more than 100% of the thickness and more than 30 μm, whichever is smaller.

As described above, the wrinkle-forming stabilizer is not a matting agent and has an average particle size of 100% or less of the thickness of the release layer. For example, various particles such as organic particles and inorganic particles are used. be able to. In the present embodiment, when the wrinkle-forming stabilizer is not used, the formation of wrinkles becomes unstable, and as a whole, the excellent visibility and texture of the matting effect due to the formation of wrinkles cannot be stably obtained.

The wrinkle-forming stabilizer used in the present embodiment is not a matting agent and preferably has an average particle size of 100% or less of the thickness of the release layer or 30 μm or less, whichever is smaller. Among them, the average particle size is 1 μm or more, and the upper limit is 100% or less of the thickness of the release layer or 30 μm or less, whichever is smaller. Wrinkle-forming stabilizer 1, average particles It is preferred to use wrinkle stabilizers 2 having a diameter of less than 1 μm. In this embodiment, as the wrinkle-forming stabilizer, one or more wrinkle-forming stabilizers 1 may be used, one or more wrinkle-forming stabilizers 2 may be used, or one or more wrinkle-forming stabilizers 2 may be used. The wrinkle-forming stabilizer 1 and one or more wrinkle-forming stabilizers 2 may be used in combination. In the present embodiment, two types of wrinkle-forming stabilizers, wrinkle-forming stabilizer 1 and wrinkling-forming stabilizer 2, are used from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matting effect. is preferably used.

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.

From the viewpoint of stabilizing the formation of wrinkles and improving the visibility and texture of the matting effect, the average particle size of the wrinkle-forming stabilizer has an upper limit of, preferably, the thickness of the release layer. 90% or less of the thickness of the mold layer, more preferably 80% or less of the thickness of the release layer, still more preferably 70% or less of the thickness of the release layer, and the absolute value is preferably 20 μm or less. It is more preferably 10 μm or less, still more preferably 8 μm or less, and even more preferably 7 μm or less, and may be the smaller of any combination of the upper limit for the thickness of the release layer and the upper limit for the absolute value. . For example, the upper limit may be 90% or less of the release layer thickness or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the release layer thickness may be the upper limit. can also The thickness of the release layer will be described later. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, and still more preferably 5 nm or more.

As described above, when wrinkle stabilizers 1 and 2 are used separately, the average particle size of wrinkle stabilizer 1 stabilizes the formation of wrinkles and stably improves the visibility and texture of the matting effect. From the viewpoint of increasing the thickness, it is preferably 1.3 μm or more, more preferably 1.5 μm or more, and still more preferably 1.8 μm or more, and the upper limit is as described above.
From the same point of view, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm. 500 nm or less, more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle-forming stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

The content of the wrinkle-forming stabilizer is 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the resin forming the release layer. If the amount is less than 0.5 parts by mass, the effect of using the wrinkle-forming stabilizer cannot be obtained and the formation of wrinkles is not stable, so that the visibility and texture of the matting effect cannot be stably obtained. On the other hand, even if it exceeds 6.0 parts by mass, it becomes difficult to stably form wrinkles, and it becomes difficult to stably obtain the visibility and texture of the matte effect. When the wrinkle-forming stabilizers 1 and 2 are used as the wrinkle-forming stabilizers, the above content means the total content of these.

From the viewpoint of stabilizing the formation of wrinkles by the wrinkle-forming stabilizer and stably improving the visibility and texture of the matting effect, the total content of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 is It is preferably 0.75 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 1.2 parts by mass or more with respect to 100 parts by mass of the resin forming the layer. From the viewpoint of improving the visibility of the erasing effect, there is no particular limitation as long as it is 6.0 parts by mass or less.

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, but the content of the wrinkle-forming stabilizer 2 is 100 mass of the resin. parts, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and the upper limit is preferably 10.0 parts by mass or less, more preferably It is 5.0 parts by mass or less, more preferably 3.5 parts by mass or less. Further, the mixing ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 (wrinkle-forming stabilizer 1/wrinkle-forming stabilizer 2) is preferably 0.05 to 0.95, more preferably 0.10 to 0.90, more preferably 0.20 to 0.80, still more preferably 0.30 to 0.70.

