JP2020049722A - Transfer sheet, method for producing transfer sheet, and decorative material - Google Patents

Abstract

To provide a transfer sheet having improved brightness and adhesion while maintaining low cost.SOLUTION: There is provided a transfer sheet 1 where a releasable support 10 and a transfer layer 2 including a decorative layer 30 are stacked, in which the decorative layer 30 has a metallic layer 32 formed of a resin R containing a plurality of metal scaly pieces L having a large particle diameter and metal scaly pieces S having a small particle diameter, the metallic layer 32 includes a resin layer 321 formed of the resin R, a first brilliant resin layer 322 containing the metal scaly pieces S having the small particle diameter and the metal scaly pieces L having the large particle diameter, and a second brilliant resin layer 323 containing the metal scaly pieces L having the large particle diameter and the metal scaly pieces S having the small particle diameter, in order from the side of the releasable support 10, and the number per area of metal scaly pieces S having the small particle diameter contained in the first brilliant resin layer 322 is larger than those in the second brilliant resin layer 323.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer sheet, a method for manufacturing a transfer sheet, and a decorative material.

  In a transfer sheet used for furniture, building materials, and the like, a high-brightness metallic design may be required. Conventionally, as a method of reproducing such a metallic design, a method of forming a vapor deposition film on a sheet serving as a support, a method of forming a coating film by printing by combining particles having different particle diameters, and the like have been proposed. ing. Among them, the latter method has an advantage that a transfer sheet can be manufactured at a lower cost than a method of forming a vapor-deposited film (for example, see Patent Documents 1 and 2).

JP 2015-214031 A JP-A-5-080746

  In the transfer sheet, it is required to improve brightness and adhesion while maintaining low cost.

  An object of the present invention is to provide a transfer sheet, a method for manufacturing a transfer sheet, and a decorative material which are improved in brightness and adhesion while maintaining low cost.

  The present invention solves the problem by the following means. In addition, in order to make it easy to understand, description is given with reference numerals corresponding to the embodiment of the present invention, but the present invention is not limited to this. Further, the configuration described with reference numerals may be appropriately improved, or at least a part may be replaced with another component.

  A first invention is a transfer sheet (1) in which a releasable support (10) and a transfer layer (2) including a decoration layer (30) are laminated, wherein the decoration layer has a large particle size. A metallic layer (32) made of a resin (R) containing a plurality of metal flakes (L) having a diameter and a plurality of metal flakes (S) having a small particle diameter, wherein the metallic layer is arranged from the side of the releasable support. In order, a resin layer (321) made of the resin, a first glittering resin layer (322) containing the metal flakes having the small particle diameter and the metal flakes having the large particle diameter, the metal flake having the large particle diameter, A second brilliant resin layer (323) containing the metal flakes having the small particle size, wherein the first brilliant resin layer has a smaller metal particle size than the second brilliant resin layer. This is a transfer sheet containing a large number of scales per unit volume.

  The second invention is the transfer sheet according to the first invention, wherein the metal flakes having a small particle diameter and the metal flakes having a large particle diameter contained in the first luminous resin layer have the second luminosity. Arranged in parallel so as to cover the surface layer on the resin layer side, the large-grain metal flakes contained in the second glittering resin layer are uniformly distributed in the thickness direction and parallel to the layer direction. The large-scale metal flakes contained in the second glittering resin layer are arranged in parallel so as to cover the surface layer on the first glittering resin layer side.

  A third invention is the transfer sheet according to the first or second invention, wherein the particle diameter of the metal flakes having the small particle diameter is less than 0.42 times the particle diameter of the metal flakes having the large particle diameter. In the metallic layer, the metal scale is 40 parts by mass or less based on 100 parts by mass of the resin.

  The transfer sheet according to a fourth aspect is the transfer sheet according to any one of the first to third aspects, wherein the decorative layer is a pattern layer (31a) on the metallic layer on the side of the releasable support. And at least one of a colored transparent layer (31b).

  A transfer sheet according to a fifth aspect of the present invention is the transfer sheet according to any one of the first to fourth aspects, wherein the decorative layer has a colored opaque layer on a side of the metallic layer opposite to the release support. (33).

  A sixth invention is the method for producing a transfer sheet according to any one of the first to fifth inventions, wherein a paint obtained by mixing a leafing type metal flake having a small particle diameter and a resin is used as a releasable support. A first coating film forming step of forming a first coating film by applying to the surface of the release layer formed in the first step, and coating the non-leafing type large scale metal flakes and resin with the first coating. A second coating film forming step of applying a second coating film to the surface of the coating film to form a second coating film. The body is arranged in parallel so as to cover the surface layer on the opposite side, and in the second coating film forming step, a portion of the metal flakes having a large particle diameter contained in the second coating film is coated with the first coating film. Are arranged in parallel so as to cover the surface layer of the first coating film together with the metal flakes having the small particle diameter arranged in the surface layer of Along with, the remainder of the metal flakes of the large particle size contained in the second coating film is uniformly distributed in the thickness direction and arranged in parallel to the layer direction, and a part of the first coating film is included. A method for producing a transfer sheet, wherein the metal flakes having a small particle diameter are arranged so as to cover a surface layer of the second coating film.

  A seventh invention is a decorative material 100 using the transfer sheet according to any one of the first to fifth inventions.

  Advantageous Effects of Invention According to the present invention, it is possible to provide a transfer sheet, a method of manufacturing a transfer sheet, and a decorative material which are improved in luminance and adhesion while maintaining low cost.

FIG. 2 is a cross-sectional view of the transfer sheet 1 according to the embodiment. It is a schematic view for explaining the relationship between the particle diameter D _L of the particle diameter Ds and the large径鱗piece L of the small径鱗piece S. It is a figure explaining the manufacturing method of makeup material 100. It is a figure explaining the manufacturing method of makeup material 100. FIG. 3 is a diagram illustrating a method for manufacturing a transfer sheet A of an example. It is a figure explaining the evaluation result of an Example and comparative examples 1 and 2.

