JP2018167566A - Transfer sheet - Google Patents

Abstract

To provide a transfer sheet which does not require a contact process with an organic solvent and is capable of reproducing, in an intended region, more natural irregularities by cracks with less limitation to materials of a layer that causes cracks.SOLUTION: A transfer sheet 1 is made up of a releasable support body 10, a printing layer 30, and a joint layer 40, which are laminated in this order. The printing layer 30 includes a crack intended region 30P and a non-crack region 30N. A crack generation joint layer is disposed as the joint layer 40 on a surface of the crack intended region 30P on the opposite side of the releasable support body 10. A crack restriction joint layer is disposed as the joint layer 40 on a surface of the non-crack region 30N on the opposite side of the releasable support body 10, or a crack restriction layer is disposed between itself and the joint layer 40.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer sheet.

Conventionally, as a building material used for building wall materials, partitions, etc., a decorative material is used in which a transfer sheet on which various designs are printed is transferred to a base material such as a metal plate or a wooden board to be transferred. ing. For example, a metallic decorative material having the same design as that of natural wood can be obtained by transferring a transfer sheet on which a pattern having the same grain as that of natural wood is printed onto a metal plate.
In the transfer sheet as described above, it has been proposed to express the appearance of the design with a coating film or a printing layer of colored ink having cracks (see, for example, Patent Document 1).

Japanese Patent Publication No. 2-5192

The building material paper manufacturing method includes a curable resin layer that is cured by heating, ultraviolet rays, or the like as a constituent layer of the transfer layer, and the curable resin layer is cracked by contacting with an organic solvent in a semi-cured state. generate. At that time, a resist layer is formed in a desired pattern in advance on the surface of the curable resin layer, and a crack is generated only in a non-formation region of the resist layer, thereby having a pattern composed of a crack region and a non-crack region. A transfer layer is obtained. By transferring this transfer layer onto the substrate to be transferred, a design appearance composed of a crack region and a non-crack region is formed on the surface of the substrate to be transferred in plan view.
However, in order to generate cracks, a wet process in which an uncured component is eluted from a semi-cured curable resin layer in contact with an organic solvent is required, and a drying time of the organic solvent is required during the manufacturing process. Therefore, the manufacturing time becomes long (productivity is low). In addition, when contacting with an organic solvent and drying, a drying apparatus having explosion-proof standards and performance is required, and regulations in the Fire Service Law for handling organic solvents become severe. As a result, the cost of introducing the manufacturing equipment increases and the maintenance management becomes complicated. Moreover, since the material of the coating film or printed layer which produces a crack is also limited to specific curable resin, the range of the material which can be selected becomes narrow.

  An object of the present invention is to provide a transfer sheet that does not require a contact step with an organic solvent, has few material restrictions on a layer that generates cracks, and can reproduce more natural unevenness in an intended region. .

The present invention solves the above problems by the following means.
(1) A releasable support, a printed layer, and a bonding layer are laminated in this order, and the printed layer includes a planned crack region and a non-cracked region, and the separation of the planned crack region is performed. A crack-generating bonding layer is disposed as the bonding layer on the surface opposite to the moldable support, and a crack as the bonding layer is formed on the surface on the opposite side of the non-cracking support in the non-cracking region. The transfer sheet in which the suppression joining layer is arrange | positioned, or the crack suppression layer is arrange | positioned between the said joining layers.

  According to the present invention, it is possible to provide a transfer sheet that does not require a contact step with an organic solvent, has few material restrictions on a layer that generates cracks, and can reproduce more natural unevenness in an intended region. .

It is a figure explaining the cosmetics 100 of 1st Embodiment. It is sectional drawing of the transfer sheet 1 of 1st Embodiment. It is sectional drawing explaining the manufacturing method of the decorative material 100 of 1st Embodiment. It is sectional drawing explaining the manufacturing method of the decorative material 100 of 1st Embodiment. It is sectional drawing of the transfer sheet 1 of 2nd Embodiment (3rd Embodiment). It is sectional drawing of the decorative material 100 of 2nd Embodiment (3rd Embodiment).

Embodiments of the present invention will be described below with reference to the drawings. In addition, each figure shown below including FIG. 1 is the figure shown typically, and the magnitude | size and shape of each part are exaggerated suitably for easy understanding.
Numerical values such as dimensions and material names of each member described in the present specification are examples of the embodiment, and are not limited thereto, and may be appropriately selected and used.

[First Embodiment]
(Configuration of decorative material 100)
FIG. 1 is a diagram illustrating a decorative material 100 according to the first embodiment. The basic configuration of the decorative material 100 shown in FIG. 1 is common to the decorative materials of the second and third embodiments described later.
As shown in FIG. 1, the decorative material 100 includes a printed layer 30, an adhesive layer 40, and a base material 60. The decorative material 100 is manufactured by transferring the transfer sheet 1 to the base material 60, as will be described later. The transfer sheet 1 before being transferred to the substrate 60 includes a substrate film 10, a release layer 20, a print layer 30, an adhesive layer 40, and a release film 50 (all of which will be described later). In FIG. In order to make the arrangement of the non-crack region 30N easy to understand, only the printing layer 30 and the adhesive layer 40 of the transfer sheet 1 are illustrated. The other layers and films will be described in FIG.

<Print layer 30>
The printed layer 30 is a printed design layer on which a design (design) of the transfer sheet 1 described later is formed. Examples of the resin constituting the printing layer 30 include an acrylic resin, a vinyl chloride-vinyl acetate copolymer (vinyl acetate) resin, and an acrylic-vinyl acetate resin. In addition, a coloring pigment, a coloring dye, and the like are added to the printing layer 30. The layer thickness (dry) of the printing layer 30 is about 5 μm.

The print layer 30 has a crack region 30C and a non-crack region 30N.
The crack region 30C is a region where a crack C is formed according to the design. Before the transfer sheet 1 is transferred to the substrate 60, in the printed layer 30, a crack planned area 30P described later is formed in the crack area 30C. At the stage of the transfer sheet 1, no crack C is formed in the planned crack region 30P. After the transfer sheet 1 is transferred to the base material 60, a crack C is formed in the planned crack region 30P over time (heating, cooling, or a combination thereof), thereby forming a crack region 30C as shown in FIG.

  In the present embodiment, the crack region 30C can be appropriately set according to the design, and is not limited to a linear (striped) rectangular region as shown in FIG. The crack region 30 </ b> C may have any shape as long as the envelope circumscribing at least one crack C forms a closed region as long as the region is partitioned by the envelope. Here, the closed region may partially include the end portion (end edge) of the printing layer 30.

The non-crack region 30N is a region where no crack is formed. In the non-crack region 30N of the first embodiment, a hard coat layer 80 (not shown in FIG. 1) to be described later is formed between the adhesive layer 40 and the non-crack region 30N.
In the present embodiment, the pattern formed on the print layer 30 is a striped pattern composed of a plurality of lines as shown in FIG. In the stripe pattern, lines L1 corresponding to the crack regions 30C (planned crack regions 30P) and lines L2 corresponding to the non-crack regions 30N are alternately arranged (in FIG. 1, a part thereof is shown). ).
In the present embodiment, an example in which the crack region 30C is formed in the line L1 that is a part of the symbol is shown, but the crack region 30C does not necessarily have to be formed according to the symbol.

The stripe pattern as shown in FIG. 1 shows an example of a pattern formed on the print layer 30, and is not limited to this example. The pattern formed on the print layer 30 may be a model imitating a natural material such as wood grain or stone.
In the printed layer 30, the crack region 30C and the non-crack region 30N do not necessarily have to be regularly arranged, and each may be randomly arranged. For example, when the almost entire surface of the printing layer 30 is the crack region 30C, the non-cracking region 30N may be partially arranged, and when almost the entire surface of the printing layer 30 is the non-cracking region 30N, the crack is generated. The region 30C may be partially arranged.

  Although not shown, a print coat layer may be laminated on the adhesive layer 40 side of the print layer 30. The print coat layer functions as a concealing layer for making the base material 60 (base) difficult to see. The print coat layer is formed so as to cover the entire surface of the print layer 30 and is colored, for example, white, gray, brown or the like. When the print coat layer is laminated, cracks in the crack region 30 </ b> C are mainly formed in the print coat layer, but are viewed by the viewer as if cracks are formed on the surface of the print layer 30. The reason why a crack occurs in the crack region 30C and the reason why no crack is formed in the non-crack region 30N will be described later.

