JP6794916B2 - Transfer sheet, manufacturing method of transfer sheet and manufacturing method of decorative molded product - Google Patents

Description

The present invention relates to a transfer sheet, a method for producing a transfer sheet, and a method for producing a decorative molded product.

In the fields of household appliances, automobile interiors, miscellaneous goods, etc., the surface of the article may be decorated by the transfer method.
In the transfer method, a transfer sheet having a transfer layer composed of a release layer, a design layer, an adhesive layer, etc. formed on a substrate is brought into close contact with an article to be transferred, and then the substrate is peeled off to be coated. This is a method of decorating by transferring only the transfer layer to the surface of the transfer material.

In the transfer method, by adjusting the composition of the transfer layer, it is possible to give a glossy feeling to the article to be transferred, or conversely, to reduce the glossy feeling and give a matte feeling.
For example, Patent Document 1 describes a release layer containing a matting agent entirely on a substrate sheet, a mask layer partially containing an active energy ray-curable resin, and a release layer and a design layer as transfer layers. A partially matte transfer sheet is disclosed, characterized in that the above is formed.

Japanese Patent No. 5095598

When the transfer layer is transferred to the surface of an article to be transferred, alignment is extremely important as described in paragraph 0034 of Patent Document 1.
Conventionally, in the printing field or the like, alignment is performed by printing a pattern for alignment called a register mark and reading the pattern with a sensor. Also in the transfer method, it is conceivable to print the alignment pattern in this way for alignment.

However, there is a problem that it is difficult to print the alignment pattern at an accurate position on the transfer sheet, and it is difficult to transfer the transfer layer to an accurate position of the object to be transferred. In addition, when printing a pattern for alignment, background stains may occur.

In order to solve the above problem, the present inventors have proposed in Japanese Patent Application No. 2016-168148 that the pattern for alignment is arranged on the release sheet. Then, as a result of further studies by the present inventors, in this configuration, a part of the alignment pattern is generated as foil dust during cutting and transfer of the transfer sheet on which the alignment pattern is printed. Foil dust may adhere to the transfer sheet, and when the transfer sheet is used to transfer to the surface of the article to be transferred, the appearance of the decorative molded product may be impaired, and there is room for improvement. It turned out that there was.

The present invention has been made in view of such circumstances, and a transfer sheet capable of transferring a transfer layer capable of suppressing the generation of foil dust and improving the appearance of a decorative molded product, a method for producing the transfer sheet, and the like. An object of the present invention is to provide a method for producing a decorative molded product using the transfer sheet.

That is, the present invention provides the following [1] to [3].
[1] A transfer sheet having a transfer layer on a release sheet, the release sheet having a first region for transferring to a transfer material and a second region for providing an alignment pattern. The second region has a convex portion on the surface side on the transfer layer side, and the transfer layer has a protruding portion based on the convex portion on the surface opposite to the surface on which the release sheet is provided. A transfer sheet having an alignment pattern portion having a color layer on the protruding portion.
[2] A step of applying a resin layer forming ink containing an ionizing radiation curable resin composition on a support to form an uncured resin layer, and a shape complementary to the first region and the second region. At the same time as shaping the uncured resin layer using the plate, the step of curing the shaped resin layer by irradiating it with ionizing radiation, and the ink for forming the release layer on the cured resin layer. To form a release layer, and to apply an ink for forming a protective layer containing an ionizing radiation curable resin composition onto the release layer to form a protective layer, and on the protective layer. In the step of applying the adhesive layer forming ink to the adhesive layer to form the adhesive layer, and applying the colored layer forming ink on the protruding portion formed at the position corresponding to the second region in the adhesive layer. The method for producing a transfer sheet according to [1], which comprises a step of forming a colored layer.
[3] A method for producing a decorative molded product, comprising a step of transferring the transfer layer of the transfer sheet according to [1] to an object to be transferred and a step of peeling off the release sheet of the transfer sheet.

According to the present invention, a transfer sheet capable of transferring a transfer layer capable of suppressing the generation of foil dust and improving the appearance of a decorative molded product, a method for producing the transfer sheet, and a decorative molded product using the transfer sheet. Manufacturing method can be provided.

It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is a top view which shows one Embodiment of the transfer sheet of this invention. It is a top view which shows one Embodiment of the alignment pattern of this invention. It is a photograph which observed the colored layer formed by melt heat transfer with a microscope from a plane direction. It is a photograph of the colored layer formed by gravure reverse printing observed from a plane direction with a microscope.

Embodiments of the present invention will be described below with reference to the drawings. However, the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness of each layer, etc. are different from the actual ones. Therefore, the specific thickness and dimensions should be determined in light of the following explanations. In addition, it goes without saying that the drawings include parts having different dimensional relationships and ratios from each other.