(Surface shape of release layer)
The release layer is a layer composed of a cured product of a resin composition for forming a release layer containing the above-mentioned specific wrinkle-forming stabilizer in a specific content, and as described above, the surface of the release layer By stabilizing the formation of wrinkles in the layer, the visibility and texture of the matte effect are stably expressed due to the light diffusion effect caused by the shape of the wrinkles. The surface shape of the release layer is reflected in the surface shape of the transfer layer. Therefore, the surface shape of the release layer is reflected as the surface shape of the decorative material obtained by transferring the transfer layer to the adherend. Therefore, the matting effect and texture of the release layer are reflected in the matting effect and texture of the decorative material obtained by transferring the transfer layer to the adherend.

FIG. 2 is a plan view showing an embodiment of the release layer side surface of the release support constituting the transfer sheet of the present embodiment. FIG. 2 is a schematic representation of an image on the transfer layer side surface of the release support obtained in the example. FIG. 2 shows that wrinkles are formed on the surface of the release support of this embodiment (the surface of the release layer of this embodiment).

The uneven shape formed by wrinkles appearing on at least one surface of the release layer is stabilized by the wrinkle-forming stabilizer, and stably exhibits the visibility and texture of the matting effect. In addition, the irregular wrinkles are preferably composed of a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions, and the protrusions are filamentous. It is preferable to have projections. In the present specification, the term "protrusion of filament" (hereinafter also referred to as "filament projection") means that the ratio of the length and width of the protrusion (length/width) is 3 or more, preferably It means 5 or more, more preferably 10 or more, and the method for determining the length and width will be described later.
In the present embodiment, the more preferable irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and recesses formed by being surrounded by the plurality of filamentary protrusions. .

Aspects related to these wrinkles include, for example, the aspect shown in FIG. FIG. 2 shows that the surface of the release support, that is, the surface of the release layer, has irregular wrinkles in a plan view, and the irregular wrinkles are formed by a plurality of curved linear projections. and a recess 2 formed by being surrounded by a plurality of protrusions (plurality of protrusions 3), and at least of the plurality of curved protrusions 3 It is also shown that a meandering recess 2 is formed in part by each meandering filament projection and surrounded by the meandering filament projections. The transfer sheet of this embodiment stably expresses the visibility and texture of the matte effect due to the stable formation of wrinkles shown in FIG.

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

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

As described above, the release layer has wrinkles on at least one surface, that is, unevenness. For the projections and recesses in the uneven shape, for example, by using the lightness difference of the image on the surface of the transfer sheet of the present embodiment, the darkest part of the density distribution image is set to gradation 255, and the lightest part of the density distribution image is set to gradation. 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.

Irregular wrinkles are preferably formed on at least a part of the surface of the release layer constituting the transfer sheet 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 on the surface of the release layer. For example, it is not limited to the location corresponding to the decorative layer described later. The visibility and texture of the matte effect are expressed.
Further, as shown in FIG. 2, the surface of the release layer has a plurality of protrusions formed by a plurality of protrusions having a certain degree of homogeneity although being irregular, and recesses surrounded by the protrusions. and preferably. Therefore, a shape in which the width and height of a single protrusion (protrusion) vary significantly is not preferable for obtaining the visibility and texture of the matte effect. Concerning the shapes of protrusions (protrusions) and recesses that form irregular wrinkles, specific aspects that can be advantageous in stably improving the visibility and texture of the matte effect will be described below.

Regarding the shape of the wrinkles formed on at least one surface of the release layer, the height of the projections (the height of the protrusions) is preferably 0.5 µm or more, more preferably 1 µm or more, and still more preferably 2 µm or more. and the upper limit is about 10 μm or less. The width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm. It is below. When the height and width of the protrusions are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the recesses.
Here, the above dimensions of the projections are arbitrary 10 projections (projections) at arbitrary 10 locations (100 μm square area × 10 locations) of the release layer constituting the transfer sheet of the present embodiment, that is, the total It is an average value of 100 convex portions. In addition, as shown in FIG. 2, 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 visibility and texture of the matte effect are stably improved in relation to the convex portions.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The distance from the top of the projection to the bottom of the recess (height difference between the projection and the recess) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 2 μm or more. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the visibility and texture of the matte effect are stably 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 projections is within the above range, the visibility and texture of the matte effect are stably improved in relation to the occupancy ratio of the recesses surrounded by the projections.
Here, the occupancy rate of the convex portions is the average value of the occupancy rate of the convex portions at arbitrary 10 locations (100 μm square area×10 locations) on the release layer constituting the transfer sheet of the present embodiment.