  In the first embodiment, an adhesive layer made of an adhesive (hereinafter also referred to as an adhesive layer) is used as the bonding layer. The pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) 40 is a layer (bonding layer) that bonds the transfer sheet 1 and the base material 60 when the transfer sheet 1 is transferred to the base material 60. The configuration of the adhesive layer 40 will be described later.

  The substrate 60 is a transfer target to which the transfer sheet 1 is transferred. Although not shown in FIG. 1, in the first embodiment, the base material 60 includes a base material body 61 and a sealer layer 62 (see FIG. 3B). The sealer layer 62 is not an essential layer, but is preferably provided in order to ensure adhesiveness with the bonding layer when the surface of the substrate body 61 is rough or porous. The details of the substrate 60 including the sealer layer 62 will be described later.

(Configuration of transfer sheet 1)
Next, the configuration of the transfer sheet 1 will be described.
FIG. 2 is a cross-sectional view of the transfer sheet 1 of the first embodiment. The transfer sheet 1 can be stored or transported in the form shown in FIG.
As shown in FIG. 2, the transfer sheet 1 includes a base film 10, a release layer 20, a print layer 30, a hard coat layer 80, an adhesive layer 40, and a release film 50.

  The transfer sheet 1 in the present embodiment employs a flexible and thin film form as a releasable support having releasability with respect to the transfer layer below the release layer (hereinafter referred to as a base film). Also called). On this base film 10, a transfer layer comprising a release layer 20, a printing layer 30, a hard coat layer 80, and an adhesive layer 40, and a release film 50 having releasability from the adhesive layer are laminated in this order. ing. The “lamination in this order” in the present invention means not only direct lamination but also indirect lamination. For example, there is another layer between the base film 10 and the release layer 20. Is also acceptable.

<Base film 10>
The base film (releasable support) 10 is a film that supports the printing layer 30. The base film 10 has releasability from the transfer layer composed of the release layer 20 and the like. After the transfer sheet 1 is transferred to the base 60 (described later), the base film 10 is released from the interface with the release layer 20. The Examples of the base film 10 include polyester resins such as polyethylene terephthalate, polyethylene aphthalate, and polybutylene terephthalate, polyolefin resins such as polypropylene and polyethylene, cellulose resins such as polycarbonate resin, polystyrene resin, and triacetyl cellulose (TAC). Examples thereof include a film made of a resin or the like. Among these, a biaxially stretched polyethylene terephthalate (PET) film is preferable in terms of excellent strength and flexibility. In addition, the conventionally well-known peeling layer may be formed in the surface at the side of the peeling layer 20 in the base film 10, and the peeling process may be performed.
The film thickness of the base film 10 is preferably 10 μm or more and 200 μm, more preferably 20 μm or more and 60 μm or less.

<Peeling layer 20>
The release layer 20 is a layer that is laminated to facilitate peeling of the base film 10 from the transfer sheet 1. The release layer 20 remains as the outermost layer of the transfer sheet 1 after the transfer sheet 1 is transferred to the substrate 60 and the substrate film 10 is released. A weather resistance imparting layer 70 (described later) is formed on the surface of the release layer 20. Examples of the resin constituting the release layer 20 include acrylic polyol, urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, acrylic-vinyl chloride-vinyl acetate copolymer, or a mixture of two or more of these resins. Examples thereof include a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer. In these compositions, a small amount of isocyanate or the like may be further added for adjusting the peel strength. Moreover, you may add weathering agents, such as a ultraviolet absorber (UVA) and light stabilizers (radical scavengers, such as a HALS (hindered amine type radical scavenger)), to these compositions, for example.
The thickness (dry) of the release layer 20 is about 1 μm or more and 2 μm or less.

  In the present embodiment, the peel strength between the base film 10 and the release layer 20 (according to JIS Z0237) is at least twice the peel strength between the release film 50 and the adhesive layer 40 described later. Is set as follows. This is to prevent the base film 10 from being released from the release layer 20 when the release film 50 is released from the transfer sheet 1. However, the present invention is not limited thereto, and the peeling strength may be reversed so that the release layer 20 remains on the base film 10 side when the release film 50 is released from the transfer sheet 1.

<Adhesive layer 40>
The pressure-sensitive adhesive layer (crack generation bonding layer) 40 of the present embodiment is made of a cured product of the pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition contains, for example, an acrylic pressure-sensitive adhesive as a main agent and an isocyanate curing agent.
The thickness of the pressure-sensitive adhesive 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. In the transfer sheet 1 of the first embodiment, the hard coat layer 80 as a crack suppression layer is provided between the adhesive layer 40 and the non-crack region 30N (printing layer 30) on the surface opposite to the base film 10. Are stacked. Therefore, in the transfer sheet 1 of the first embodiment, the layer thickness of the adhesive layer 40 is partially different.

[Acrylic adhesive]
A preferable acrylic pressure-sensitive adhesive includes, for example, an acrylate copolymer obtained by copolymerizing an acrylate ester with another monomer. Examples of the acrylate ester include ethyl acrylate, acrylate-n-butyl, acrylate-2-ethylhexyl, isooctyl acrylate, isononyl acrylate, hydroxylethyl acrylate, propylene glycol acrylate, acrylamide, glycidyl acrylate, and the like. Is mentioned. These can be used alone or in combination of two or more.

Other monomers include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide Methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and n-ethylhexyl methacrylate. These can be used alone or in combination of two or more.
In addition, as a commercial item of the said acrylic adhesive, Nisset (made by Nippon Carbide), SK dyne (made by Soken Chemical Co., Ltd.) etc. can be used suitably, for example.

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

  Examples of the isocyanate 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 3 of this urethane prepolymer. Examples include a polymer.

  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, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.

  It is preferable that content of the said isocyanate hardening agent in the adhesion layer 40 is 0.1 to 1.0 mass part in conversion of solid content with respect to 100 mass parts of solid content of an acrylic adhesive. When the blending amount is less than 0.1 parts by mass, stress relaxation is exhibited, but internal destruction may occur, which is not preferable. On the other hand, when the content is greater than 1.0 part by mass, the adhesive layer 40 is excessively cured by crosslinking, and the print layer 30 is likely to crack.

<Hard coat layer 80>
The hard coat layer 80 is a layer that suppresses the stress generated by the fluidity of the adhesive layer 40 from acting on the non-cracked region 30N of the printing layer 30 (crack suppression layer), and the stress generated by the fluidity of the adhesive layer 40 It can be said that the buffer layer. The hard coat layer 80 is laminated on the surface opposite to the base film 10 in the non-crack region 30N of the printing layer 30.
In the printed layer 30, since the hard coat layer 80 is laminated on the surface on the adhesive layer (cracking joining layer) 40 side, stress due to the fluidity of the adhesive layer 40 hardly acts in the non-crack region 30 </ b> N. C is not formed.

  Examples of the resin constituting the hard coat layer 80 include acrylic-vinyl acetate (vinyl chloride-vinyl acetate copolymer) resin, vinyl acetate resin, and the like. The resin that can be used as the hard coat layer 80 preferably has a glass transition point (Tg) of room temperature or higher. This is because if the glass transition point of the hard coat layer 80 is lower than room temperature, the hard coat layer 80 itself is deformed due to a change in temperature, and the deformation acts on the printing layer 30 as stress. In addition, it is preferable that the glass transition point of the hard coat layer 80 is lower than that of the printing layer 30 and higher than that of the bonding layer. This is because, when the viscoelasticity of each layer changes, if it is in this relationship, stress due to deformation is easily absorbed.

  The hard coat layer 80 is preferably softer than the printing layer 30 and harder than the adhesive layer 40. This is because if the hard coat layer 80 is harder than the printing layer 30, a crack occurs in itself due to the stress generated by the fluidity of the adhesive layer 40. Further, if the hard coat layer 80 is softer than the adhesive layer 40, stress due to the fluidity of the adhesive layer 40 is transmitted to the printing layer 30 and the printing layer 30 is likely to crack. The hardness of the hard coat layer 80, the printing layer 30, and the adhesive layer 40 can be specified by a measuring method such as indentation hardness, scratch hardness, rebound hardness, and the like.