[Transfer sheet]
As shown in FIG. 1, the transfer sheet 100 according to the embodiment of the present invention is a transfer sheet having a transfer layer 20 on the release sheet 10, and the release sheet 10 is to be transferred to a transfer material. a second region R ₂ for providing the first region R ₁ and the alignment pattern of the second region R ₂ have the convex portion 4 on the side of the transfer layer 20 side, the transfer layer 20 , A positioning pattern portion AL having a protruding portion 23 based on the convex portion 4 is provided on the surface opposite to the surface on which the release sheet 10 is provided, and the colored layer 30 is provided on the protruding portion 23. ..

<Release sheet>
The release sheet 10 includes a support 1, a resin layer 2, and a release layer 3. The release sheet 10 is peeled off after the transfer layer 20 is transferred to an object to be transferred such as a resin molded body.

(Support)
Examples of the support 1 include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymers, vinyl resins such as ethylene / vinyl alcohol copolymers, polyethylene terephthalates, and the like. Represented by polyester resins such as polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as methyl poly (meth) acrylate and ethyl poly (meth) acrylate, styrene resins such as polystyrene, nylon 6 or nylon 66 and the like. Examples thereof include a plastic film made of a resin such as a polyamide resin.
Among these plastic films, a biaxially stretched polyester film having excellent heat resistance, dimensional stability, and alignment suitability is preferable.

The thickness of the support 1 is preferably 12 to 150 μm, more preferably 25 to 100 μm, from the viewpoint of moldability, shape followability, and handling.
In the present specification, the numerical values relating to the height, roughness, width and thickness shall be the average value of the values measured 10 times unless otherwise specified.

The surface of the support 1 may be subjected to physical treatment such as corona discharge treatment and oxidation treatment, or a coating material called an anchor agent or a primer may be applied in advance in order to enhance the adhesiveness with the resin layer 2 and the like. ..

(Resin layer)
The resin layer 2 is preferably formed of a resin component containing a solid content such as a thermoplastic resin, a cured product of a thermosetting resin composition, and a cured product of an ionizing radiation curable resin composition. The resin component used for forming the resin layer 2 preferably has a solid content of 20 to 100% by mass, more preferably 25 to 95% by mass, and even more preferably 30 to 90% by mass.
Among the above resin components, a cured product of an ionizing radiation curable resin composition which is excellent in strength and can impart an accurate and precise shape because it cures instantly is preferable. Further, from the viewpoint of facilitating the effect of the ionizing radiation curable resin composition, it is preferable that the cured product of the ionizing radiation curable resin composition is contained in an amount of 70% by mass or more among all the resin components constituting the resin layer 2. It is more preferably contained in an amount of 90% by mass or more, further preferably contained in an amount of 95% by mass or more, and further preferably contained in an amount of 100% by mass or more.

The resin layer 2 may be formed by coating, but from the viewpoint of forming an accurate and precise shape, the resin layer 2 is printed by printing using a plate having a shape complementary to the first region R ₁ and the second region R _2. It is preferable to form. When the resin layer 2 has other regions, the plate preferably has a shape complementary to the other regions. Details of the method for forming the resin layer 2 using the plate will be described later.

Examples of the thermoplastic resin include acrylic resin, cellulose resin, urethane resin, vinyl chloride resin, polyester resin, polyolefin resin, polycarbonate, nylon, polystyrene and ABS resin.
The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group and an allyl group, and an epoxy group and an oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable. Further, from the viewpoint of suppressing damage to the resin layer in the process of producing the transfer sheet, as the ionizing radiation curable resin, a compound having two or more ethylenically unsaturated bond groups is more preferable, and among them, ethylenically unsaturated. A polyfunctional (meth) acrylate compound having two or more saturated bond groups is more preferable. As the polyfunctional (meth) acrylate compound, either a monomer or an oligomer can be used.
In addition, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays can also be used.

Among the polyfunctional (meth) acrylate-based compounds, the bifunctional (meth) acrylate-based monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexane. Examples thereof include diol diacrylate.
Examples of the trifunctional or higher functional (meth) acrylate-based monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and di. Examples thereof include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
Further, the (meth) acrylate-based monomer may have a part of the molecular skeleton modified, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol and the like. Can also be used.

Examples of the polyfunctional (meth) acrylate-based oligomer include acrylate-based polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained, for example, by reacting a polyhydric alcohol or organic diisocyanate with a hydroxy (meth) acrylate.
Further, the preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting a (meth) acrylic acid with a trifunctional or higher functional aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin or the like, and a bifunctional epoxy resin. (Meta) acrylate obtained by reacting the above aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with polybasic acid and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resin, It is a (meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with phenols and (meth) acrylic acid.
The ionizing radiation curable resin may be used alone or in combination of two or more.

When the ionizing radiation curable resin is an ultraviolet curable resin, the resin layer forming ink preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones and the like.
Further, the photopolymerization accelerator can reduce the polymerization inhibition by air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.

The thickness of the resin layer 2 is not particularly limited, but is preferably 1 to 15 μm, more preferably 2 to 12 μm, and even more preferably 3 to 10 μm.