The protrusions and recesses may have portions of approximately the same direction and approximately the same width, but from the viewpoint of stably improving the visibility and texture of the matting effect, the length thereof is preferably short. 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, wrinkles become more irregular, so that the visibility and texture of the matte effect are stably improved.
Here, for arbitrary 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 release layer constituting the transfer sheet of the present embodiment, It is preferable that 80% or more thereof satisfy the above conditions, more preferably 85% or more, still more preferably 90% or more, and even 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 visibility and texture of the matte effect are stably improved.
The number of protrusions is the average number of protrusions at 10 locations (100 μm square area×10 locations) on the release layer constituting the transfer sheet of the present embodiment.

FIG. 3 is a cross-sectional view showing one embodiment of the releasable support 10 that constitutes the transfer sheet of the present embodiment. It is sectional drawing cut|disconnected by the plane.
The shape of the concave portion may be, for example, an acute-angled one as shown in FIG. 3a, a semicircular or semielliptical shape as shown in 2b, or a combination thereof. Alternatively, a shape such as 2c in FIG. 3, 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 3a and 3b of FIG. 3, although the width is wide or narrow, it exhibits a semicircular or semielliptical shape.

The thickness of the release layer is not particularly limited as long as it is a thickness capable of forming the above wrinkles to the extent that the visibility and texture of the matte effect can be stably expressed, but it is easy to produce. 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 200 μm or less. It is 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.

The release layer is preferably provided over the entire surface of the support from the viewpoint of improving the visibility of the stable matte effect and texture.
When the release layer is partially provided on the support, the surface shape of the transfer layer transferred to the adherend partially does not reflect the surface shape of the release layer. In addition, when the release layer is partially provided on the support, it is preferable to have a second release layer in a part of the support which does not have the release layer. The shape and composition of the second release layer are not particularly limited as long as it has releasability and does not impair the effects of the present invention.

(resin)
As the resin for forming the release layer, a resin composition for forming a release layer containing a predetermined amount of the wrinkle-forming stabilizer is formed and cured to form a cured product and a resin that constitutes the release layer. good. Such resins include ionizing radiation-curable resins.

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

From the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, surface properties such as scratch resistance and weather resistance, and improving processing properties, polyfunctionality (meta ) The number of functional groups of the 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. 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 stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, surface properties such as scratch resistance and weather resistance, and processing properties, 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 are preferred, and urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are preferred. ) 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 visibility and texture of the matting effect, and further improves surface properties such as scratch resistance and weather resistance, and processing properties. From the viewpoint of improvement, it is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, further preferably 4 or less, and even more preferably 3 or less.
From the same viewpoint, the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and more preferably 3,500 or more and 6,000. More preferred are: Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the present embodiment, it is preferable to use a combination of the polymerizable oligomer and the polymerizable monomer as the resin forming the release layer. In this case, the content of the polymerizable oligomer with respect to the total 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, still more preferably 55 parts by mass or more, and still more. It is 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. When the content of the polymerizable oligomer is within the above range, the formation of wrinkles can be stabilized, the visibility and texture of the matte effect can be stably improved, and the surface such as scratch resistance and weather resistance can be improved. Properties and processing properties can also be improved.

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

Moreover, when the resin is an ultraviolet-curable resin that is cured by ultraviolet rays, it preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Inclusion of these additives promotes the formation of wrinkles and improves the visibility and texture of the matte effect.
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.

Also, the release layer preferably has good releasability from the transfer layer. Therefore, the release layer preferably contains a 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.

[60° gross value]
In the transfer sheet of the present embodiment, the release layer has an uneven shape formed by the irregular wrinkles, and the 60 ° gloss value of the release layer is 5.0 or less. A transfer layer having the visibility and texture of a matte effect can be formed on an adherend. In the present specification, the term "matte" means that the glossiness is difficult to see, and it cannot be said unconditionally because it varies depending on the color tone of the transfer layer. shall be treated as "delete". In addition, the transfer sheet of the present embodiment has a release layer that imparts matte finish, and can impart the uneven shape and 60° gloss value of the release layer. Therefore, the 60° gloss value of the release layer means the 60° gloss value that can be imparted by the transfer sheet of the present embodiment (the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend). .