Moreover, it is preferable that the hard coat layer 80 does not add a color pigment. As described above, a color pigment is added to the printing layer 30, but the color pigment may trigger cracks. Therefore, by not adding the color pigment to the hard coat layer 80, it is possible to more effectively suppress the occurrence of cracks in the non-crack region 30N of the print layer 30.
The layer thickness (dry) of the hard coat layer 80 is preferably 1 μm or more.

<Peeling film 50>
The release film 50 prevents the adhesive layer 40 from adhering to the base film 10 which is a releasable support and being unable to be released when the transfer sheet 1 is wound up and stored in a roll shape. It is a film. The release film 50 is released from the transfer sheet 1 when the transfer sheet 1 is transferred to the substrate 60. Examples of the release film 50 include silicon release type polyethylene terephthalate (PET), untreated polyethylene terephthalate, and polypropylene.
The thickness of the release film 50 is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 60 μm or less.

  In addition, when the surface on the opposite side to the transfer layer of the base film 10 has sufficient releasability from the adhesive layer 40, the release film 50 is omitted. For example, when a release agent layer made of silicon resin, fluorine resin, or the like is formed on the surface of the base film 10 opposite to the transfer layer, it is usually wound without the release film 50.

<About generation | occurrence | production etc. of the crack in the printing layer 30 of 1st Embodiment>
The reason why after the transfer sheet 1 described above is transferred to the base material 60, cracks occur in the planned crack region 30P of the print layer 30 over time and the reason why no crack occurs in the non-crack region 30N of the print layer 30 will be described.

  Before the transfer sheet 1 is transferred to the substrate 60, the stress generated by the fluidity of the adhesive layer 40 acts on the printing layer 30, but is printed by the release film 50 and the substrate film 10 that are more rigid than the printing layer 30. Expansion and contraction of the layer 30 is suppressed. Therefore, the printed layer 30 is less likely to crack even when stored and stocked for a long time, and can maintain its shape.

  On the other hand, when the transfer sheet 1 from which the release film 50 is released is transferred to the base material 60 and the adhesive layer 40 is attached to the hard base material 60, the stress generated by the fluidity of the adhesive layer (cracking joining layer) 40 Acts on the printing layer 30, but the expansion and contraction of the printing layer 30 is suppressed to some extent by the base film 10. Thereafter, when the base film 10 is released from the transfer sheet 1, the shape of the planned crack region 30 </ b> P of the printing layer 30 cannot be maintained due to the stress generated by the fluidity of the adhesive layer 40, and a crack occurs. The planned crack region 30P becomes a crack region 30C when a crack occurs (see FIG. 1).

  The printing layer 30 may be formed in a state where tension is applied to the base film 10 side. Moreover, after forming the printing layer 30 in the base film 10, shrinkage | contraction etc. may generate | occur | produce by drying of a solvent. In this case, the printing layer 30 is internally stressed along the surface direction of the transfer sheet 1 (the direction in which cracks occur). Therefore, when the stress generated by the fluidity of the adhesive layer 40 acts on the printed layer 30 (scheduled crack region 30P), the stress and the stress applied to the inside interact with each other, so that cracks further occur. It tends to occur.

As a specific example of the pressure-sensitive adhesive layer (crack-generating bonding layer) 40 that causes cracks in the printed layer 30, a cured product of the pressure-sensitive adhesive composition as described above can be exemplified. A composition containing an adhesive and an isocyanate curing agent can be exemplified.
Moreover, the crack generation joining layer can illustrate the layer whose glass transition point is between about -20 degreeC and 20 degreeC as a viscoelasticity from a viewpoint of the physical property surface which generates a crack, for example. Such a layer having a glass transition point has a large change in viscoelasticity around room temperature, and therefore can generate cracks even with a slight temperature change.

  On the other hand, in the non-cracked region 30N of the printed layer 30, the stress generated by the fluidity of the adhesive layer (crack generation joining layer) 40 is suppressed by the hard coat layer (crack suppression layer) 80 that is harder than the adhesive layer 40. It hardly acts on the non-cracked region 30N of the printed layer 30. Thus, in the non-cracked region 30N of the printed layer 30, the stress due to the fluidity of the adhesive layer 40 hardly acts, so that the shape can be maintained. Therefore, in the non-crack region 30N of the printed layer 30, the occurrence of cracks is suppressed as shown in FIG.

Further, as shown in FIG. 2, in the adhesive layer 40, the thickness of the adhesive layer 40 in the region corresponding to the non-cracked region 30N where the hard coat layer 80 is laminated is thinner than the region corresponding to the planned crack region 30P. Therefore, the stress generated by the fluidity of the adhesive layer 40 is further relaxed. Therefore, the generation of cracks in the non-crack region 30N can be more effectively suppressed.
Therefore, according to the decorative material 100 of the present embodiment, more natural irregularities can be reproduced by cracking in the intended crack planned area 30P, and cracks are generated in the non-cracked area 30N which is the other area. It can be prevented from occurring.

  In addition, in the transfer sheet 1 of the present embodiment, since a crack is generated in the planned crack region 30P, a contact process with an organic solvent is not required, so that productivity can be improved by shortening the manufacturing time. Furthermore, the material of the coating film or the printing layer 30 that generates cracks is not limited to a specific curable resin, so that the range of selectable materials can be made wider.

<Other embodiment of the adhesion layer 40>
In the transfer sheet 1 of the first embodiment, the layer (bonding layer) that becomes a bonding layer between the transfer sheet 1 and the substrate 60 may be an adhesive layer. The adhesive layer preferably has high fluidity, and examples thereof include acrylic adhesives, epoxy adhesives, urethane adhesives, silicon adhesives, and UV curable adhesives.
The layer thickness (dry) of the adhesive layer is preferably 10 μm or more and 500 μm or less, and more preferably 15 μm or more and 300 μm or less.
Even when an adhesive layer is used as the bonding layer, after transferring the transfer sheet 1 to the base material 60, for example, by repeatedly changing the temperature in the furnace or the like, and promoting the expansion and contraction of the adhesive layer, the expected crack region 30P can be cracked.

(Method for manufacturing cosmetic material 100)
Next, the manufacturing method of the decorative material 100 of 1st Embodiment is demonstrated.
FIG.3 and FIG.4 is sectional drawing explaining the manufacturing method of the decorative material 100 of 1st Embodiment, respectively.

  First, as shown in FIG. 3A, the release film 50 is released from the transfer sheet 1. By releasing the release film 50 from the transfer sheet 1, the surface (adhesive surface) of the adhesive layer 40 opposite to the printed layer 30 is exposed. As described above, in the present embodiment, the peel strength between the base film 10 and the release layer 20 is at least twice the peel strength between the release film 50 and the adhesive layer 40. Therefore, when the release film 50 is released from the transfer sheet 1, the base film 10 is not released from the release layer 20.

  Next, as shown in FIG. 3B, the transfer sheet 1 from which the release film 50 is released is transferred (applied) to the base material 60. The transfer of the transfer sheet 1 to the base material 60 can be continuously performed, for example, in the form of a roll-to-roll, a roll-to-sheet, or the like. Here, “roll-to-roll” means that the belt-like transfer sheet 1 is pulled out from a roll (winding) and supplied to a flat plate-like transfer body (substrate body 61), and the transfer layer is placed on the transfer body. This is a processing mode in which the belt-like releasable support (base film 10) after releasing the transfer layer is again wound on a roll. “Roll-to-sheet” refers to a belt-like transfer sheet 1 that is drawn before and after being transferred from a roll (winding) to a flat plate-like transfer material and the transfer layer is transferred onto the transfer material. This is a processing mode in which the sheet 1 is cut into approximately the size of one sheet to be transferred to form a sheet, and the transfer layer is removed (discarded) for each sheet after the release layer is released. Alternatively, the transfer sheet 1 may be manually transferred to the substrate 60 and then pressed with a spatula or the like so as to be in close contact with the surface of the substrate 60.

The substrate 60 includes a substrate main body 61 and a sealer layer 62.
The base body 61 is a transfer target body onto which the transfer sheet 1 is transferred. Examples of the base body 61 include plates and walls made of materials such as inorganic materials, wood, and resins. Among these, examples of the inorganic material include stone, concrete, glass, and metal. The base body 61 may be a ceramic ware made of an inorganic material.