(Release layer)
The release sheet 10 of the transfer sheet 100 is formed so as to be peelable at the interface with the transfer layer 20 when it is in close contact with the object to be transferred. In order to improve the releasability, it is preferable that the releasing sheet 10 has the releasing layer 3 on at least a part of the surface on the side in contact with the transfer layer 20. Further, from the viewpoint of making the in-plane releasability of the transfer sheet 100 uniform, as shown in FIG. 1, the release sheet 10 has the release layer 3 on the entire surface of the surface in contact with the transfer layer 20. Is preferable.

If having a concave-convex portion 5 in the first region R _1, by release layer 3 on the uneven portion 5 is formed, unevenness is reduced, forming a less irregular shape of the high frequency component to the surface of the decorative molded article It is possible to suppress whitening and glare of the decorative molded product.
Here, the "glare" refers to a phenomenon in which minute variations in brightness can be seen in the image light due to the uneven structure of the surface. That is, by forming the release layer 3 on the uneven portion 5, glare can be suppressed when the decorative molded product is used on the front surface of a display element such as a liquid crystal display element.

The release layer 3 is preferably composed mainly of resin.
The resin of the release layer 3 is not particularly limited as long as it is a material having a predetermined film strength and a low adhesive force with the transfer layer 20, and is a general-purpose thermoplastic resin, a cured product of a thermosetting resin composition, and the like. Examples thereof include a cured product of an ionizing radiation curable resin composition. Specifically, fluororesins, silicone resins, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, nitrified cotton. And so on.
Among these, a cured product of the thermosetting resin composition is preferable, and a thermosetting resin composition which is a polyurethane-based resin containing an acrylic polyol and an isocyanate is more preferable.

The release layer 3 may further contain a release agent in order to improve the release property. Examples of the release agent include waxes such as synthetic wax and natural wax. As the synthetic wax, a polyolefin wax such as polyethylene wax or polypyrene wax is preferable.

The thickness of the release layer 3 is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and even more preferably 0.3 to 1.0 μm.

(Other layers)
The release sheet 10 may have other layers.
Examples of the other layer include an antistatic layer. By having the antistatic layer, the release sheet 10 can suppress the release charge when the release sheet is peeled off, and can improve the workability of transfer.

(Antistatic layer)
The antistatic layer preferably contains an antistatic agent such as an electron conduction type antistatic agent and an ion conduction type antistatic agent, and a binder resin.
The antistatic layer is preferably formed on the surface of the release sheet opposite to the surface in contact with the transfer layer.
The surface resistivity of the antistatic layer is preferably adjusted to the range of 1.0 × 10 ^-9 Ω / □ to 1.0 × 10 ^-12 Ω / □.
In addition, an antistatic agent may be contained in another layer such as a resin layer to exhibit antistatic properties.

(1st area)
The first region R ₁ of the release sheet 10 is a region for providing the transfer layer 20 to be transferred to the transfer target.
The surface shape of the first region R ₁ is not particularly limited. As shown in FIG. 1, for example, the surface shape of the first region R ₁ may have an uneven shape or may be substantially smooth.
As shown in FIG. 1, if having an uneven portion 5 in the first region R _1, the object to be transferred, the transfer layer 20 (uneven portion 5 release layer on 3 having a complementary shape of the uneven portion 5 The transfer layer 20) having a complementary shape of the uneven shape relaxed by the release layer 3 is transferred, and the uneven shape can be imparted to the surface of the obtained decorative molded product.
Further, when the surface shape of the first region R ₁ is substantially smooth, increasing the substantially can be made smooth, gloss resulting decorative molded article surface shape of the transfer layer 20 has been transferred to the transfer target Can be done.

Since the surface shape given to the decorative molded product differs depending on the purpose, the absolute value of the degree of unevenness in the first region R ₁ is not particularly limited, but the maximum height roughness Rz is 0.2 to 4.0 μm. It is preferable to set the degree. Similarly, the arithmetic mean roughness Ra is preferably about 0.05 to 2.0 μm.
In the present specification, the maximum height means the maximum height roughness Rz of JISB0601: 2001 at a cutoff value of 0.8 mm, and the average roughness is the arithmetic of JISB0601: 2001 at a cutoff value of 0.8 mm. It means the average roughness Ra. In the present specification, the values relating to height and roughness shall be the average value of the values measured at 10 points unless otherwise specified.

Although not shown, it may be formed by dividing the first region R ₁ to two or more locations. In that case, it may be each of the first region R ₁ of the surface shape as different. By forming the first region R ₁ by dividing it into two or more locations and making the surface shape of each first region R ₁ different, the design of the decorative molded product can be enhanced.

(Second area)
The second region R ₂ of the release sheet 10 is a region for providing the alignment pattern used for transferring the transfer target (alignment marks).
The second region R ₂ has a partially arranged convex portion 4 that is the basis of the alignment pattern. From the viewpoint of forming an accurate and precise shape, the convex portion 4 is preferably formed on the resin layer 2 by printing using a plate having a shape complementary to the second region R ₂ .