If the release 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. In addition, it can be a decorative material with a high-class feeling that stably has the visibility and texture of the matting effect. The 60° gloss value of the release support (release layer) constituting the transfer sheet and the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend are similar in color tone. , there are some differences, 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, even if a transfer sheet containing a matting agent is used in the release layer, the excellent visibility of the matting effect with a 60 ° gloss value of 5.0 or less has been achieved. It is possible to give "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 release layer, so that it is not easy to manufacture, and there is a problem that the strength of the release layer is lowered. In addition, for decorative materials exhibiting color tones other than dark, it is difficult to reduce the 60° gloss value to a level called matte. There is a limit to the value reduction.
Such a tendency becomes more remarkable as the 60° gloss value becomes smaller. Therefore, in the conventional technology using a matting agent, it is necessary to suppress the amount of the matting agent used for manufacturing reasons, etc., and it is not possible to obtain a better visibility of the matting effect. .

In the transfer sheet of the present embodiment, the wrinkle-forming stabilizer is used and the content thereof is small as described above, thereby stabilizing the formation of wrinkles and stably providing an excellent matting effect and texture. I got it. 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 release layer.

As described above, the transfer sheet of the present embodiment changes depending on the color tone, so it cannot be defined unconditionally. It can express excellent visibility of the matte effect. Further, as described above, the 60° gloss value on the release layer side of the release support of the transfer sheet of the present embodiment is the surface of the decorative material obtained by transferring the transfer layer to the adherend. It is substantially the same as the 60° gloss value.
As used herein, the 60° gloss value is the 60° specular gloss measured in accordance with JIS K 5600-4-7: 1999, and can be measured using a gloss meter or the like at any 10 points. is the average of the values. 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.

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

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

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

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

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

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

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

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 resin composition containing an ionizing radiation-curable resin for the release layer include those exemplified in the resin composition containing an ionizing radiation-curable resin for the release layer, and urethane acrylic resins such as urethane (meth)acrylate oligomers. preferable.

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

As described above, when the release layer is transferred to the adherend, it becomes the outermost layer of the transfer layer. of the weather resistant agent. In this embodiment, it is more preferable to contain an ultraviolet absorber and a light stabilizer in order to improve light resistance.

General-purpose compounds can be used as the ultraviolet absorber and light stabilizer.
Examples of the UV absorber include benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, and hydroxyphenyltriazine UV absorbers, among which hydroxyphenyltriazine UV absorbers are preferred. The hydroxyphenyltriazine compound is less likely to bleed out from the release agent, that is, less likely to bleed out from the cured resin composition for forming the release layer. Therefore, deterioration of the aesthetic appearance of the surface of the decorative material after transfer, such as stickiness due to bleeding out of the ultraviolet absorbent, is suppressed, and not only the aesthetic appearance is maintained in good condition, but also the bleeding out of the ultraviolet absorbent is prevented by rain. It suppresses deterioration in weather resistance due to gradual loss due to outflow and the like and the concentration of the ultraviolet absorber in the release layer decreases over time, and excellent light resistance can be obtained over a long period of time.

Preferred examples of the light stabilizer include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers, and among them, hindered amine compounds are preferred.
Moreover, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group or allyl group in the molecule. This is because it is less likely to bleed out due to the reaction with the curable resin that is preferably employed for forming the release agent.

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

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

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

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

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

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

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

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

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

The adhesive layer may contain a coloring agent as needed.
By including a coloring agent in the adhesive layer, the adhesive layer alone or the combination of the adhesive layer and the 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 the transfer layer, in order to improve the adhesion between the layers constituting the transfer layer,
If necessary, each layer of the transfer layer is subjected to a physical surface treatment such as the oxidation method described above, a roughening method, or a surface treatment such as a chemical surface treatment, and a primer layer is provided between these layers as an easy adhesion layer. It may be provided, or a combination of these surface treatments and a primer layer may be employed. 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 end and side chain), 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.
The binder resin may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins, followed by cross-linking and curing.
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 and the urethane component in the polycarbonate-based urethane-acrylic copolymer is preferably 30 parts by mass or more, more preferably 30 parts by mass or more, of the urethane component with respect to 100 parts by mass of the total amount of the acrylic component and the urethane component. It is 70 parts by mass or more, more preferably 85 parts by mass or more, and the upper limit is preferably 95 parts by mass or less, more preferably 93 parts by mass or less, and still more preferably 90 parts by mass or less. By setting the mass ratio of the acrylic component to the urethane component within the above range, the primer layer does not become an excessively hard coating film, and sufficient processability is obtained, and in particular, the release layer is made of a urethane (meth)acrylate oligomer or the like. When the urethane-acrylic resin is used, the interlayer adhesion with the release layer is improved.