The sealer layer 62 is an undercoat layer for smoothening the surface of the base body 61 and improving the adhesion between the base body 61 and the transfer sheet 1. The sealer layer 62 is omitted when the surface (transfer surface) of the base body 61 is sufficiently smooth.
After the transfer sheet 1 is transferred to the substrate 60, a crack is formed in the planned crack region 30P of the printed layer 30 with time, and becomes a crack region 30C. Whether or not a crack is formed in the planned crack region 30P can be visually observed.

  Next, as shown in FIG. 4C, the base film 10 is released from the transfer sheet 1 transferred to the base 60. By releasing the base film 10 from the transfer sheet 1, the surface of the release layer 20 opposite to the printed layer 30 is exposed. In FIG. 4C, since the adhesive layer 40 and the substrate 60 of the transfer sheet 1 are bonded with a strong adhesive force, when the substrate film 10 is released from the transfer sheet 1, the transfer sheet 1 is There is no release from the substrate 60.

  4C and 4D show an example in which a crack occurs in the printed layer 30 over time after the base film 10 is released from the transfer sheet 1 bonded onto the base 60. FIG. ing. Usually, a crack occurs in the printing layer 30 due to the stress caused by the fluidity of the adhesive layer 40 after the substrate film 10 is released from the transfer sheet 1 and the suppression of the stress acting on the printing layer 30 is released. Since it takes about 1 to 30 days, such a form is obtained. However, the printing layer 30 is in a state in which the base film 10 exists on the transfer layer by using a thin material having a low elastic modulus for the base film 10 and repeating repeated heating and cooling to the transfer layer. In the case where a sufficient stress can be applied, the base film 10 may be released from the transfer sheet 1 after a crack is formed in the planned crack region 30P.

Next, as shown in FIG. 4D, a weather resistance imparting layer 70 is formed on the exposed surface of the release layer 20. The weather resistance imparting layer 70 is a so-called overprint layer (OP layer) and is a layer that serves as a protective layer of the release layer 20.
Note that the step of forming the weather resistance imparting layer 70 on the release layer 20 needs to be performed after a crack is formed in the planned crack region 30P. This is because if the weather resistance imparting layer 70 is formed before the crack is formed in the planned crack region 30P, the crack is less likely to occur in the planned crack region 30P.
The thickness of the weather resistance imparting layer 70 is not particularly limited, but is preferably in the range of 10 μm or more and 50 μm or less, and more preferably 15 μm or more and 40 μm or less.

  As the weather resistance imparting layer 70, for example, a layer containing an ionizing radiation curable resin and a wax can be used. By using an ionizing radiation curable resin, it is possible to eliminate the pressing step for smoothing, which is necessary in the conventional aqueous OP layer.

  The weather resistance imparting layer 70 can be formed using a coating method such as die coating, curtain flow coating, comma coating, spray coating or the like. As a material, for example, a resin layer forming ink (paint) made of a resin composition, a fluororesin composition, a silicon resin composition or the like containing various ionizing radiation curable resins and waxes is used as a release layer. It is possible to form a laminated layer by applying the film on the substrate 20. The resin layer forming ink may contain an organic solvent as a solvent.

  The ionizing radiation curable resin is a resin that is cured by ionizing radiation such as ultraviolet rays and electron beams. Examples of the ionizing radiation curable resin include a resin obtained by polymerizing and curing a photopolymerizable monomer such as a bifunctional or higher polyfunctional acrylate and a bifunctional or higher polyfunctional methacrylate with a photopolymerization initiator or the like. .

The wax is contained in order to adjust the surface state of the weather resistance imparting layer 70. As the wax, synthetic wax, natural wax or the like can be used. Examples of the synthetic wax include polyethylene wax, and examples of the natural wax include petroleum wax such as paraffin wax, animal wax such as beeswax and whale wax, plant wax such as wood wax and rice bran wax, and mineral wax such as montan wax. Can be used.
By passing through the above process, the decorative material 100 by which the transfer sheet 1 was transcribe | transferred to the base material 60 can be obtained.

  Although the said embodiment demonstrated the example which transfers the transfer sheet 1 which has the adhesion layer 40 and the hard-coat layer 80 to the base material 60, and manufactures the cosmetics 100, it is not limited to this. The adhesive layer 40 and the hard coat layer 80 are laminated on the substrate 60 side, and the adhesive layer 40 and the hard coat layer 80 are laminated on the transfer sheet 1 in which the substrate film 10, the release layer 20 and the print layer 30 are laminated. The decorative material 100 may be manufactured by transferring it to the substrate 60. The manufacturing form of the decorative material 100 according to such a form is common to second and third embodiments described later.

[Second Embodiment]
Next, a second embodiment of the present invention will be described.
The basic configuration of the decorative material 100 of the second embodiment is the same as that of the first embodiment (see FIG. 1). The decorative material 100 of the second embodiment is different from the first embodiment in that a part of the adhesive layer 140 also serves as a crack suppression layer. In the decorative material 100 of the second embodiment, other configurations are the same as those of the decorative material 100 of the first embodiment.

  In the description and drawings of the second embodiment, parts, members, and the like that perform the same functions as those of the first embodiment are denoted by the same reference numerals as the first embodiment or the same reference numerals at the end (last two digits). The overlapping description will be omitted as appropriate. For example, the same reference numerals “1” and “100” as those in the first embodiment are assigned to the transfer sheet and the decorative material, and “140” is assigned to the adhesive layer.

(Configuration of transfer sheet 1)
FIG. 5 is a cross-sectional view of the transfer sheet 1 of the second embodiment. FIG. 6 is a cross-sectional view of the decorative material 100 of the second embodiment.
As shown in FIG. 5, the transfer sheet 1 of the second embodiment includes a base film 10, a release layer 20, a print layer 30, an adhesive layer 140, and a release film 50. The transfer sheet 1 according to the second embodiment is different from the transfer sheet 1 according to the first embodiment in that the hard coat layer 80 is not provided.
In the transfer sheet 1 of the second embodiment, the configuration (material, thickness, etc.) of the base film 10, the release layer 20, the print layer 30, and the release film 50 is substantially the same as that of the first embodiment, and therefore description is made. Are omitted as appropriate.

  As shown in FIG. 5, the adhesive layer (joining layer) 140 of the second embodiment includes a first adhesive layer 141 (cracking joining layer) corresponding to the planned crack region 30P and a second corresponding to the non-cracked region 30N. An adhesive layer (crack-inhibiting bonding layer) 142. These pressure-sensitive adhesive layers are formed by applying pressure-sensitive adhesive compositions having different compositions in accordance with the corresponding regions.

The first adhesive layer 141 and the second adhesive layer 142 are each made of a cured product of the adhesive composition. Among these, the adhesive composition which comprises the 1st adhesion layer 141 contains the acrylic adhesive as a main ingredient, and an isocyanate hardening agent. Moreover, the adhesive composition which comprises the 2nd adhesion layer 142 contains the acrylic adhesive as a main ingredient, and an isocyanate hardening agent, and also contains a plasticizer (after-mentioned).
In addition, since the structure of the acrylic adhesive and isocyanate type hardening agent used as the material common to the 1st adhesion layer 141 and the 2nd adhesion layer 142 is the same as 1st Embodiment, description is abbreviate | omitted.

[Plasticizer]
Hereinafter, the plasticizer added to the second adhesive layer 142 will be described.
By adding a plasticizer to the pressure-sensitive adhesive constituting the second pressure-sensitive adhesive layer 142, it is possible to suppress the occurrence of cracks in the non-cracked region 30N of the print layer 30 over time. Examples of the plasticizer contained in the adhesive layer 140 include a phthalate ester plasticizer and an adipate ester plasticizer.

  Examples of the phthalate ester plasticizer contained in the pressure-sensitive adhesive composition include di-2-ethylhexyl phthalate (DOP), dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), Heptylnonyl phthalate (HNP), di-n-octyl phthalate (DNOP), di-i-octyl phthalate (DCapP), diisononyl phthalate (DINP), di-i-decyl phthalate (DIDP), ditridecyl phthalate (DTDP), dicyclohexyl phthalate (DCHP), butyl benzyl phthalate (BDP), ethyl phthalyl ethyl glycolate (EPEG), butyl phthalyl butyl glycolate (BPBG), etc., one or two of these You may use the above together.