The convex portion 4 is preferably formed of a line-shaped structure extending in an arbitrary direction. The arbitrary direction is not particularly limited and may be an oblique direction (for example, 45 degrees with respect to the width direction of the transfer sheet), but is preferably a direction parallel to any one side of the transfer sheet 100. , The flow direction of the transfer sheet 100 is more preferable. By forming the convex portion 4 in this configuration, alignment can be facilitated.
Further, it is preferable that the directions of the plurality of convex portions 4 are parallel to each other.
Further, the convex portion 4 may be formed continuously without interruption in any direction in the second inner region R _2, but may be one that extends in any direction partially interrupted.

The height h of the convex portion 4 is preferably 1.0 to 10.0 μm, more preferably 1.5 to 9.0 μm, and even more preferably 2.0 to 8.0 μm.
By setting the height h of the convex portion 4 to 3.0 μm or more, it is possible to easily form the protruding portion 23 based on the convex portion 4 on the surface of the transfer layer 20. Further, by setting the height h of the convex portion 4 to 10 μm or less, the convex portion 4 is less likely to be deformed by a load, and the accuracy of alignment can be easily maintained.
The height h of the convex portion 4 does not have to be the same. However, from the viewpoint of uniformly forming the height H of the protruding portion 23 and facilitating the uniform formation of the colored layer 30, the height h of the convex portion 4 is formed.
Are all the same.
In the present specification, the height h of the convex portion 4 means the height of the central portion of the cross section obtained by cutting the structure forming the convex portion 4 in the direction orthogonal to the extending direction of the structure. ..

The distance between the ends of the convex portions 4 is preferably 0.05 to 2.0 mm, more preferably 0.075 to 1.0 mm, and further preferably 0.10 to 0.7 mm. preferable.
By setting the distance between the ends of the convex portions 4 to 0.01 mm or more, the recognition rate of the alignment mark can be improved.
Further, by setting the distance between the ends of the convex portions 4 to 2.0 mm or less, it is possible to prevent the area of the second region R _{2 from} becoming wider than necessary.

The width of the convex portion 4 is preferably 0.01 to 2.0 mm, more preferably 0.025 to 1.0 mm, and even more preferably 0.05 to 0.5 mm. By setting the width of the convex portion 4 to 0.05 mm or more, the strength of the convex portion 4 can be maintained and the convex portion 4 can be easily formed uniformly. Further, by setting the width of the convex portion 4 to 3.0 mm or less, it is possible to prevent the area of the second region R _{2 from} becoming wider than necessary.

The cross section of the structure forming the convex portion 4 cut in a direction orthogonal to the stretching direction of the structure is preferably substantially square.

The convex portion 4 and the transfer layer 20 described later preferably satisfy the relationship of [height of the convex portion / thickness of the transfer layer] of 0.1 to 5.0, preferably 0.1 to 3.5. It is more preferable to satisfy the relationship, and it is further preferable to satisfy the relationship of 0.1 to 1.0.
By setting the above ratio to 0.1 or more, it is possible to easily form the protruding portion 23 based on the convex portion 4 on the surface of the transfer layer 20. Further, by setting the ratio to 5.0 or less, the convex portion 4 is less likely to be deformed by the load, and the alignment accuracy can be easily maintained.

Transfer sheet 100 of the present embodiment may have a second region R ₂ of two or more. When there are two or more second regions R ₂ , it is preferable to change the role of each region. For example, when a plurality of second regions R ₂ are provided, it is preferable that one of them is aligned in the width direction and the other is aligned in the flow direction. By configuring the second region R ₂ as described above, the alignment in both the width direction and the flow direction becomes possible, and the accuracy of the alignment can be improved.

It is preferable that the second region R ₂ is transferred to the object to be transferred and removed when the decorative molded product is obtained. The timing for removing the second region R ₂ is, for example, (1) a step of slitting the transfer sheet 100 into a long length, (2) a step of die-cutting the transfer sheet 100 into a single sheet, and (3) a transfer sheet. Examples thereof include a trimming step after transferring 100 to a transfer material. The transfer layer 20 from the viewpoint of transferring the exact position of the object to be transferred, it is preferable to remove the second region R ₂ at the timing of (3).

<Transfer layer>
A transfer layer 20 is formed on at least a part of the release sheet 10.
The transfer layer 20 is a layer that is transferred to the object to be transferred. For example, as shown in FIG. 1, the transfer layer 20 has a protective layer 21 and an adhesive layer 22 in order from the side closer to the release sheet 10. The transfer layer 20 has a protruding portion 23 on the surface based on the convex portion 4.
As shown in FIG. 1, the transfer layer 20 is preferably formed on the entire surface of the release sheet 10.