Hereinafter, embodiments of the present invention will be described. In addition, each drawing attached to this specification is a schematic diagram, and the shape, scale, aspect ratio, etc. of each part are changed or exaggerated from the real thing in consideration of easy understanding. In each drawing, hatching indicating a cross section of some members is omitted.
Numerical values, shapes, material names, and the like described in this specification are merely examples of the embodiments, and are not limited thereto, and may be appropriately selected and used.

FIG. 1 is a cross-sectional view of the transfer sheet 1 according to the present embodiment.
As shown in FIG. 1, the transfer sheet 1 of the present embodiment includes a release support 10, a release layer 20, a decorative layer 30, a bonding layer 40, and a release sheet 50. In the transfer sheet 1 of the present embodiment, the release layer 20, the decoration layer 30, and the bonding layer 40 constitute the transfer layer 2. Note that, in the present invention, the configuration of the transfer layer 2 is not limited to the combination of the present embodiment, and may include other functional layers or may not include some functional layers from the combination of the present embodiment. It may be configured.

(Configuration of Transfer Sheet 1)
The transfer sheet 1 of the present embodiment employs a flexible and thin-film sheet as the releasable support 10 having releasability from the transfer layer 2 (release layer 20). On the releasable support 10, the release layer 20, the decorative layer 30, and the bonding layer 40 constituting the transfer layer 2 are laminated in this order. Note that “laminated in this order” in the present invention means not only direct lamination but also indirect lamination, and for example, between the release support 10 and the release layer 20, This means that even if there is a layer of

<Releaseable support 10>
The release support 10 is a sheet that supports the transfer layer 2 including the bonding layer 40. The releasable support 10 has a releasability (peeling property) with respect to the transfer layer 2, and after the transfer sheet 1 is adhered to the base material 60 (described later), the release layer 20 (the transfer layer 2). )). Examples of the release support 10 include a sheet made of a polyester resin such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, a polyolefin resin such as polypropylene, polyethylene, and polymethylpentene, and a thermoplastic resin such as a polyamide resin. Is mentioned. Further, as the releasable support 10, a form in which a transfer layer 2 and a resin layer having releasability are laminated on the surface of the paper on which the transfer layer 2 is formed is exemplified. As the paper, fine paper, linter paper, glassine paper, parchment paper, kraft paper and the like can be used. Examples of the resin layer having releasability from the transfer layer 2 include melamine resin, epoxy resin, and silicon resin in addition to the various thermoplastic resins. Among these releasable supports, a biaxially stretched polyethylene terephthalate (PET) sheet is preferable in terms of excellent strength and flexibility. A known release layer may be formed on the surface of the release support 10 on the release layer 20 side, or a release treatment may be performed.
The thickness of the releasable support 10 is preferably from 10 μm to 250 μm, more preferably from 20 μm to 60 μm.

  The release layer 20 is a layer that is laminated to facilitate release of the releasable support 10 from the transfer layer 2. The release layer 20 remains as the outermost layer of the transfer layer 2 after the transfer layer 2 of the transfer sheet 1 is adhered to the transfer substrate 60 and the release support 10 is released. The release layer 20 can be used as a protective layer on the outermost surface of the decorative material to which the transfer sheet 1 has been transferred, but a top coat layer 70 (described later) may be further formed on the surface of the release layer 20. By forming the top coat layer 70 on the surface of the release layer 20, the durability of the surface of the decorative material 100 such as abrasion resistance, stain resistance, water resistance, and weather resistance can be further enhanced.

  Examples of the resin forming the release layer 20 include poly (methyl) acrylate, poly (ethyl) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate-butyl methacrylate. One or more of an acrylic resin such as a coalescence, an alkyl (meth) acrylate monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; Two or more kinds, and having an OH group in a molecule such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or 2-hydroxy-3-phenoxypropyl (meth) acrylate Acrylic obtained by copolymerizing one or more (meth) acrylate monomers and, if necessary, a styrene monomer or the like. Triol, vinyl chloride - vinyl acetate copolymer, urethane resin, (meth) acrylate - and vinyl acetate copolymer - vinyl chloride. Here, (meth) acrylic acid is a notation meaning acrylic acid or methacrylic acid.

Further, in these compositions, a small amount of an isocyanate compound or the like may be further added for adjusting the peel strength. Further, these compositions may contain, for example, an organic compound such as a benzotriazole-based compound, a benzophenone-based compound, or a triazine-based compound, or an ultraviolet absorber (UVA) composed of fine particles such as titanium oxide, zirconium oxide, and cerium oxide; A radical scavenger such as (HALS) may be added.
The layer thickness (dry) of the release layer 20 is, for example, about 1 μm or more and 10 μm or less.

<Decoration layer 30>
The decorative layer 30 is a layer on which the picture (design) of the transfer sheet 1 is formed, and is formed by printing or the like. The decoration layer 30 is composed of a picture pattern layer 31, a metallic layer 32, and a colored opaque layer 33.
In the present embodiment, a configuration including a picture pattern layer 31, a metallic layer 32, and a colored opaque layer 33 as the decorative layer 30 will be described. However, the decorative layer 30 is formed of an example (and comparative examples 1 and 2) described later. Thus, it is sufficient that at least the metallic layer 32 is provided.