  Examples of the adipate plasticizer contained in the pressure-sensitive adhesive composition include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), dimethyl adipate (DMA), and adipic acid. Examples include diethyl (DEA), diisopropyl adipate (DIPA), dipropyl adipate (DPA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), and the like. Good.

  From the viewpoint of environmentally controlled substances, it is preferable to use an adipate ester plasticizer rather than a phthalate ester plasticizer. Of the adipate ester plasticizers, dioctyl adipate (DOA) is preferably used from the viewpoint of versatility and compatibility with resins.

  It is preferable that the compounding quantity of a plasticizer is 0.1-10 mass parts in conversion of solid content with respect to 100 mass parts of solid content of an acrylic adhesive, and it is more preferable that it is 1-7 mass parts. When the blending amount is less than 0.1 parts by mass, sufficient stress relaxation property is hardly expressed in the obtained adhesive layer 140, and durability may not be obtained. On the other hand, when the content is more than 10 parts by mass, the stress applied to the print layer 30 is less likely to be relaxed inside the second adhesive layer 142 as described later, so that the print layer 30 is shaped by the stress applied to itself. May not be maintained, and cracks may occur. Further, when the content is more than 10 parts by mass, the adhesive force is greatly reduced by the bleed-out plasticizer, so that it mainly floats on the second adhesive layer 142 and easily peels off. If it is the said range, since the printing layer 30 comes to be able to maintain a shape for the reason mentioned later, generation | occurrence | production of a crack can be suppressed. In addition, after the transfer sheet 1 is transferred to the base material 60, it is possible to prevent the second adhesive layer 142 from mainly floating or peeling off from the base material 60 in a high-temperature and high-humidity environment.

<About generation | occurrence | production of the crack in the printing layer 30 of 2nd Embodiment, etc.>
The reason why after the transfer sheet 1 described above is transferred to the base material 60, cracks occur in the planned crack region 30P of the print layer 30 over time and the reason why no crack occurs in the non-crack region 30N of the print layer 30 will be described.

  Before the transfer sheet 1 is transferred to the substrate 60, the stress generated by the fluidity of the adhesive layer 140 (the first adhesive layer 141 and the second adhesive layer 142) acts on the printing layer 30, but more than the printing layer 30. Expansion and contraction of the printing layer 30 is suppressed by the rigid release film 50 and the base film 19. Therefore, the printed layer 30 can maintain its shape.

  On the other hand, when the transfer sheet 1 from which the release film 50 is released is transferred to the base material 60 and the adhesive layer 140 is attached to the hard base material 60, the stress generated by the fluidity of the adhesive layer 140 acts on the printing layer 30. However, expansion and contraction of the printing layer 30 is suppressed to some extent by the base film 10. Thereafter, when the base film 10 is released from the transfer sheet 1, the planned crack region 30 </ b> P of the printing layer 30 cannot be maintained in shape due to the stress generated by the fluidity of the first adhesive layer (cracking joining layer) 141. . Therefore, the crack planned area 30P of the printed layer 30 is cracked and becomes a crack area 30C (see FIG. 1).

  The printing layer 30 may be formed in a state where tension is applied to the base film 10 side. Moreover, after forming the printing layer 30 in the base film 10, shrinkage | contraction etc. may generate | occur | produce by drying of a solvent. In this case, the printing layer 30 is internally stressed along the surface direction of the transfer sheet 1 (the direction in which cracks occur). Therefore, when the stress generated by the fluidity of the first adhesive layer 141 acts on the printing layer 30 (scheduled crack region 30P), the stress and the stress applied to the inside will interact with each other, and therefore, further. Cracks are likely to occur.

  In contrast, in the second adhesive layer 142 of the adhesive layer 140, 0.1 to 10 parts by mass of a plasticizer in terms of solid content is blended with respect to 100 parts by mass of the solid content of the acrylic adhesive. According to this, since the viscosity of the second pressure-sensitive adhesive layer (crack-suppressing bonding layer) 142 is lowered when the fluidity is further increased, the stress caused by the fluidity is relieved (reduced). Therefore, after the transfer sheet 1 is transferred to the base material 60, the stress generated by the fluidity of the second adhesive layer 142 hardly acts on the non-cracked region 30N of the printing layer 30, so the non-cracked region 30N has a shape. Can be maintained. Therefore, in the non-crack region 30N of the printed layer 30, the occurrence of cracks is suppressed as shown in FIG.

In order to increase the fluidity of the first adhesive layer 141, it is desirable to increase the layer thickness, but it is conceivable that the productivity is reduced. Therefore, by setting the thickness of the pressure-sensitive adhesive layer 140 to the range of 10 μm to 50 μm (more preferably 15 μm to 30 μm) described above, the planned crack region corresponding to the first pressure-sensitive adhesive layer 141 without reducing productivity. At 30P, the occurrence of cracks can be promoted.
Since the manufacturing method of the decorative material 100 of 2nd Embodiment is substantially the same as 1st Embodiment, description is abbreviate | omitted.

[Third Embodiment]
Next, a third embodiment of the present invention will be described.
The basic configuration of the decorative material 100 of the third embodiment is the same as that of the first embodiment (see FIG. 1). The decorative material 100 of the third embodiment is different from the first embodiment in that a part of the adhesive layer 240 also serves as a crack suppression layer. In the decorative material 100 of the third embodiment, other configurations are the same as those of the decorative material 100 of the first embodiment.

  In the description and drawings of the third embodiment, parts, members, and the like that perform the same functions as those of the first embodiment are denoted by the same reference numerals as the first embodiment or the same reference numerals at the end (last two digits). The overlapping description will be omitted as appropriate. For example, the same reference numerals “1” and “100” as those in the first embodiment are assigned to the transfer sheet and the decorative material, and “240” is assigned to the adhesive layer.

(Configuration of transfer sheet 1)
Since the configuration of the transfer sheet 1 of the third embodiment is the same as that of the second embodiment, description will be made with reference to FIGS. 5 and 6 of the second embodiment.
As shown in FIG. 5, the transfer sheet 1 of the third embodiment includes a base film 10, a release layer 20, a printing layer 30, an adhesive layer 240 and a release film 50. The transfer sheet 1 according to the third embodiment is different from the transfer sheet 1 according to the second embodiment in that a part of the adhesive layer 240 contains blocked isocyanate.
In the transfer sheet 1 of the third embodiment, the configurations (material, thickness, etc.) of the base film 10, the release layer 20, the print layer 30, and the release film 50 are substantially the same as those of the first embodiment. Are omitted as appropriate.

  As shown in FIG. 5, the adhesive layer (bonding layer) 240 of the third embodiment includes a first adhesive layer (cracking bonding layer) 241 corresponding to the planned crack region 30P and a second corresponding to the non-cracked region 30N. An adhesive layer (crack-inhibiting bonding layer) 242. These pressure-sensitive adhesive layers are formed by applying pressure-sensitive adhesives having different compositions in accordance with the corresponding regions.

The first adhesive layer 241 and the second adhesive layer 242 are each made of a cured product of the adhesive composition. Among these, the adhesive composition which comprises the 1st adhesion layer 241 contains the acrylic adhesive as a main ingredient, and an isocyanate hardening agent. Moreover, the adhesive composition which comprises the 2nd adhesion layer 242 contains the acrylic adhesive as a main ingredient, and an isocyanate hardening agent, and also contains block isocyanate (after-mentioned).
In addition, since the structure of the acrylic adhesive and isocyanate hardening agent used as the material common to the 1st adhesion layer 241 and the 2nd adhesion layer 242 is the same as 1st Embodiment, description is abbreviate | omitted.

In this embodiment, the pressure-sensitive adhesive layer 240 before heating described later contains a first cured product of a composition containing an acrylic pressure-sensitive adhesive and an isocyanate-based curing agent. The gel fraction at that time is 30% or more and 70% or less. Moreover, in the adhesion layer 240 after a heating, the 1st adhesion layer 241 contains the said 1st hardened | cured material. The gel fraction at that time is in the above range. In addition, in the adhesive layer 240 after heating, the second adhesive layer 242 contains the second cured product of the first cured product and the blocked isocyanate. The gel fraction at that time is preferably 80% or more.
The layer thickness of the adhesive layer 240 is preferably 10 μm or more and 50 μm or less, and more preferably 15 μm or more and 30 μm or less.