For each layer such as the protective layer 21 and the adhesive layer 22 constituting the transfer layer 20, for example, an ink containing the constituent components of each layer is adjusted, and a coating method such as a gravure coating method or a roll coating method is applied on the release sheet 10. , It can be formed by applying and drying by a printing method such as a gravure printing method or a screen printing method, and curing by irradiating ionizing radiation as necessary.
The ink for forming the transfer layer for forming the transfer layer 20 has a solvent ratio of 90% by mass or less from the viewpoint of facilitating the formation of the protruding portion 23 that follows the convex portion 4 as a base. preferable.

The height H of the protrusion 23 is preferably 1.0 to 10.0 μm, more preferably 1.5 to 9.0 μm, and even more preferably 2.0 to 8.0 μm.
By setting the height H of the protruding portion 23 to 1.0 μm or more, it is possible to easily provide the colored layer 30 by selecting the vicinity of the top of the protruding portion 23. Further, by setting the height H of the protruding portion 23 to 10.0 μm or less, the protruding portion 23 is less likely to be deformed by a load, and the accuracy of alignment can be easily maintained.
The heights H of the protrusions 23 do not have to be the same. However, from the viewpoint of facilitating the uniform formation of the colored layer 30, it is preferable that the heights H of the protruding portions 23 are all the same.
In the present specification, the height H of the protruding portion 23 means the height of the central portion of the cross section obtained by cutting the structure forming the protruding portion 23 in the direction orthogonal to the extending direction of the structure. ..

The distance W between the ends of the protruding portions 23 is preferably 0.05 to 3.0 mm, more preferably 0.07 to 2.0 mm, and preferably 0.1 to 1.0 mm. More preferred. If the distance W between the ends of the protruding portions 23 is too narrow, the colored layers 30 may stick to each other, which may adversely affect the alignment.
By setting the distance W between the ends of the protruding portions 23 to 0.05 mm or more, it is possible to prevent the adjacent colored layers 30 from sticking to each other when the colored layers 30 are formed. Further, by setting the distance W between the ends of the protruding portions 23 to 3.0 mm or less, it is possible to prevent the area of the alignment pattern portion AL from becoming wider than necessary.
In the present specification, the distance W between the ends of the protruding portions 23 means the distance between the ends of the hem of the protruding portion 23, and in the present embodiment, the flatness that is the end of the hem of the adjacent protruding portions 23. The distance in the adhesive layer 22.

(Protective layer)
The protective layer 21 has a role of protecting the decorative molded product from abrasion, light, chemicals, and the like after the transfer layer 20 is transferred from the transfer sheet 100 to the object to be transferred.
If having a concave-convex portion 5 release sheets first region R ₁ of 10, protective layer 21 having a complementary shape to the irregular shape is imparted to the surface of the decorative molded article. Further, when the first region R ₁ of the release sheet 10 is substantially smooth, it can be surface substantially smooth protective layer 21 is applied to the surface of the decorative molded article, increasing the gloss of the decorative molded article.

The protective layer 21 preferably contains a resin component such as a thermoplastic resin, a cured product of a thermosetting resin composition, or a cured product of an ionizing radiation curable resin composition as a main component. The main component means 50% by mass or more of the total solid content constituting the protective layer, and the ratio is preferably 70% by mass or more, and more preferably 80% by mass or more.
Further, among the above resin components, a cured product of an ionizing radiation curable resin composition having excellent strength is preferable. Further, from the viewpoint of improving the effect of the ionizing radiation curable resin composition, it is preferable to contain 70% by mass or more of the cured product of the ionizing radiation curable resin composition among all the resin components constituting the protective layer, 90%. It is more preferably contained in an amount of 95% by mass or more, further preferably contained in an amount of 95% by mass or more, and further preferably contained in an amount of 100% by mass or more.
The transfer layer forming ink for forming the protective layer 21 preferably has a solvent ratio of 60 to 90% by mass or less from the viewpoint of facilitating the formation of the protruding portion 23 that follows the convex portion 4 as a base. It is more preferably ~ 90% by mass, and even more preferably 70 to 90% by mass.

The embodiment of the resin component such as the ionizing radiation curable resin composition of the protective layer 21 is the same as the embodiment of the resin component of the resin layer 2 described above.
When a thermosetting resin composition and / or an ionizing radiation curable resin composition is used as the material for forming the protective layer 21, the thermosetting resin is formed at the time of forming the protective layer 21 from the viewpoint of moldability. The composition and / or the ionizing radiation curable resin composition is left in a semi-cured state, and after being transferred to the transferred material, the thermosetting resin composition and / or the ionizing radiation curable resin composition is cured. It is preferable to completely cure.

The protective layer 21 may contain particles such as organic particles and inorganic particles. By containing the particles in the protective layer 21, glare and defects can be made less noticeable due to the expression of internal haze due to the difference in refractive index from the resin component. These particles may be contained in an adhesive layer, an anchor layer, etc., which will be described later, for the same purpose.

Examples of the organic particles include particles composed of polymethylmethacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, polyester resin and the like. Can be mentioned.
Examples of the inorganic particles include particles made of silica, alumina, antimony, zirconia, titania and the like.