The picture pattern layer 31 includes a picture layer 31a and a colored transparent layer 31b.
The design layer 31a is a layer on which designs such as a design, a design, and a pattern are formed. The picture layer 31a is formed such that the color pigment is 15 parts by mass or more based on 100 parts by mass of the resin. As a resin constituting the picture layer 31a, for example, an acrylic resin, a vinyl chloride-vinyl acetate copolymer (vinyl chloride acetate), a urethane resin, a polyamide resin, a polyester resin, or a mixture of two or more selected from these resins For example, a composition in which an acrylic resin and vinyl chloride vinegar are mixed at an appropriate mass ratio in the range of 1: 9 to 9: 1. The pattern layer 31a has a coloring agent for coloring into a desired color and various additives as necessary (an ultraviolet absorber, a heat stabilizer, a light stabilizer, a surfactant, a plasticizer, an extender, etc.). ) Is added.

The colored transparent layer 31b is a transparent colored layer laminated on the picture layer 31a. The colored transparent layer 31b is formed such that the colored pigment is less than 15 parts by mass with respect to 100 parts by mass of the resin. As the colored transparent layer 31b, for example, a mixture of an acrylic resin and a coloring agent can be used. In the present embodiment, an example in which the pattern layer 31a and the colored transparent layer 31b are provided as the pattern layer 31 will be described. However, the present invention is not limited thereto, and the pattern layer 31 may be only the pattern layer 31a. Only the colored transparent layer 31b may be used.
The layer thickness (dry) of the picture layer 31a including the picture layer 31a and the colored transparent layer 31b is about 5 μm.

  The metallic layer 32 is a layer that gives the transfer sheet 1 a high-brightness metallic design, and has a mirror surface. The metallic layer 32 includes a resin layer 321, a first glittering resin layer 322, and a second glittering resin layer 323 in this order from the release support 10 side. The layer configuration of the metallic layer 32 will be described later.

  The colored opaque layer 33 is a concealing layer that makes it difficult to see the transfer substrate 60 when the transfer layer 2 transferred to the transfer substrate 60 (described later) is viewed from the release layer 20 side. The colored opaque layer 33 is formed so that the color pigment is 100 parts by mass or more based on 100 parts by mass of the resin. The colored opaque layer 33 is formed so as to cover the entire surface of the decorative layer 30, and is colored, for example, white, gray, brown, or the like. Examples of the resin constituting the colored opaque layer 33 include an acrylic resin, a vinyl chloride-vinyl acetate copolymer (vinyl acetate), an acrylate-vinyl chloride-vinyl acetate copolymer, and the like. The resin material that can be used as the colored opaque layer 33 preferably has a glass transition point (Tg) of room temperature or higher.

Further, the coloring opaque layer 33 may be added with a coloring agent for coloring into a desired color and various additives as necessary. As the colorant and the additive, those suitable for exhibiting a desired color, hiding property and various physical properties are appropriately selected and used from those exemplified in the description of the picture pattern layer 31 described above.
The thickness (dry) of the colored opaque layer 33 is preferably 1 μm or more.

<Joining layer 40>
The joining layer 40 is a layer that joins the transfer sheet 1 and the transfer substrate 60 when the transfer sheet 1 is transferred to the transfer substrate 60. The material of the bonding layer 40 may be appropriately selected from various well-known materials and those which exhibit an adhesive force. As the bonding layer 40, for example, a cured product of an adhesive composition can be used. The pressure-sensitive adhesive composition contains an acrylic pressure-sensitive adhesive as a main agent and an isocyanate-based curing agent.
The thickness of the bonding layer 40 is preferably 10 μm or more and 50 μm or less, and more preferably 15 μm or more and 30 μm or less.

[Acrylic adhesive]
Preferred acrylic pressure-sensitive adhesives include, for example, (meth) acrylate copolymers obtained by copolymerizing (meth) acrylate and other monomers. Examples of the (meth) acrylate include ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and (meth) acrylic acid. Examples include isononyl, hydroxylethyl (meth) acrylate, propylene glycol (meth) acrylate, acrylamide, and glycidyl (meth) acrylate. These can be used alone or in combination of two or more.

Other monomers include, for example, methyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, (meth) acrylic acid, itaconic acid, hydroxylethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Examples thereof include tert-butylaminoethyl (meth) acrylate and n-ethylhexyl (meth) acrylate. These can be used alone or in combination of two or more.
In addition, as a commercially available product of the acrylic pressure-sensitive adhesive, for example, Nissetsu (manufactured by Nippon Carbide Co., Ltd.), SK Dyne (manufactured by Soken Chemical Co., Ltd.) and the like can be suitably used.

[Isocyanate curing agent]
The pressure-sensitive adhesive composition contains an isocyanate-based curing agent. The isocyanate-based curing agent is added in order to obtain adhesiveness when the transfer sheet 1 is transferred to a transfer substrate 60 (described later). Since the acrylic pressure-sensitive adhesive has a hydroxyl group, partial crosslinking can be further improved by using an isocyanate-based curing agent, and when the bonding layer 40 is formed, an appropriate storage elastic modulus without internal destruction is obtained. Can be

  Examples of the isocyanate-based curing agent include a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having a terminal isocyanate group obtained by reacting a polyisocyanate compound and a polyol compound, and a urethane prepolymer of 3 And the like.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.
The content of the isocyanate-based curing agent in the bonding layer 40 is set according to the gel fraction.

  Further, a heat seal layer can be used as the bonding layer 40. As the heat seal layer, for example, acryl-epoxy resin, acryl-urethane resin, acrylate-vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer and the like can be used. When the bonding layer 40 is a heat seal layer, the film thickness is preferably, for example, about 2 to 4 μm. When the bonding layers 40 are alternately formed, materials having different compositions may be appropriately selected from the above-described materials.

In addition, the bonding layer 40 is formed not only on the transfer sheet 1 but also on a transfer substrate 60 (described later), and the transfer sheet 1 without the bonding layer 40 is transferred to the transfer substrate 60. May be. The bonding layer 40 in that case is selected according to the use of the transfer sheet 1.
In an example described later, an example is shown in which a heat seal layer serving as the bonding layer 40 is formed on the side of the substrate 60 to be transferred, and the transfer sheet 1 is thermally transferred to the substrate 60 to be transferred.