[Block isocyanate]
The pressure-sensitive adhesive composition contains a blocked isocyanate. The block isocyanate is added to transfer the transfer sheet 1 to the substrate 60 and then cause a crosslinking reaction by heating to reduce the fluidity of the second adhesive layer 242. The second adhesive layer 242 has a gel fraction of 80% or more due to a crosslinking reaction by heating, and the fluidity is lowered, but the adhesion to the substrate (transfer object) 60 is not lowered.

  The blocked isocyanate is obtained by protecting the active isocyanate group of the isocyanate compound with a blocking agent. Since the blocked isocyanate functions as a crosslinking agent, the above isocyanate compound has two or more isocyanate groups in one molecule. A block isocyanate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the isocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); alicyclic diisocyanates such as isophorone diisocyanate (IPDI); xylylene diisocyanate (XDI) Aromatic diisocyanates such as tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI); dimer acid diisocyanate (DDI), hydrogenated TDI (HTDI), hydrogenation Hydrogenated diisocyanates such as XDI (H6XDI) and hydrogenated MDI (H12MDI); dimers, trimers, and higher molecular weight polyisocyanates of these diisocyanate compounds Over preparative like; an adduct of trimethylol propane polyhydric alcohols or water, or a low molecular weight polyester resins.

  Specific examples of the blocking agent include, for example, oximes such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenols such as m-cresol and xylenol; methanol, ethanol, butanol, 2-ethylhexanol, cyclohexane Examples include alcohols such as hexanol and ethylene glycol monoethyl ether; lactams such as ε-caprolactam; diketones such as diethyl malonate and acetoacetate; mercaptans such as thiophenol. Other examples include ureas such as thiourea; imidazoles; carbamic acids and the like.

The blocked isocyanate can be obtained by reacting the above isocyanate compound and the blocking agent by a conventional method until free isocyanate groups disappear. Moreover, as a block isocyanate, a commercial item can also be used. Examples of commercially available products include trade name Duranate (manufactured by Asahi Kasei Co., Ltd.) and trade name K-16 curing agent (manufactured by Showa Ink Industries, Ltd.).
The content of the blocked isocyanate in the second adhesive layer 242 is set according to the gel fraction.

  The blocked isocyanate is preferably selected from the types having a crosslinking temperature of 110 ° C. or higher, more preferably 120 ° C. or higher. This is because the pressure-sensitive adhesive layer 240 is formed at a temperature of about 80 to 100 ° C., and therefore, when a blocked isocyanate having a crosslinking temperature of 100 ° C. or lower is selected, a crosslinking reaction proceeds at the stage of film formation. . When the crosslinking reaction proceeds at the stage of forming the second adhesive layer 242, the gel fraction of the second adhesive layer 242 becomes 80% or more before the transfer sheet 1 is transferred to the substrate 60. An appropriate adhesive force cannot be obtained when transferring to the material 60. Therefore, the transfer sheet 1 is selected by selecting as the blocked isocyanate from among the types having a crosslinking temperature of 110 ° C. or higher and blending so that the gel fraction of the second adhesive layer 242 is 30% or more and 70% or less. An appropriate adhesive force can be obtained when transferring to the substrate 60. Moreover, since a gel fraction can be 80% or more by a crosslinking reaction after heating, the fluidity | liquidity of the 2nd adhesion layer 242 can be reduced.

  Although the heating time of the base material 60 to which the transfer sheet 1 has been transferred varies depending on the crosslinking temperature of the blocked isocyanate, it is about 5 minutes to 30 minutes. For example, when the crosslinking temperature of the blocked isocyanate is 110 ° C., the heating time is about 15 minutes to 30 minutes. Even when a blocked isocyanate having a crosslinking temperature of 110 ° C. is added, the crosslinking reaction can be advanced more quickly by setting the heating temperature to 110 ° C. or higher, for example, 120 ° C.

<About generation | occurrence | production of the crack in the printing layer 30 of 3rd Embodiment, etc.>
The reason why after the transfer sheet 1 described above is transferred to the base material 60, a crack is generated in the planned crack region 30P of the print layer 30 by heating, and the reason why no crack is generated in the non-crack region 30N of the print layer 30 will be described.

  Before the transfer sheet 1 is transferred to the substrate 60, the stress generated by the fluidity of the adhesive layer 240 (the first adhesive layer 241 and the second adhesive layer 242) acts on the printing layer 30, but more than the printing layer 30. Expansion and contraction of the printing layer 30 is suppressed by the release film 50 and the base film 10 having rigidity. Therefore, the printed layer 30 can maintain its shape.

  On the other hand, when the transfer sheet 1 from which the release film 50 is released is transferred to the base material 60 and the adhesive layer 240 is attached to the hard base material 60, the stress generated by the fluidity of the adhesive layer 240 acts on the printing layer 30. However, expansion and contraction of the printing layer 30 is suppressed to some extent by the base film 10. After that, when the base film 10 is released from the transfer sheet 1, the planned crack region 30 </ b> P of the printing layer 30 cannot be maintained in shape due to the stress generated by the fluidity of the first adhesive layer (cracking joining layer) 241. . Therefore, the crack planned area 30P of the printed layer 30 is cracked and becomes a crack area 30C (see FIG. 1).

  The printing layer 30 may be formed in a state where tension is applied to the base film 10 side. Moreover, after forming the printing layer 30 in the base film 10, shrinkage | contraction etc. may generate | occur | produce by drying of a solvent. In this case, the printing layer 30 is internally stressed along the surface direction of the transfer sheet 1 (the direction in which cracks occur). Therefore, when the stress generated by the fluidity of the first adhesive layer 241 acts on the printed layer 30 (scheduled crack region 30P), the stress and the stress applied to the inside will interact with each other, and thus, Cracks are likely to occur.

  On the other hand, in the second adhesive layer 242 of the adhesive layer 240, block isocyanate is blended with the acrylic adhesive. According to this, after the transfer sheet 1 is transferred to the base material 60, the second adhesive layer (crack-inhibiting bonding layer) 242 has a gel fraction of 80% or more by being subjected to a crosslinking reaction by heating, and the fluidity is improved. Since it decreases, the stress caused by the fluidity is relaxed (reduced). As described above, since the fluidity of the second adhesive layer 242 is reduced by the cross-linking reaction, the stress caused by the fluidity hardly acts on the non-cracked region 30N of the printing layer 30, and thus the non-cracked region 30N maintains the shape. can do. Therefore, in the non-crack region 30N of the printed layer 30, the occurrence of cracks is suppressed as shown in FIG.

  Moreover, since the adhesiveness of the 2nd adhesion layer 242 and the base material 60 improves because the fluidity | liquidity of the 2nd adhesion layer 242 falls by a crosslinking reaction, the 2nd adhesion layer 242 floats from the base material 60. It can suppress more effectively. Further, the fluidity of the second adhesive layer 242 is reduced by the cross-linking reaction, so that the non-cracked region 30N caused by the difference in fluidity between the printed layer 30 and the second adhesive layer 242 caused by the temperature change in the use environment. Cracks can be suppressed in the long term.

  In order to further reduce the fluidity of the second adhesive layer 242, it is desirable to make the adhesive layer 240 thinner, but it is conceivable that the adhesiveness with the base material 60 is reduced. Therefore, by setting the thickness of the adhesive layer 240 in the range of 10 μm or more and 50 μm or less (more preferably 15 μm or more and 30 μm or less) as described above, the non-cracking of the printing layer 30 is performed without reducing the adhesiveness with the substrate 60. Generation of cracks in the region 30N can be suppressed.

  The manufacturing method of the decorative material 100 of 3rd Embodiment is substantially the same as the decorative material 100 of 1st Embodiment. The decorative material 100 of the third embodiment is different from the first embodiment in that the decorative material 100 is heated after releasing the base film 10 from the transfer sheet 1 transferred to the base material 60. When the decorative material 100 is heated, the blocked isocyanate blocking agent contained in the second adhesive layer 242 of the adhesive layer 240 is dissociated and the active isocyanate group is regenerated, so that the second adhesive layer 242 is subjected to a crosslinking reaction. Harden.