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

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

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

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

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

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

As the ink used for the colored layer and pattern layer, a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. are appropriately mixed with a 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 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 30 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. More preferred are:

The colored layer and pattern layer may contain additives such as ultraviolet absorbers, light stabilizers and colorants.
The thickness of the colored layer and the pattern layer may be appropriately selected according to the desired pattern. In order to improve the design, the thickness is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and 2 μm or more and 5 μm. More preferred are: 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 single 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; and the like. Examples of alloys include brass, bronze, stainless steel, and the like.
The film thickness of the metal thin film can be about 0.1 μm or more and 1 μm or less.

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

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

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

[Method for producing a releasable support]
The release support that constitutes the transfer sheet of the present embodiment can be produced, for example, by the following method.
A release layer-forming resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a wrinkle-forming stabilizer with respect to 100 parts by mass of the resin is applied to one main surface of the support. It is preferable to manufacture through a step of forming a coating layer and a release layer forming step of curing the coating layer by irradiation with light having a wavelength of at least 100 nm or more and less than 200 nm to form a release layer. Moreover, when the resin composition contains a solvent, a solvent drying step may be performed after the step of forming the coating layer.

The transfer sheet manufacturing method can be particularly suitable for manufacturing a transfer sheet capable of imparting a matte effect such that the release layer side has a 60° gloss value of 5.0 or less. Among them, the method for producing a release support of the present embodiment is particularly effective in suppressing the addition amount of micrometer-order particles to a low content of 15 parts by mass or less with respect to 100 parts by mass of the resin, and furthermore, achieving a 60° gloss value. In that a matte (low luster, low gloss) surface having a .DELTA.
Such a production method makes it possible to easily obtain the release support of the present embodiment. Specifically, in forming the release layer, a resin composition containing a wrinkle-forming stabilizer that forms the release layer is irradiated with ultraviolet rays having a low wavelength of at least 100 nm or more and less than 200 nm, thereby forming the release layer. Wrinkles can be formed on at least one surface, and the surface of the release support (≈the surface of the release layer) can be stably imparted with the visibility and texture of the matte effect.

By irradiating the resin composition for forming the release layer with such a low-wavelength ultraviolet ray, the formation of wrinkles on at least one surface of the release layer is stabilized, and the visibility of the matting effect is stabilized. And although the details of the mechanism by which the texture is expressed are unknown, it is presumed to be due to the following mechanism.

When a coating material coated with a resin composition for forming a release layer with a predetermined thickness is irradiated with ultraviolet rays of a low wavelength, the energy of the ultraviolet rays penetrates 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 harden, and it is thought that wrinkles are formed due to curing shrinkage occurring only on the surface. Thus, it is considered that the stable formation of wrinkles occurs in a state in which only a certain thickness direction from the surface of the release layer-forming resin composition is cured by irradiation with low-wavelength ultraviolet rays.
In addition, from the comparison of the examples and comparative examples described later, the formation of wrinkles is unstable when the wrinkle-forming stabilizer is not included, and the visibility of the matting effect is stable over the entire surface of the release layer. Therefore, the stable expression of the matting effect cannot be explained only by the curing of only the surface portion by the low-wavelength ultraviolet rays. That is, in order for the transfer sheet of the present embodiment to stably have wrinkles to express the visibility of the matting effect, it is essential to contain a wrinkle-forming stabilizer. Considering that the visibility of a stable matting effect due to stabilization of wrinkle formation is not obtained when wrinkle-forming stabilizers are not included, the wrinkle-forming stabilizer functions like a nucleus that triggers wrinkle formation. Around the nucleus, the resin on the surface of the resin composition gathers to form wrinkle protrusions (projections) and recesses along with the formation of the protrusions (projections), resulting in wrinkles It is thought that the formation of The wrinkles formed in this manner stably impart the visibility of the matting effect to the surface of the releasable support due to the light diffusion effect resulting from the shape thereof, and also stably impart texture. It is considered that

The wrinkle-forming stabilizer and the release layer-forming resin composition containing the wrinkle-forming stabilizer used in this production method are the wrinkle-forming stabilizer and release layer-forming resin composition that can be used in the release layer of the present embodiment. The contents are the same as those described for the resin composition for

In this production method, it is preferable to irradiate the release layer-forming resin composition with light having a wavelength of at least 100 nm or more and less than 200 nm. Due to this irradiation, the energy of the ultraviolet rays permeates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition starts curing, so only the surface causes curing shrinkage. Thus, the formation of wrinkles is stabilized, and the surface layer of the resin composition becomes a cured product having wrinkles. Then, after that, curing progresses from the near-surface portion where curing progresses slowly to the deep portion away in the depth direction, the resin composition is cured over the entire thickness, and a light diffusion effect is exhibited on the surface. It constitutes a release layer having wrinkles. From the viewpoint of accelerating the progress of curing to the deep portion, it is preferable to perform another irradiation treatment after irradiation with light having a wavelength of 100 nm or more and less than 200 nm, as described later.