<Release sheet 50>
The release sheet 50 is a member that is released from the transfer sheet 1 when the transfer sheet 1 is transferred to the transfer target substrate 60. Examples of the release sheet 50 include silicone release type polyethylene terephthalate (PET), untreated polyethylene terephthalate, and polypropylene.
The thickness of the release sheet 50 is preferably from 10 μm to 100 μm, and more preferably from 20 μm to 60 μm.
When a heat seal layer is used as the bonding layer 40, the release sheet 50 becomes unnecessary.

(Configuration of Metallic Layer 32)
Next, the configuration of the metallic layer 32 provided on the decorative layer 30 will be described.
As shown in FIG. 1, the metallic layer 32 includes a resin layer 321, a first glittering resin layer 322, and a second glittering resin layer 323 in this order from the release support 10.
Note that FIG. 1 conceptually shows a range of the resin layer 321, the first glittering resin layer 322, and the second glittering resin layer 323 that constitute the metallic layer 32.

  The resin layer 321 is a layer composed of only the resin R, and does not substantially include the small-grain scales S and the large-grain scales L described later. The phrase “substantially not contained” means that even if rare particles S or large particles L are rarely present in the resin layer 321, the amount thereof affects the optical performance of the resin layer 321. It means not to the extent.

  The resin R is not particularly limited as long as it can be used as a binder. Examples of the resin R include acrylic resin, vinyl chloride-vinyl acetate copolymer (vinyl chloride acetate), acrylic resin and vinyl chloride-vinyl acetate copolymer. And the like. As the resin R, these materials are used alone or in combination of two or more. Further, a coloring pigment, a coloring dye, or the like may be added to the resin R. The resin R is also included in a first glittering resin layer 322 and a second glittering resin layer 323 described later. The resin R included in the first glittering resin layer 322 and the second glittering resin layer 323 may be the same as the resin R of the resin layer 321 or may be a different material.

The first glittering resin layer 322 is a layer containing metal flakes S having a small particle diameter, metal flakes L having a large particle diameter, and a resin R. The first glittering resin layer 322 contains many small metal flakes S having a small particle diameter, and contains very little metal flakes L having a large particle diameter.
The second glittering resin layer 323 is a layer containing a metal flake L having a large particle diameter, a metal flake S having a small particle diameter, and a resin R. The second glittering resin layer 323 contains a large amount of metal flakes L having a large particle diameter, and contains very little metal flakes S having a small particle diameter.
That is, the first glittering resin layer 322 contains a larger number of metal flakes S having a small particle diameter per unit volume than the second glittering resin layer 323.
In the following description, metal flakes S having a small particle diameter are referred to as “small particle flakes S”, and metal flakes L having a large particle diameter are referred to as “large-particle flakes L”.

  The small particle scale S and the large particle scale L are made of metal. For example, metals having metallic luster such as aluminum, gold, silver, copper, tin, nickel, chromium, and brass can be used. Typically, aluminum particles are used because they have good metallic luster, are inexpensive, and have a flat (ie, colorless) reflected light spectrum throughout the visible light band. Hereinafter, the aluminum particles formed in a scale shape are referred to as aluminum pigments. Aluminum pigments are broadly classified into leafing types and non-leafing types. In the present embodiment, the small particle scale S is a leafing type pigment. The large-particle scale L is a non-leafing type pigment.

The leafing type pigment has a characteristic of floating on the surface side of the coating film in the process of drying after forming the coating film. The small-sized scales S made of the leafing type pigment are arranged in parallel in the first glittering resin layer 322 so as to cover the surface layer on the second glittering resin layer 323 side. In addition, as a leafing type pigment, it is preferable to use a high-brightness type pigment with enhanced glitter.
On the other hand, non-leafing type pigments have the property of being uniformly dispersed in the thickness direction of a coating film during the drying process when the coating film is formed. Most of the large-grain scales L made of a non-leafing type pigment are uniformly distributed in the thickness direction of the second glittering resin layer 323 and arranged in parallel to the layer direction.

In the second glittering resin layer 323 (≒ the second coating film 32B), the mixing ratio of the large-grain scale L to the resin R is preferably 40 parts by mass or less with respect to 100 parts by mass of the resin R. In addition, the lower limit of the mixing ratio of the large-particle scale L is preferably 20 parts by mass or more in consideration of the limit of the luminance and the amount of coating. When the amount of the large-particle scale L added is 35 to 40 parts by mass, the area (volume) ratio between the resin R and the large-particle scale L is approximately 4: 1. According to this, when one layer of the coating film having the same thickness as the large-grain scale L is applied, the large-grain scale L in a square (one side having a particle size D _L × 2) shown in FIG. Becomes one calculation. Therefore, when four layers of the coating film having the same thickness as the large-grain scale L are applied, four large-grain scales L fit in a square frame in plan view as shown in FIG. become.

Here, a description will be given of the relationship between the particle diameter D _L of the particle diameter Ds and the large径鱗piece L of the small径鱗piece S.
Figure 2 is a schematic diagram for explaining the relationship between the particle diameter D _L of the particle diameter Ds and the large径鱗piece L of the small径鱗piece S.
In Figure 2, the range of a unit area of the coating film is shown in a square frame which one side is twice the particle diameter D _L of the large径鱗piece L. When the thickness of the metallic layer 32 (second coating film 32B) is four times the thickness of the large-grain scale L, as shown in FIG. Filled with particle flakes L. On the other hand, since there is a gap between the large-sized scales L, a feeling of grain (insufficient specularity) is conspicuous only with the four large-sized scales L.