The average particle size of the particles is preferably 0.05 to 5.0 μm, more preferably 0.5 to 3.0 μm.
In the present specification, the average particle size is 50% particle size (d50: median size) when the particles in a solution are measured by a dynamic light scattering method and the particle size distribution is expressed by a mass cumulative distribution. The 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

The content of the particles is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the protective layer 21.

The thickness of the protective layer 21 is preferably 0.5 to 30 μm, more preferably 1.0 to 20 μm, and more preferably 2.0 to 10 μm from the viewpoint of the balance between surface hardness and moldability. Is even more preferable.

(Adhesive layer)
The adhesive layer 22 has a role of improving the adhesiveness between the object to be transferred such as a resin molded product and the transfer layer 20 and improving the transfer work.

The surface of the transfer layer 20 is provided with a positioning pattern portion AL having a protruding portion 23 based on the convex portion 4. When the surface of the transfer layer 20 is composed of the adhesive layer 22, the surface of the adhesive layer 22 is provided with a positioning pattern portion AL having a protruding portion 23 based on the convex portion 4. The protruding portion 23 is formed following the convex portion 4 by providing a transfer layer 20 composed of a protective layer 21 and an adhesive layer 22 on the convex portion 4 provided on the release sheet 10. It is a part.

For the adhesive layer 22, it is preferable to use a heat-sensitive or pressure-sensitive resin suitable for the material of the transferred material. For example, when the material of the object to be transferred is an acrylic resin, it is preferable to use an acrylic resin. When the material of the object to be transferred is a polyphenylene oxide polystyrene resin, a polycarbonate resin, or a styrene resin, an acrylic resin, polystyrene resin, polyamide resin, or the like having an affinity for these resins should be used. Is preferable. Further, when the material of the transferred material is polypropylene resin, it is preferable to use chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and kumaron inden resin.
Additives such as an ultraviolet absorber and an infrared absorber may be blended in the adhesive layer 22. The ultraviolet absorber may be inorganic or organic, but an organic ultraviolet absorber is preferable from the viewpoint of excellent transparency. Examples of the inorganic ultraviolet absorber include titanium dioxide, cerium oxide, zinc oxide and the like. Examples of organic UV absorbers include benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, benzoate-based UV absorbers, cyanoacrylate-based UV absorbers, and hydroxy. Examples thereof include phenyltriazine-based ultraviolet absorbers and nickel-chelate-based ultraviolet absorbers. Examples of the infrared absorber include titanium oxide, zinc oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide, antimony-doped tin oxide (ATO), zinc sulfide metal oxide-based infrared absorber, and the like.
The adhesive layer forming ink for forming the adhesive layer 22 preferably has a solvent ratio of 80 to 90% or less from the viewpoint of facilitating the formation of the protruding portion 23 that follows the convex portion 4 as a base. More preferably, it is 85 to 90% by mass.

The thickness of the adhesive layer 22 is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and even more preferably 1.0 to 10 μm.
The adhesive layer 22 may be configured to include two types of layers, an anchor coat layer and an adhesive layer. When the anchor coat layer and the adhesive layer are included, the thickness of the anchor coat layer is preferably 0.5 to 10 μm, more preferably 1.0 to 8.0 μm, and 2.0 to 6. It is more preferably 0 μm. The thickness of the adhesive layer is preferably 0.1 to 10 μm, more preferably 0.5 to 8.0 μm, and even more preferably 1.0 to 5.0 μm.

(Colored layer)
The colored layer 30 is provided on the protruding portion 23 of the alignment pattern portion AL provided on the surface of the transfer layer 20. The colored layer 30 has a role of producing a contrast of light transmittance or light reflectance between a portion where the colored layer 30 is present and a portion where the colored layer 30 is not present in the alignment pattern portion AL.
The colored layer 30 is arranged so as to be located at least a part of the alignment pattern portion AL of the transfer layer 20 (adhesive layer 22) as shown in FIG. 2 when the transfer sheet 100 is observed from the plane direction. It is preferable to do so.

As shown in FIG. 3, the colored layer 30 is preferably composed of three parts: a line portion 30a, a solid coating center portion 30b, and a solid coating portion 31.
The light transmittance or light reflectance is different between the line portion 30a and the solid coating center portion 30b, and the transfer sheet 100 can be aligned in an arbitrary step by utilizing the contrast of the light transmittance or light reflectance. It becomes. As the light transmittance, any of the transmittance in the normal transmittance direction, the diffusion transmittance, and the total transmittance may be used. Similarly, as the light reflectance, any of the transmittance in the specular reflection direction, the diffuse reflectance, and the total reflectance may be used.
The ratio of the area of the line portion 30a in the colored layer 30 in the second region _{R 2} is preferably 15 to 85%, more preferably from 20% to 80%, more preferably from 30% to 70% .. By setting the ratio of the area of the line portion 30a to the above range, it is possible to easily clarify the contrast of the light transmittance or the light reflectance between the solid coating center portion 30b and the solid coating portion 31, and to improve the alignment accuracy. Can be done.
Except the second region _{R 2} of the line portion 30a and the solid fill central portion 30b, it is preferable that the solid color portion 31. Areafill portion 31 may be wider than the second region R ₂ of the line portion 30a is wide is preferably easier to see more alignment pattern portion AL in different width.