As the light having a wavelength of at least 100 nm or more and less than 200 nm, 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) 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, and the visibility and texture of the matting effect are stably improved.

From the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matting effect, 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 155 nm. The upper limit is less than 200 nm, particularly preferably 172 nm (Xe ₂ ). Thus, in the present production method, from the viewpoint of stably improving the visibility and texture of the matting effect, it is preferable to use light with a shorter wavelength. It can also be said that low-wavelength ultraviolet rays in the region of less than 200 nm are preferable.

In the present production method, the integrated amount of light of the above wavelength is preferably 1 mJ/cm ² or more, more preferably 10 mJ, from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matting effect. /cm ² or more, more preferably 30 mJ/cm ² or more, and even more preferably 50 mJ/cm ² or more. The upper limit is not particularly limited, and from the viewpoint of productivity such as reducing the number of lamps required for irradiation of wavelength light and improving production efficiency, the upper limit is preferably 1,000 mJ/cm ² or less, more preferably 1,000 mJ/cm 2 or less. It is 500 mJ/cm ² or less, more preferably 300 mJ/cm ² or less.
From the same point of view, the ultraviolet power density is preferably 0.01 W/cm or more, more preferably 0.1 W/cm or more, still more preferably 0.5 W/cm or more, and the upper limit is preferably 10 W. /cm or less, more preferably 5 W/cm or less, and still more preferably 3 W/cm or less.
Further, the oxygen concentration at the time of irradiation with light of the above wavelength is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

In the release layer forming step in the present production method, in addition to irradiation with light having a wavelength of at least 100 nm or more and less than 200 nm, other treatments that contribute to curing of the resin composition for forming the release 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, 200 nm or more. of wavelength light, for example, 380 nm or more, preferably about 385 nm or more and 400 nm or less wavelength light. Alternatively, after irradiation with light having a wavelength of 100 nm or more and less than 200 nm, post-curing may be performed to further cure the resin composition. Pre-curing and post-curing may be appropriately determined depending on desired properties (for example, surface properties such as scratch resistance and stain resistance, and processing properties) required for the release layer. Moreover, although the above wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiation such as electron beams. For example, in post-curing, an electron beam can be preferably used to improve the durability of the release layer.

In this production method, the release layer is coated by applying a resin composition for forming a release layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, comma coating, etc. A layer (uncured resin layer) can be formed by irradiating light with a wavelength of at least 100 nm or more and less than 200 nm.

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

In the transfer sheet of the present embodiment, the surface shape of the release support (≈the surface shape of the release layer) has the visibility and texture of a matte effect. The surface shape of the release layer is reflected in the surface shape of the transfer layer. Therefore, according to the manufacturing method of the decorative material of the present embodiment using the transfer sheet of the present embodiment, it is possible to obtain a decorative material excellent in the visibility and texture of the matting effect.

[Substrate]
The adherend in the step (1) is not particularly limited, and an adherend made of fibrous materials such as paper, non-woven fabrics and woven fabrics, resins, wood-based materials, metals, non-metallic inorganic materials, etc. can be selected as appropriate.
The form (or shape) of the adherend may be film, sheet, plate, polyhedron, polygonal prism, cylinder, cone, sphere, spheroid, etc., and is not particularly limited. The film, sheet, and plate are the same as those described above for the support.

The adherend may be a single layer, or may be a laminate of two or more layers made of the above materials, like the support. When the adherend is a laminate of two or more layers, it is preferable to laminate two or more layers of different materials so that the properties of the materials of each layer complement each other. Examples of substrates formed by laminating two or more layers include:
In addition to the laminates (1) to (3) exemplified in the support above, laminates (4) to (9) below are also exemplified. In addition, "/" indicates the interface of each layer.
(4) Resin/metal (5) Resin/fibrous material (6) Metal/wood material (7) Metal/non-metallic inorganic material (8) Metal/fibrous material (9) Metal 1/metal 2 (for example, If metal 1 has multiple layers composed of copper and metal 2 is composed of chromium)

The adherend made of fibrous material such as paper, non-woven fabric and woven fabric, resin, and wood-based material can be appropriately selected from the materials described above as the support.
Metals include alloys containing aluminum such as aluminum and duralumin; alloys containing iron such as iron, carbon steel and stainless steel; alloys containing copper such as copper, brass and bronze; gold, silver, chromium, nickel, cobalt; Tin, titanium and the like can be mentioned. In addition, as the metal substrate composed of metal, those metals subjected to a treatment such as plating can also be used.
In addition, non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (light cellular concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as ceramics, earthenware, glass, and enamel; (including marble), natural stones such as granite and andesite.