Particle size Ds of small径鱗piece S in order to achieve both adhesion and luminance, is preferably less than 0.42 of particle size D _L of the large径鱗piece L. Specifically, the particle diameter Ds of the small particle scale S that fits in the gap is obtained by (√2-1), assuming that the particle diameter DL of the large particle scale _L is 1, and is approximately 0.42. . Therefore, the particle size Ds of small径鱗pieces S, by less than 0.42 in particle size D _L of the large径鱗piece L, and the gap between the large径鱗piece L, a small particle径鱗piece S Almost can be filled. As shown in FIG. 2, the number of small径鱗piece S becomes four in the range of the square (unit area) that one side is twice the particle diameter D _L of the large径鱗piece 11a. Particle size Ds of small径鱗piece S shown in FIG. 2, the maximum diameter that can be filled 0.42 particle size D _L of the large径鱗piece L, and the gap between the large径鱗piece L. Thus, the particle size Ds of small径鱗piece S, if less than 0.42 of particle size D _L of the large径鱗piece L, the small径鱗piece S the gap between the large径鱗piece L Since it can be buried, it is possible to suppress a decrease in adhesion while making the particle feeling less noticeable.

The shape of the metal scale is represented by a major axis (average particle diameter D ₅₀ ) and a minor axis (average particle thickness).
The average particle diameter can be measured by a microscope method, a sieving method, a sedimentation method, a Coulter counter method, a laser light scattering / diffraction method, or the like.
The average particle thickness can be indirectly calculated by the following equation (1) by measuring the water surface diffusion area by the JIS method (JIS K5906: 1998).
Average particle thickness (μm) =
10,000 / [density of pigment × diffusion area on water surface (cm ² / g)] Formula (1)

The addition number ws of the small-grain scale S is calculated by the following equation (2). In the following description of the equations, the reference numerals of the members are appropriately omitted.
The number of added parts w of the small particle scale S =
Number of Resins (= 100)] × [Weight of Small Grain Scale in Unit Coating Film]
/ [Weight Wm of resin in unit coating film] Formula (2)
Equation (2) can be replaced as follows:
ws = [number of resin parts (= 100)] × [volume Vs of small particle scale in coating film] × [density of aluminum scale dp]
/ (([Unit coating volume Vcs] -Vs) × [resin density (≒ specific gravity) dm])

Here, in the coating film (unit coating film) per unit area of the first coating film 32A, the volume Vs of the small-scale scale in the coating film and the unit coating film volume Vcs are expressed as follows.
Vs = π / 4 × [particle size Ds of small particle scale] ² × [thickness ts of small particle scale] × [number per unit area (= 4)]
Vcs = [square area of 2 double-diameter particle size _{D L} of the large径鱗piece] × [film thickness tcs]

Therefore, the number of added parts ws of the small-grain scale can be calculated by the following equation (3).
ws =
100 × dp / dm × (π × Ds ² × ts)
^{_{/ (4 × D L 2 ×}} tcs-π × Ds 2 × ts) ··· (3)

In the present embodiment, the density dp of the aluminum scale is about 2.5 g / cm ³ . In addition, the resin density dm is about 1.2 to 1.4 g / cm ³ . Particle size Ds of small径鱗piece, the particle size D _L of the large径鱗piece is the value of the selected material. Further, the thickness ts of the small-grain scale is a value calculated from the water surface diffusion area of the selected material. Therefore, by arbitrarily setting the coating thickness tcs of the first coating film 32A, it is possible to determine the number of added parts ws of the small-grain scales. The coating thickness tcs is desirably set to 1 μm or more in order to obtain a stable and uniform coating.

Among the above-described metallic layers 32, the resin layer 321 and the first glittering resin layer 322 are formed by coating a mixture of small-scale flakes S, resin R, and a solvent by gravure printing, offset printing, screen printing, or the like. It is formed by applying to the surface of the release layer 20 formed on the release support 10 and drying. In addition, the second glittering resin layer 323 is formed by applying a coating material obtained by mixing the large-grain scale L, the small-grain scale S, the resin R, and the solvent on the surface of the first glittering resin layer 322 by the printing method. And dried.
The layer thickness (dry) of the metallic layer 32 provided with each of the above layers is, for example, about 5 μm.

(Method of manufacturing cosmetic material 100)
Next, a method for manufacturing the decorative material 100 using the transfer sheet 1 of the present embodiment will be described.
3 and 4 are diagrams illustrating a method of manufacturing the decorative material 100, respectively. Here, the manufacturing steps (A) to (D) of the decorative material 100 will be described with reference to FIGS.
First, as shown in FIG. 3A, the release sheet 50 is released from the transfer sheet 1. By peeling the release sheet 50 from the transfer sheet 1, the surface of the bonding layer 40 opposite to the release support 10 is exposed.

Next, as shown in FIG. 3B, the transfer sheet 1 from which the release sheet 50 has been peeled off is attached to the base material 60 to be transferred. The transfer sheet 1 can be continuously attached to the transfer-receiving base material 60 in the form of, for example, a roll-to-roll or a roll-to-sheet.
“Roll-to-roll” means that the belt-shaped transfer sheet 1 is pulled out from a roll (winding), supplied to a flat transfer substrate, and the transfer layer 2 is attached to the transfer substrate. It refers to a processing mode in which the strip-shaped releasable support from which the transfer layer 2 has been peeled off is wound up again on a roll.

  The term “roll-to-sheet” refers to a process in which a belt-shaped transfer sheet 1 is pulled out from a roll (take-up), supplied to a flat substrate to be transferred, and before and after the transfer layer 2 is attached to the transferred substrate. In step (1), the transfer sheet 1 is cut into sheets each having a size substantially equivalent to one of the base material to be transferred, and the release support of the sheet from which the transfer layer 2 has been peeled is removed one by one ( This refers to the form of processing to be discarded). Alternatively, the transfer sheet 1 may be manually adhered to the transfer substrate 60, and then pressed with a spatula or the like to uniformly adhere to the surface of the transfer substrate 60.