In the heating process, hot air may be blown on the decorative material 100, or the decorative material 100 may be installed in a heating furnace set to a predetermined temperature. Moreover, you may move a roller provided with the heat source over predetermined time, pressing the surface (peeling layer 20) of the decorative material 100. FIG.
Further, the heating to the decorative material 100 may be performed after the weather resistance imparting layer 70 is formed on the release layer 20. In that case, after releasing the base film 10 from the transfer sheet 1, it is necessary to form the weather resistance imparting layer 70 on the release layer 20 as soon as possible. Since the pressure-sensitive adhesive layer 240 before heating has fluidity as a whole, after the transfer sheet 1 is transferred to the base material 60, cracks are likely to occur in the non-cracked region 30N of the printed layer 30 due to stress caused by the fluidity. Because it becomes.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples of the above embodiments. However, the present invention is not limited to the following examples.

<First Embodiment>
[Example 1]
A 26 μm thick PET film (“Diafoil” manufactured by Mitsubishi Resin Co., Ltd.) is prepared as the base film 10, and an acrylic-urethane resin composition (“KSI” manufactured by Showa Ink Industries, Ltd.) is applied to one surface thereof. Thus, a release layer 20 having a film thickness (dry) of 1 μm was formed. On this release layer 20, printing is performed a plurality of times using a gravure ink ("EIS" manufactured by Showa Ink Industries, Ltd.) composed of an acrylic-vinyl chloride resin composition and a color pigment, and printing as shown in FIG. Layer 30 was formed.

Next, in the printed layer 30, a vinyl chloride resin (“FHS” manufactured by DIC Graphics Co., Ltd.) is applied on a plurality of regions to be non-cracked regions 30N, and a crack suppressing layer having a film thickness (dry) of 2 μm. (Hard coat layer 80 shown in FIG. 2) was formed.
In addition, as the release film 50, a 25 μm-thick PET separator (“Tokuro release film” manufactured by Toyo Cloth Co., Ltd.) is prepared, and an acrylic ester resin (“Nissetsu” manufactured by Nippon Carbide Industries Co., Ltd.) is formed thereon. The pressure-sensitive adhesive layer was coated so as to have a film thickness (dry) of 20 μm and dried to form a layer in which the pressure-sensitive adhesive layer 40 and the hard coat layer 80 were mixed as shown in FIG.
And after bonding together the exposed surface formed with the printed layer 30 (crack planned area 30P) and the hard coat layer 80 on the base film 10 side, and the adhesive layer 40 on the release film 50 (PET separator) side, The transfer sheet of Example 1 was obtained by heating and curing at 40 ° C. for 3 days.

[Comparative Example 1]
A transfer sheet of Comparative Example 1 was obtained under the same conditions as in Example 1 except that the hard coat layer 80 (crack suppression layer) was formed on the entire surface of the printing layer 30.
[Comparative Example 2]
A transfer sheet of Comparative Example 2 was obtained under the same conditions as in Example 1 except that the hard coat layer 80 was not formed in the region corresponding to the non-cracked region 30N of the printed layer 30.

  The three types of transfer sheets were each transferred onto an aluminum plate (base material) having a thickness of 1 mm to prepare a cosmetic material. After a predetermined time, the appearance of each cosmetic material was visually observed. As a result, in the decorative material of Comparative Example 1 in which the hard coat layer 80 was formed on the entire surface of the printing layer 30, no crack was observed in any of the printing layers 30 (the crack planned region 30P and the non-cracked region 30N). Further, the decorative material of Comparative Example 2 in which the hard coat layer 80 is not formed in the region corresponding to the non-cracked region 30N of the printed layer 30 has innumerable cracks in the printed layer 30 (the crack planned region 30P and the non-cracked region 30N). Was observed.

On the other hand, it was observed that the decorative material of Example 1 in which the hard coat layer 80 was formed only in the non-crack region 30N had innumerable cracks formed in the planned crack region 30P and became crack regions 30C. Further, no crack was observed in the non-crack region 30N.
From the above results, it was confirmed that the decorative material of Example 1 can reproduce more natural irregularities in the planned crack region 30P by cracks, and can prevent cracks from occurring in the non-cracked region 30N. .

Second Embodiment
[Example 2]
A 26 μm thick PET film (“Diafoil” manufactured by Mitsubishi Resin Co., Ltd.) is prepared as the base film 10, and an acrylic-urethane resin composition (“KSI” manufactured by Showa Ink Industries, Ltd.) is applied to one surface thereof. Thus, a release layer 20 having a film thickness (dry) of 1 μm was formed. Printing is performed a plurality of times on the release layer 20 using a gravure ink ("EIS" Showa Ink Industry Co., Ltd.) composed of an acrylic-vinyl chloride resin composition and a color pigment, and a printing layer 30 as shown in FIG. Formed. In the printed layer 30, a planned crack region 30P and a non-crack region 30N are formed in accordance with the design.

A 25 μm-thick PET separator (“Takuro Release Film” manufactured by Toyo Cloth Co., Ltd.) is prepared as the release film 50, and an acrylate ester is formed on the area corresponding to the planned crack area 30 </ b> P (see FIG. 5) 100 parts of the pressure-sensitive adhesive composition (“OC3949”, solid content 39.5%, made by Seiden Chemical Co., Ltd.) and 0.05 part of an isocyanate curing agent (“K-130”, solid content 80%, made by Seiden Chemical Co., Ltd.), ethyl acetate The first pressure-sensitive adhesive layer 141 was formed by coating the solution diluted in step 1 with a film thickness (dry) of 30 μm and drying.
In the release film 50, the region corresponding to the planned crack region 30 </ b> P of the print layer 30 is a planned crack region of the print layer 30 in the adhesive layer 140 when the release film 50 and the base film 10 are bonded together. This is a region overlapping with 30P in a plane.

  Further, in the same release film 50 (PET separator), on the region corresponding to the non-cracked region 30N (see FIG. 5) of the printed layer 30, the acrylic acid ester adhesive composition (“OC3949” solid content 39.5% 100 parts by Chemical Co., Ltd., 0.05 parts by weight isocyanate-based curing agent (“K-130” solid content 80%, made by Seiden Chemical Co., Ltd.), and adipate plasticizer (“DOA” solid content by 100%, JPLUS) A second adhesive layer 142 was formed by coating a solution obtained by diluting 0.5 part with ethyl acetate with a film thickness (dry) of 30 μm and drying.

In the release film 50, the region corresponding to the non-cracked region 30 </ b> N of the print layer 30 is the non-cracked region of the print layer 30 in the adhesive layer 140 when the release film 50 and the base film 10 are bonded together. This is a region overlapping with 30N in a plane.
And after bonding the printing layer 30 by the side of the base film 10 and the adhesion layer 140 by the side of the peeling film 50 (PET separator), the transfer sheet of Example 2 is obtained by curing at room temperature for 7 days. Obtained.

[Comparative Example 3]
A transfer sheet of Comparative Example 3 was obtained under the same conditions as in Example 2 above, except that the entire area of the adhesive layer 140 was formed of a cured product of an adhesive composition to which no plasticizer (adipate plasticizer) was added. It was.
[Comparative Example 4]
A transfer sheet of Comparative Example 4 was obtained under the same conditions as in Example 2 above, except that the entire area of the adhesive layer 140 was formed of a cured product of an adhesive composition to which a plasticizer (adipic acid ester plasticizer) was added. It was.

  The above three types of transfer sheets are each transferred onto a 1 mm thick aluminum plate (base material) to prepare a cosmetic material, and left in an atmosphere at room temperature of 20 ° C. to 25 ° C. After 21 days have passed, The appearance of the decorative material was visually observed. As a result, the decorative material of Comparative Example 3 in which the entire region of the adhesive layer 140 is formed of a cured product of the adhesive composition to which no plasticizer is added has cracks not only in the planned crack region 30P but also in the non-crack region 30N. Observed. Further, in the decorative material of Comparative Example 4 in which the entire region of the adhesive layer 140 is formed of a cured product of the adhesive composition to which a plasticizer is added, cracks are observed not only in the non-crack region 30N but also in the planned crack region 30P. Was not.

On the other hand, in the decorative material of Example 1, innumerable cracks were observed in the planned crack region 30P of the printing layer 30, and it was observed that the crack region 30C was formed. Further, no crack was observed in the non-crack region 30N.
From the above results, it was confirmed that the decorative material of Example 2 can reproduce more natural unevenness in the planned crack region 30P by cracks, and can prevent cracks from occurring in the non-crack region 30N. . This is because in the decorative material to which the transfer sheet of Example 2 was transferred, the fluidity of the second adhesive layer 142 was further enhanced by the plasticizer added to the second adhesive layer 142, so that the viscosity decreased. It is presumed that the stress caused by the above is relaxed and hardly acts on the non-cracked region 30N.