The colored layer 30 preferably has a line-like pattern having an average value of line width L of 0.01 to 4.0 mm from the viewpoint of ease of alignment when the transfer sheet 100 is observed from a plane direction. From the above viewpoint, the average value of the line width L of the colored layer 30 is more preferably 0.01 to 2.0 mm, further preferably 0.025 to 1.0 mm, and 0.05 to 0. It is even more preferably 5 mm. In this specification, the average value of the line width L means the average value of the line width of the colored layer 30 measured at 10 or more points.
From the above viewpoint, the variation of the line width L of the colored layer 30 is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less. Here, the fluctuation of the line width L within 10% means that all the line widths are within ± 10% with respect to the average value of the line width L. It is considered that the cause of the fluctuation of the line width L is the change in the shape of the protruding portion 23 caused by forming the protective layer, the adhesive layer and the like.

The thickness of the colored layer 30 is preferably 0.3 to 5.0 μm, more preferably 0.4 to 4.0 μm, and more preferably 0.4 to 4.0 μm, from the viewpoint of easily obtaining contrast for alignment. It is more preferably 5 to 3.0 μm.

The colored layer 30 is composed of, for example, a binder resin and a pigment.
The pigment of the colored layer 30 preferably contains a pigment having a high hiding property. As the pigment having high hiding power, a black pigment such as carbon black is preferable.
The binder resin of the colored layer 30 is not particularly limited, and for example, (meth) acrylic resin, polyurethane resin, polyester resin, polyamide resin, (meth) acrylic acid ester-olefin copolymer resin, vinyl chloride acetate resin, ethylene. Thermoplastic resins such as vinyl acetate copolymer resin (EVA resin), ionomer resin, olefin-α olefin copolymer resin fat; polyurethane resin, polyester resin, acrylic resin, epoxy resin, phenol resin, urea resin, polyester resin , Melamine resin, alkyd resin, polyimide resin, silicone resin, curable resin such as amide functional copolymer, and the like. Here, the curable resin includes a thermosetting resin, an ionizing radiation curable resin, a two-component curable resin, and the like. The binder resin of the colored layer 30 is preferably a thermoplastic resin from the viewpoint of suppressing foil dust.
The colored layer 30 preferably does not contain a curing agent from the viewpoint of suppressing blocking.

The colored layer 30 can be formed by transferring the colored layer forming ink onto the protruding portion 23 of the alignment pattern portion AL by, for example, a transfer method such as melt heat transfer or sublimation heat transfer. As a transfer method for forming the colored layer 30, melt thermal transfer is particularly preferable from the viewpoint of suppressing foil dust.
The colored layer 30 can also be formed by applying a colored layer forming ink on the protruding portion 23 of the alignment pattern portion AL by a printing method such as gravure reverse printing or gravure printing, and then drying the colored layer 30. it can. Gravure reverse printing is particularly preferable as a printing method for forming the colored layer 30.
FIG. 4 shows a photograph of the colored layer 30 formed by melt heat transfer observed from a plane direction with a microscope. FIG. 5 shows a photograph of the colored layer 30 formed by gravure reverse printing observed from a plane direction with a microscope. Comparing the photographs of FIGS. 4 and 5, the colored layer 30 formed by the melt heat transfer of FIG. 4 is clearer and more suitable. The colored layer 30 formed by the gravure reverse printing of FIG. 5 had some background stains, but the sharpness for alignment was maintained.

The thickness of the colored layer 30 is preferably 0.3 to 5.0 μm, preferably 0.4 to 4.0 μm, from the viewpoint that the thickness may be adjusted within a range in which contrast for alignment can be obtained. Is more preferable, and 0.5 to 3.0 μm is even more preferable.

(Other layers)
The transfer layer 20 may have other layers.
Examples of other layers include an anchor layer and a printing layer.

(Anchor layer)
The anchor layer is a layer provided as needed to improve heat resistance when placed in a high temperature environment such as in-mold molding. The anchor layer is preferably formed between the protective layer 21 and the adhesive layer 22.

The anchor layer preferably contains a cured product of the curable resin composition.
Examples of the curable resin composition include a thermosetting resin composition and an ionizing radiation curable resin composition.
The embodiment of the thermosetting resin composition and the ionizing radiation curable resin composition of the anchor layer is the same as the embodiment of the thermosetting resin composition and the ionizing radiation curable resin composition of the resin layer.
The thickness of the anchor layer is preferably 0.1 to 6 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 4 μm.
The anchor layer forming ink for forming the anchor layer preferably has a solvent ratio of 70 to 90% by mass or less, preferably 75 to 90% by mass, from the viewpoint of facilitating the formation of the protruding portion 23 that follows the convex portion 4 as a base. It is more preferably 90% by mass, and even more preferably 80 to 90% by mass.