  When the bonding layer 40 is formed of a pressure-sensitive adhesive composition or the like, the transfer sheet 1 can be attached to the base material 60 at normal temperature. When a heat-sealing layer is used as the bonding layer 40, the transfer sheet 1 is attached to the transfer target substrate 60 by a heat pressure of several hundred degrees. That is, when a heat seal layer is used as the bonding layer 40, it is necessary to bring the transfer sheet 1 into close contact with the substrate to be transferred 60 by applying heat to the heat seal layer and melting it by thermocompression bonding, in-mold molding, or the like. .

As shown in FIG. 3B, the transfer target substrate 60 includes a transfer target substrate body 61 and a sealer layer 62.
The transfer-receiving substrate main body 61 is the transfer-receiving substrate itself onto which the transfer sheet 1 is transferred. Examples of the substrate body 61 to be transferred include a plate, a wall, and the like made of a material such as an inorganic material, wood, and resin. Among them, examples of the inorganic material include calcium silicate, various stone materials, concrete, ceramics (ceramic-based sintered product), glass, and metal. Examples of the wood include cedar, pine, cypress, oak, oak, lauan, and teak. Examples of the resin include polyvinyl chloride, polyolefin resin, polyester resin, acrylic resin, polycarbonate resin, epoxy resin, urethane resin, and the like.

  The sealer layer 62 smoothes the surface of the base material 61 to be transferred, and when the base material to be transferred is porous or liquid-absorbing, fills or fills the surface to form a body. An undercoat layer for improving the adhesion between the transfer sheet 61 and the transfer sheet 1. When the smoothness of the surface (transfer surface) of the substrate body 61 to be transferred is sufficient and the porosity and absorbency of the surface do not hinder the transfer, the sealer layer 62 can be omitted.

Next, as shown in FIG. 4C, the releasable support 10 is peeled off from the transfer sheet 1 adhered on the substrate 60 to be transferred. The transfer step is completed by peeling the releasable support 10 from the transfer sheet 1, and the surface of the peeling layer 20 opposite to the decorative layer 30 is exposed. By peeling the release support 10 from the transfer sheet 1, the decorative material 100 is completed. As described later, another functional layer (for example, a top coat layer) is formed on the exposed surface of the release layer 20. May be.
By appropriately adjusting the peel strength between the bonding layer 40 of the transfer sheet 1 and the base material 60 to be transferred, when the release support 10 is peeled from the transfer sheet 1, the transfer sheet 1 It does not peel off from the transfer substrate 60.

Next, as shown in FIG. 4D, a top coat layer 70 is formed on the exposed surface of the release layer 20. Hereinafter, a laminate of the transfer layer 2 including the top coat layer 70 and the base material 60 to be transferred is also referred to as “decorative material 100”. The top coat layer 70 is a layer that imparts color, gloss, and the like to the surface of the decorative material 100 as a finishing agent and protects the decorative layer 30. Further, by forming the top coat layer 70, durability such as weather resistance, stain resistance, and abrasion resistance can be imparted to the decorative material 100. Examples of the top coat layer 70 include an acrylic resin, a silicon-based resin, a fluorine resin, and a urethane resin that are cured by ionizing radiation such as ultraviolet rays (UV resin) or electron beam (EB) or by heat.
The thickness of the top coat layer 70 is not particularly limited, but is preferably 5 μm or more and 1000 μm or less, more preferably 10 μm or more and 300 μm or less.
Through the above steps, it is possible to obtain the decorative material 100 in which the transfer sheet 1 has been transferred to the base material 60 to be transferred.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
In Examples and Comparative Examples 1 and 2 described later, “leafing type aluminum scale” corresponds to the small-grain scale S of the embodiment. The “non-leafing type aluminum scale” corresponds to the large-grain scale L of the embodiment. Comparative Example 1 shows an example in which non-leafing type aluminum scales were used as the small particle scales S.

(Example)
FIG. 5 is a diagram illustrating a method for manufacturing the transfer sheet A of the example. The transfer sheet A of the embodiment includes only the metallic layer 32 as the decorative layer 30. Hereinafter, manufacturing steps (A) to (C) of the transfer sheet A of the example will be described with reference to FIG. 5, the same components as those of the transfer sheet 1 of the embodiment (FIG. 1) are denoted by the same reference numerals.

As shown in FIG. 5A, a biaxially stretched PET film (“E5001” manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm was prepared as the release support 10.
An ink composed of an acrylic resin composition ("46-7" manufactured by Showa Ink Industry Co., Ltd.) was applied to one surface thereof to form a release layer 20 having a thickness of 2 m (dry).

  Next, as an ink containing an aluminum pigment, a composition ("Chem. XZ" manufactured by Showa Ink Industries, Ltd.) obtained by mixing an acrylic resin and a vinyl chloride-vinyl acetate copolymer was used. Gravure ink was prepared by adding a leafing type aluminum scale (17 μm) (“0870TS” manufactured by Toyo Aluminum Co., Ltd.) in an amount of 3.8 parts by mass with respect to 100 parts by mass of the resin. Then, as shown in FIG. 5B, this gravure ink was printed on the surface of the release layer 20 to form a first coating film 32A having a thickness of 1 μm. By drying the first coating film 32A, a resin layer 321 and a first glittering resin layer 322 are formed as described later.

  The leafing type aluminum scales (small particle scales S) included in the first coating 32A are opposite to the releasable support 10 when the first coating 32A is dried, as shown in FIG. 5B. Move to the side and arrange in parallel to cover the surface layer. In the first coating film 32 </ b> A, the region where the leafing type aluminum scales are arranged becomes the first glittering resin layer 322. On the other hand, in the first coating film 32A, when the leafing type aluminum scale moves to the surface layer on the side opposite to the releasable support 10, a resin layer 321 made of a resin is formed in a region on the releasable support 10 side. It is formed.