Other possible aspects of the support include, for example, that the substrate may be colored, additives may be added, surface treatment may be performed, a primer layer may be formed, and the like. are the same as those described for the above support.

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

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

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

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

The decorative material obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. And various uses, for example, interior members of buildings such as walls, ceilings and floors, exterior members such as outer walls, eaves, roofs, fences and fences, window frames, doors, door frames, handrails, baseboards, In addition to fittings or fixtures such as rims and malls, general furniture such as chests, shelves, desks, etc., kitchen furniture such as dining tables and sinks, various types of furniture used around water such as kitchens, toilets, bathrooms, washbasins, etc. It is suitably used as various members such as members, surface decorative boards for cabinets of home appliances and OA equipment, interior and exterior members of 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, 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.

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 1-1.60° 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. Using a gloss meter (“Microgloss (model name)” manufactured by BYK Gardner), the 60° specular gloss was measured from the release layer side of the sample in accordance with JIS K5600-4-7:1999.

1-2. 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 matte effect was high.

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

2. Production of transfer sheet, production of decorative material using transfer sheet [Example 1]
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).
On the easy-adhesion layer, the following resin composition for forming a release layer is applied by gravure (coating amount: 5 g/m ² (dry)), and then using a UV irradiation device composed of LEDs. UV irradiation (wavelength: 395 nm, UV dose: 0.6 W/cm ² ), then UV irradiation using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), UV output density: 1 W/cm, cumulative Light intensity: 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration: 200 ppm or less)), and then UV irradiation using a high-pressure mercury lamp (wavelength: 365 nm, UV output density: 200 W/cm) to form a release layer. did.
Through the above steps, a release support having an easy-adhesion layer and a release layer on the support was obtained.

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

The adhesive layer of the transfer sheet of Example 1 and one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC, trade name "Carbo Polish") as an adherend were opposed and laminated. After that, from the transfer sheet side, using a laminator (Roll type thermal transfer machine, "RT-300 (model number)", manufactured by Navitas Co., Ltd.), heat and pressurize 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.
Then, the release film 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 for forming release layer>
· Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Monofunctional acrylate monomer: 35 parts by mass · Wrinkle-forming stabilizer (silica particles, average particle size: 3 µm): 1.0 parts by mass · Photoinitiator ( Benzophenone system): 0.8 parts by mass

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

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

[Examples 2-3]
In Example 1, except that the wrinkle-forming stabilizer in the resin composition for forming the release layer was changed to the amount shown in Table 1, the transfer of Examples 2 and 3 was performed in the same manner as in Example 1. got a sheet. Using the obtained transfer sheets, the decorative materials of Examples 2 and 3 were obtained in the same manner as in Example 1.

[Example 4]
In Example 1, the wrinkle-forming stabilizer in the release layer-forming resin composition was changed to the amount shown in Table 1. Furthermore, the resin composition 1 for forming the peeling layer was changed to the following resin composition 2 for forming the peeling layer. A transfer sheet of Example 4 was obtained in the same manner as in Example 1 except for the changes described above. A decorative material of Example 4 was obtained in the same manner as in Example 1 using the obtained transfer sheet.

<Resin composition 2 for forming release layer>
・Ionizing radiation curable resin (mass ratio of bifunctional urethane acrylate oligomer and hexafunctional urethane acrylate oligomer 4:6): 100 parts by mass ・UV absorber (BASF, trade name: Tinuvin479): 2 parts by mass ・Light stable Agent (Nippon Emulsifier Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[Comparative Example 1]
A transfer sheet was obtained in the same manner as in Example 1, except that the amount of the wrinkle-forming stabilizer in the release layer-forming resin composition was changed to 0 parts by mass. A decorative material was obtained in the same manner as in Example 1 using the obtained transfer sheet.