<Third Embodiment>
[Example 3]
A 26 μm thick PET film (“Diafoil” manufactured by Mitsubishi Resin Co., Ltd.) is prepared as the base film 10, and an acrylic-urethane resin composition (“KSI” manufactured by Showa Ink Industries, Ltd.) is applied to one surface thereof. Thus, a release layer 20 having a film thickness (dry) of 1 μm was formed. Printing is performed a plurality of times on the release layer 20 using a gravure ink ("EIS" Showa Ink Industry Co., Ltd.) composed of an acrylic-vinyl chloride resin composition and a color pigment, and a printing layer 30 as shown in FIG. Formed. In the printed layer 30, a planned crack region 30P and a non-crack region 30N are formed in accordance with the design.

A 25 μm-thick PET separator (“Takuro Release Film” manufactured by Toyo Cloth Co., Ltd.) is prepared as the release film 50, and an acrylate ester is formed on the area corresponding to the planned crack area 30 </ b> P (see FIG. 5) 100 parts of the pressure-sensitive adhesive composition (“OC3949”, solid content 39.5%, made by Seiden Chemical Co., Ltd.) and 0.05 part of an isocyanate curing agent (“K-130”, solid content 80%, made by Seiden Chemical Co., Ltd.), ethyl acetate The first pressure-sensitive adhesive layer 241 was formed by coating the solution diluted with 1 to a film thickness (dry) of 30 μm and drying.
In the release film 50, the region corresponding to the planned crack region 30 </ b> P of the print layer 30 is a crack planned region of the print layer 30 in the adhesive layer 240 when the release film 50 and the base film 10 are bonded together. This is a region overlapping with 30P in a plane.

  Moreover, in the same peeling film 50 (PET separator), the acrylic ester adhesive composition ("Nissetsu" manufactured by Nippon Carbide Industries Co., Ltd., containing 2 parts by mass of TDI as a curing agent with respect to 100 parts by mass of the acrylic ester adhesive) A pressure-sensitive adhesive layer in which blocked isocyanate (“K16 curing agent” manufactured by Showa Ink Co., Ltd.) is added to have a solid content of 2 parts by mass with respect to 100 parts by mass of the solid content so that the film thickness (dry) is 20 μm. The second adhesive layer 242 was formed by coating and drying.

In the release film 50, the region corresponding to the non-cracked region 30 </ b> N of the printed layer 30 is a non-cracked region of the printed layer 30 in the adhesive layer 240 when the release film 50 and the base film 10 are bonded together. This is a region overlapping with 30N in a plane.
And after bonding the printing layer 30 by the side of the base film 10 and the adhesion layer 240 by the side of the peeling film 50 (PET separator), it heat-curs at 40 degreeC for 3 days, The transfer sheet of an Example Got.

[Comparative Example 5]
A transfer sheet of Comparative Example 5 was produced under the same conditions as in Example 3 except that the entire region of the adhesive layer 240 was formed of a cured product of the same adhesive composition as that of the first adhesive layer 241 to which no blocked isocyanate was added.
[Comparative Example 6]
A transfer sheet of Comparative Example 6 was produced under the same conditions as in Example 3 except that the entire region of the adhesive layer 240 was formed of a cured product of the same adhesive composition as that of the second adhesive layer 242 to which blocked isocyanate was added.

  The three types of transfer sheets were each transferred onto a 1 mm thick aluminum plate (base material) to prepare a cosmetic material, and the cosmetic material was heated at 120 ° C. for 20 minutes. Then, after the lapse of a predetermined time, the appearance of each decorative material was visually observed. As a result, in Comparative Example 5 decorative material in which the entire region of the adhesive layer 240 was formed of a cured product of the adhesive composition to which no blocked isocyanate was added, cracks were observed not only in the planned crack region 30P but also in the non-cracked region 30N. It was done. Further, in the decorative material of Comparative Example 6 in which the entire region of the adhesive layer 240 was formed of the cured product of the adhesive composition to which blocked isocyanate was added, cracks were observed not only in the non-crack region 30N but also in the planned crack region 30P. Was not.

On the other hand, in the decorative material of Example 3, innumerable cracks were observed in the planned crack region 30P of the printed layer 30, and it was observed that the crack region 30C was formed. Further, no crack was observed in the non-crack region 30N.
From the above results, it was confirmed that the decorative material of Example 3 can reproduce more natural irregularities in the planned crack region 30P by cracks, and can prevent cracks from occurring in the non-crack region 30N. . This is because in the decorative material to which the transfer sheet of Example 3 was transferred, the blocked isocyanate added to the second adhesive layer 242 was cross-linked by heating at 120 ° C. for 20 minutes, resulting in a gel fraction of 80% or more. Since the fluidity of the second adhesive layer 242 has decreased, it is assumed that the stress caused by the fluidity hardly acts on the non-cracked region 30N corresponding to the second adhesive layer 242.

(Measurement of gel fraction)
The gel fraction of the adhesive layer was measured by the following method.
It was formed on the surface of the separator (release film) by coating so that the thickness of the pressure-sensitive adhesive layer after drying was 20 μm. Thereafter, a separator was similarly bonded to the other surface of the adhesive layer to obtain a test piece, which was stored at 40 ° C. for 3 days (can be stored at room temperature for 7 days). Here, the test piece that does not contain the blocked isocyanate in the adhesive layer is referred to as “Sample 1”, and the test piece that contains the blocked isocyanate in the adhesive layer is referred to as “Sample 2”.

The test piece was cut into a size of 50 cm ² and weighed (hereinafter, the pressure-sensitive adhesive weight of the cut-out test piece is also referred to as “the pressure-sensitive adhesive weight of the test piece”). This test piece was put in a sample bottle, immersed in 50 cc of ethyl acetate, and filtered through a SUS wire mesh of 200 mesh (200 mesh per inch) after 24 hours. The adhesive residue collected with a stainless steel (SUS) wire mesh was dried together with the SUS wire mesh at 80 ° C. for 2 hours, and the residue was weighed (hereinafter, the weight of the dried residue was referred to as “adhesive residue weight”). Also called).
Based on these values, the gel fraction was measured from the following formula.
Gel fraction [%] = (weight of adhesive residue) / (weight of adhesive of test piece) × 100
In addition, the weight of a separator, a sample bottle, and a SUS wire net is measured separately, and it subtracts from the said measured value.

(Measurement result)
For Sample 1 containing no blocked isocyanate, the gel fraction was 57.2%.
For Sample 2 containing blocked isocyanate, the gel fraction was 57.2%. And the gel fraction after heating the sample 2 at 120 degreeC for 1 hour was 94.1%. For sample 2, when the heating time was 4 hours, the gel fraction was 94.8%, and no significant difference was confirmed compared to the case where the heating time was 1 hour.
From the above, in sample 2 of the example, it can be understood that the gel fraction changes before and after heating (crosslinking step).

  The transfer sheet according to the present invention can give excellent design properties and weather resistance to the transfer target (base material). These decorative materials include building wall materials (exterior materials, interior materials), partitions, doors, window frames, furniture, interior decorations, etc., as well as indoor cover materials for automobiles, railway vehicles, ships, aircraft, etc. It can also be applied to panel materials for signs and outdoor advertisements.

DESCRIPTION OF SYMBOLS 1 Transfer sheet 10 Base film 20 Release layer 30 Print layer 30C Crack area 30P Planned crack area 30N Non-crack area 40,140,240 Adhesive layer 50 Release film 60 Base material 70 Weather resistance imparting layer 80 Hard coat layer 141,241 First 1 adhesive layer 241, 242 2nd adhesive layer

Claims (1)

A releasable support, a printing layer, and a bonding layer are laminated in this order,
The printed layer has a planned crack region and a non-crack region,
On the surface opposite to the releasable support in the planned crack region, a crack generation bonding layer is disposed as the bonding layer,
A transfer in which a crack suppressing bonding layer is disposed as the bonding layer or a crack suppressing layer is disposed between the non-cracked region and the surface opposite to the releasable support. Sheet.

Images