  Further, a gravure ink was prepared by adding non-leafing type aluminum scales (“MG600” manufactured by Toyo Aluminum Co., Ltd.) having a particle size of 25 μm (0.40 μm thickness) so as to be 36 parts by mass with respect to 100 parts by mass of the resin. . Then, as shown in FIG. 5C, the gravure ink was printed on the surface of the first coating film 32A to form a second coating film 32B having a thickness of 3 μm. Through the above steps, the transfer sheet A of the example was obtained. The first coating film 32A and the second coating film 32B become the metallic layer 32 in the transfer sheet A of the embodiment.

  When the gravure ink that becomes the second coating film 32B is printed on the surface of the first coating film 32A, the resin of the outermost layer of the first coating film 32A is slightly melted by the gravure ink. Due to this melting, of the non-leafing-type aluminum scales (large-diameter scales L) contained in the gravure ink, some non-leafing-type aluminum scales existing at the interface with the first coating film 32A have Move to the side of one coating. Thereby, as shown in FIG. 5 (C), non-leafing type aluminum scales (large-grain scales L) are arranged on the outermost layer of the first coating film 32A on the second coating film 32B side. Together with the aluminum scales (small particle size scales S) are arranged in parallel so as to cover the surface layer of the first coating film 32A. Therefore, the first glittering resin layer 322 composed of the first coating film 32A is a layer containing many small metal flakes S having a small particle diameter and very few large metal flakes L having a large particle diameter.

  As described above, when the second coating film 32B is printed on the surface of the first coating film 32A, the resin of the outermost layer of the first coating film 32A melts, so that the first coating film 32A and the second coating film 32B The interface becomes virtually indistinguishable. Therefore, in the following description, a region corresponding to the interface between the first coating film 32A and the second coating film 32B in the metallic layer 32 is also referred to as an “interface region of the metallic layer 32”. The interface region of the metallic layer 32 includes the outermost layer of the first coating 32A on the second coating 32B side.

In the second coating film 32B, other non-leafing type aluminum scales (large-grain scales L) are uniformly distributed in the thickness direction of the second coating film 32B as shown in FIG. 5C. Arrange in parallel with the layer direction.
In addition, when the resin of the outermost layer of the first coating film 32A is slightly melted by the gravure ink to be the second coating film 32B, the leafing type aluminum scales (small particle scales S) included in the first coating 32A are reduced. Among them, some leafing-type aluminum scales existing at the interface of the second coating film 32B move to the second coating film 32B side as shown in FIG. 5C. Therefore, the second glittering resin layer 323 composed of the second coating film 32B is a layer containing a large amount of metal flakes L having a large particle diameter and containing very little metal flakes S having a small particle diameter.

  Next, an acrylic plate serving as the transfer substrate 60 is prepared, and an acrylic-urethane resin composition (“KSI primer” manufactured by Showa Ink Industries, Ltd.) is applied to the surface of the acrylic plate, and a heat seal layer serving as the bonding layer 40 is formed. (Not shown). Then, the transfer sheet A was thermally transferred at 180 ° C. to the surface of the heat seal layer formed on the acrylic plate to obtain the decorative material of the example.

(Comparative Example 1)
In the transfer sheet, the leafing type aluminum scales were changed to non-leafing type aluminum scales (“260MS” manufactured by Toyo Aluminum Co., Ltd.) having a particle size of 9 μm (0.15 μm in thickness), and the aluminum scales were converted to 100 masses of resin. A decorative material of Comparative Example 1 was obtained under the same conditions as in the above example, except that 2.8 parts by mass was added to the parts.
(Comparative Example 2)
The leafing type aluminum scales were changed to aluminum scales having a particle size of 15 μm (thickness 0.13 μm) (“30T” manufactured by Toyo Aluminum Co., Ltd.), and the aluminum scales were changed to 3.9 parts by mass with respect to 100 parts by mass of the resin. It was added so that it might become. The non-leafing type aluminum scale was changed to “MG2030” manufactured by Toyo Aluminum Co., Ltd. to have a particle size of 33 μm (thickness 0.73 μm). Except for this, a decorative material of Comparative Example 2 was obtained under the same conditions as in the above Example.

The three types of decorative materials were evaluated for the cross section and adhesion of the metallic layer.
The cross section of the metallic layer was photographed with a scanning electron microscope (SEM), and evaluated with SEM images. In the SEM image, the case where the small-grain scales S and the large-grain scales L are arranged in the interface region of the metallic layer 32 in parallel is indicated by “○”, and the others are indicated by “x”.

The adhesion was tested by a cross-cut method according to JIS K5600-5-6. In the adhesion test, the presence or absence of peeling in the metallic layer was observed. When the classification of the test result was 0 (no peeling) or 1 (peeling was within 5%), it was marked as “○”, and other than that, it was marked as “x”.
FIG. 6 shows the evaluation results of the above test items for each of the decorative materials of Example and Comparative Examples 1 and 2. FIG. 6 is a diagram illustrating evaluation results of the example and comparative examples 1 and 2.

(Evaluation results)
In the SEM image of the cosmetic material of the example, it was observed that the small-grain scales S and the large-grain scales L were arranged in parallel to the interface region of the metallic layer 32. As described above, when the small-grain scales S and the large-grain scales L are arranged in parallel to the interface region of the metallic layer 32, the main sense of luminance as a decorative material can be obtained by the large-grain scales L. it can. In addition, the feeling of particles (insufficient specularity) caused by the gaps between the large particle scales L can be interpolated by the small particle scales S arranged between the large particle scales L. Therefore, it was clarified that the luminance of the cosmetic material of the example was improved.
In addition, in the adhesion test, no peeling in the metallic layer was observed, and it was confirmed that the decorative materials of Examples were excellent in adhesion.