[Comparative Example 2]
In Example 1, the amount of the wrinkle-forming stabilizer used in the resin composition for forming the release layer was set to 0 parts by mass, and instead, 15.0 parts by mass of the matting agent (average particle size: 5.0 µm) was used. A transfer sheet was obtained in the same manner as in Example 1, except that a high-pressure mercury lamp was used to irradiate ultraviolet rays (wavelength: 365 nm, ultraviolet output density: 200 W/cm). A decorative material was obtained in the same manner as in Example 1 using the obtained transfer sheet.

[Comparative Example 3]
One surface of the support (100 μm thick PET) was sandblasted. Next, on the sandblasted surface, a release layer, a primer layer and an adhesive layer were formed in the same manner as in Example 1 to obtain a transfer sheet of Comparative Example 3. Next, using the obtained transfer sheet, a decorative material was obtained in the same manner as in Example 1.

From the results in Table 1, the decorative materials obtained using the transfer sheets of Examples 1 to 4 had a 60° gloss value of the decorative materials of 1.4 to 1.8, and the matting effect was visually recognized. It was confirmed that the properties are extremely excellent.
On the other hand, the decorative material obtained using the transfer sheet of Comparative Example 1 containing no wrinkle-forming stabilizer in the release layer had some wrinkles on the surface as shown in FIG. Generally, the visibility of the matte effect could not be obtained, and excellent texture could not be imparted. The decorative sheet of Comparative Example 2, which contains a matting agent in the release layer, contains 15.0 parts by mass, which is a surface layer corresponding to the release layer, even if the wrinkle-forming stabilizer is contained in an amount larger than the content of the wrinkle-forming stabilizer in the examples. There is no wrinkle formation, and the 60 ° gloss value of the decorative material obtained using this is 8.3, which is a larger amount of the matting agent than the wrinkle-forming stabilizer in the example. It was confirmed that the cosmetic materials of Examples were inferior in gloss value and inferior in texture. Further, the decorative material obtained using the transfer sheet of Comparative Example 3 containing the sandblasted support had a high 60° gloss value of 21.4 and was inferior in matting effect.

According to the optical microscope images of the release layer-side surfaces of the release supports of Examples 1 to 3 (FIGS. 4 to 6, respectively), the transfer sheets of these Examples have irregularities on the surface of the release layer. It can be confirmed that wrinkles are uniformly formed. On the other hand, according to the optical microscope image (FIG. 7) of Comparative Example 1, as described above, there are some wrinkles on the surface, and although there are some areas with wrinkles similar to those of Examples, It can be seen that the formation of wrinkles is unstable (not uniform) and intermingled with areas without wrinkles. Further, according to the optical microscope image (FIG. 8) of Comparative Example 2, wrinkles unlike the transfer sheet of Example were not observed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the transfer sheet of the present embodiment exhibited extremely excellent visibility of the matting effect due to wrinkles on the surface.

100: Transfer sheet 10: Release support 11: Support 12: Release layer 20: Transfer layer 21: Release layer 22: Primer layer 23: Decorative layer 24: Adhesive layer 2: Concave portion 3: Convex portion (projection part)

Claims (11)

A transfer sheet having a transfer layer on a release support,
The release support has a release layer on the support,
The release layer is composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a wrinkle-forming stabilizer with respect to 100 parts by mass of the resin, and the transfer layer of the release layer A transfer sheet, wherein the side surface has an uneven shape composed of irregular wrinkles, and the release layer has a 60° gloss value of 5.0 or less. 2. The transfer sheet according to claim 1, wherein the wrinkle-forming stabilizer contains wrinkle-forming stabilizer 1 having an average particle size of 1 μm or more and 100% or less of the thickness of the release layer. 3. The transfer sheet according to claim 1, wherein the wrinkle stabilizer comprises wrinkle stabilizer 2 having an average particle size of less than 1 [mu]m. Any one of claims 1 to 3, wherein the 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. The transfer sheet according to item 1. The transfer sheet according to any one of claims 1 to 4, wherein the release layer is provided over the entire surface of the support. The transfer sheet according to any one of claims 1 to 5, wherein the resin is an ionizing radiation-curable resin. 7. The transfer sheet according to any one of claims 1 to 6, wherein the transfer layer has a release layer and an adhesive layer in this order from the release support side. 8. The transfer sheet according to claim 7, comprising one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. 9. The transfer sheet according to claim 7, 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 7 to 9, wherein the release layer contains an ultraviolet absorber or a light stabilizer. 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 side of the transfer sheet according to any one of claims 1 to 10 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.

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