As for the decorative material of Comparative Example 1, the same result as that of the example was obtained in the adhesiveness. However, in the decorative material of Comparative Example 1, it was confirmed that the small-grain scales S and the large-grain scales L were not arranged in parallel in the interface region of the metallic layer 32. This is because in the decorative material (transfer sheet) of Comparative Example 1, the small-grain scales S and the large-grain scales L were all non-leafing types, so that the small-grain scales S were dispersed in the first coating film 32A. This is probably because the first coating film 32A was not arranged on the outermost layer on the second coating film 32B side. As described above, in the decorative material of Comparative Example 1, since the small-grain scales S and the large-grain scales L are not arranged in parallel in the interface region of the metallic layer 32, the same brightness as in the example cannot be obtained. Became clear.
The “scale area ratio of the interface” in Comparative Example 1 shown in FIG. 6 is based on the assumption that the small-grain scales S contained in the first coating film 32A are arranged in the interface region of the metallic layer 32. Value. In Comparative Example 1, it is considered that there is a high possibility that the small-grain scale S does not actually exist in the interface region of the metallic layer 32 because the number of added small-grain scales S is small.

In the decorative material of Comparative Example 2, a result equivalent to that of the example was obtained for the layer configuration of the metallic layer 32. However, in the decorative material of Comparative Example 2, peeling was observed in the metallic layer 32, and it was confirmed that adhesion was low. This is because, in the decorative material of Comparative Example 2, the ratio of the small-grain scale S and the large-grain scale L was too large in the same plane due to the large particle size of the small-grain scale S, and Is considered to have decreased.
From the above results, it was clarified that the decorative materials of Examples were excellent in both luminance and adhesion, while being lower in cost than the method of forming a vapor deposition film as a decorative layer.

  As described above, the embodiments of the present invention have been described. However, the present invention is not limited to the above-described embodiments, and various modifications and changes can be made as in the modifications described below. Within the technical scope of In addition, the effects described in the embodiments are merely the most preferable effects generated from the present invention, and are not limited to those described in the embodiments. The above-described embodiment and the modified examples described below can be used in appropriate combinations, but detailed description is omitted.

(Modified form)
In the embodiment, the example in which the aluminum pigment is used as the preferable material of the small-grain scale S and the large-grain scale L forming the metallic layer 32 has been described. However, the present invention is not limited to this. The material of the large-grain scale L and the small-grain scale S may be another metal material (for example, iron, copper, nickel, or the like) or an alloy material thereof.

REFERENCE SIGNS LIST 1 transfer sheet 2 transfer layer 10 releasable support 20 release layer 30 decorative layer 31 picture pattern layer 31a picture layer 31b colored transparent layer 32 metallic layer 32A first coating film 32B second coating film 33 colored opaque layer 40 bonding layer 50 Release sheet 60 Transfer-receiving substrate 70 Top coat layer 321 Resin layer 322 First brilliant resin layer 323 Second brilliant resin layer S Small scale metal flakes (small particle flakes)
L Large-scale metal scales (large-scale scales)
R resin

Claims (7)

Releasable support, a transfer layer including a decorative layer, a transfer sheet laminated,
The decorative layer has a metallic layer made of a resin containing a plurality of metal flakes having a large diameter and metal flakes having a small diameter,
The metallic layer, in order from the side of the release support,
A resin layer made of the resin,
A first glittering resin layer containing the metal flakes having the small particle diameter and the metal flakes having the large particle diameter,
A second glittering resin layer containing the metal flakes having the large particle diameter and the metal flakes having the small particle diameter,
With
The first glittering resin layer contains a larger number of metal flakes having a small particle diameter per unit volume than the second glittering resin layer,
Transfer sheet. The transfer sheet according to claim 1,
The metal flakes having a small particle diameter and the metal flakes having a large particle diameter contained in the first glittering resin layer are arranged in parallel so as to cover a surface layer on the second glittering resin layer side,
The large-scale metal flakes contained in the second glittering resin layer are uniformly distributed in the thickness direction and arranged in parallel to the layer direction,
The large-scale metal scales contained in the second glittering resin layer are arranged in parallel so as to cover a surface layer on the first glittering resin layer side,
Transfer sheet. The transfer sheet according to claim 1 or claim 2,
The particle size of the metal flakes having the small particle size is less than 0.42 times the particle size of the metal flakes having the large particle size,
In the metallic layer, the metal flakes are 40 parts by mass or less with respect to 100 parts by mass of the resin.
Transfer sheet. The transfer sheet according to any one of claims 1 to 3, wherein
The decorative layer has at least one of a picture layer and a colored transparent layer on the side of the releasable support of the metallic layer,
Transfer sheet. The transfer sheet according to any one of claims 1 to 4, wherein
The decorative layer has a colored opaque layer on the side of the metallic layer opposite to the release support,
Transfer sheet. It is a manufacturing method of the transfer sheet as described in any one of Claim 1 to 5, Comprising:
A first coating film forming step of forming a first coating film by applying a coating in which a leaf-type small-sized metal flake and a resin are mixed on the surface of a release layer formed on a release support; ,
A second coating film forming step of forming a second coating film by applying a coating material obtained by mixing a non-leafing type large metal flake and a resin onto the surface of the first coating film,
In the first coating film forming step, the metal flakes having a small particle diameter are arranged in parallel so as to cover the surface layer on the side opposite to the releasable support,
In the second coating film forming step, a part of the large-grain metal flakes contained in the second coating film, together with the small-grain metal flakes arranged in the surface layer of the first coating film, Along with arranging in parallel so as to cover the surface layer of the first coating film, the remainder of the large-sized metal flakes contained in the second coating film is uniformly distributed in the thickness direction and parallel to the layer direction. Arranged, a part of the small scale metal flakes contained in the first coating, arranged to cover the surface layer of the second coating,
Transfer sheet manufacturing method.   A decorative material using the transfer sheet according to any one of claims 1 to 5.

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