(Print layer)
The transfer layer 20 may further have a print layer. The printed layer has a role of imparting a desired design property to the decorative molded product.

Printed layer, when observed the transfer sheet 100 from the planar direction, is preferably disposed so as to be positioned on at least a portion of the first region R _1.
Further, the position of the print layer in the thickness direction may be arranged on the adhesive layer 22, may be arranged between the adhesive layer 22 and the protective layer 21, and may be released from the protective layer 21. It may be arranged between the sheet 10 and the sheet 10. From the viewpoint of protection of the print layer and adhesion to the transferred material, it is preferable to arrange the print layer between the adhesive layer 22 and the protective layer 21. Further, from the viewpoint of dealing with small lot products, it is preferable to arrange the printing layer on the adhesive layer 22. When the printing layer is arranged on the adhesive layer 22, the resin component of the printing layer is a resin of the same type as the resin component of the adhesive layer 22 from the viewpoint of making the adhesiveness with the transferred material uniform. It is preferable, and it is more preferable to use the same resin.

The pattern of the printing layer is arbitrary, and examples thereof include wood grain, stone grain, cloth grain, sand grain, circle, quadrangle, polygon, geometric pattern, character, and solid printing.

The printing layer preferably contains a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, and a cellulosic resin, and a pigment and / or a dye.
The thickness of the print layer is preferably 0.25 to 20 μm, more preferably 0.5 to 15 μm, and even more preferably 0.7 to 10 μm from the viewpoint of designability.

Alignment is important when forming the print layer, but the print layer can be formed at an accurate position by performing alignment using the alignment pattern portion AL.

[Manufacturing method of transfer sheet]
The method for producing the transfer sheet 100 according to the embodiment of the present invention is a step of applying an ink for forming a resin layer containing an ionizing radiation curable resin composition onto a support 1 to form an uncured resin layer 2. The uncured resin layer 2 is shaped by using a plate having a shape complementary to the first region R ₁ and the second region R ₂ , and at the same time, the shaped resin layer 2 is irradiated with ionizing radiation. A step of applying a release layer forming ink on the cured resin layer 2 and a step of forming a release layer 3 and a step of applying a protective layer forming ink on the release layer 3 a step of forming a protective layer 21 on the protective layer 21, an adhesive layer forming ink was applied, forming an adhesive layer 22, the position corresponding to the second region R ₂ in the adhesive layer 22 Includes a step of applying a colored layer forming ink on the protruding portion 23 formed in the above to form the colored layer 30.

A plate having a shape complementary to the first region R ₁ and the second region R ₂ is to engrave the surface of the cylinder in a desired shape by, for example, etching, sandblasting, cutting and laser processing, or a combination thereof. Can be obtained by Alternatively, laser engraving, by stereolithography or the like to prepare a plate of male long (plate having a first region R ₁ and the second region R ₂ and the same shape), a material obtained by inverting it to the surface of the cylinder It can be obtained by wrapping. The surface of these plates is preferably hard-plated with chrome or the like.

The transfer sheet 100 is preferably manufactured by multi-imposition from the viewpoint of manufacturing efficiency. The transfer sheet 100 manufactured by multi-imposition in this way is subjected to a transfer step as a long transfer sheet or a single-wafer transfer sheet.

The transfer sheet 100 produced by the above step can facilitate the formation of the colored layer 30 which is the pattern printing for alignment on the protrusion 23, and the light transmission in the alignment pattern formed by the colored layer 30. The contrast of the rate or the light reflectance becomes clear, and the alignment can be facilitated.

Examples of the arbitrary step of aligning include a step of slitting the transfer sheet 100 into a long length, a step of die-cutting the transfer sheet 100 into a single sheet, and a step of transferring the transfer sheet 100 to a transfer material.
When the alignment is performed by the light transmittance of the colored layer 30 which is the pattern printing for the alignment, for example, the light source installed below the transfer sheet 100 and the light source installed above the transfer sheet 100 are installed at positions facing each other. Positioning can be performed by detecting with a light detecting means.
When the alignment is performed by the light reflectance of the colored layer 30 which is the pattern printing for the alignment, it can be detected by, for example, a light source and a light detecting means installed at an arbitrary angle above the transfer sheet 100.

[Manufacturing method of decorative molded products]
The method for producing a decorative molded product according to an embodiment of the present invention includes the above-mentioned step of transferring the transfer layer 20 of the transfer sheet 100 of the present invention to the object to be transferred and the release sheet 10 of the transfer sheet 100. It has a process.
Examples of the transferred product include a resin molded product and the like.

In the decorative molded product produced by the above step, the transfer sheet 100 to be used does not generate foil dust, and the appearance after transfer can be improved.

A known transfer method can be used as a method for producing a decorative molded product. For example, (i) a method of attaching a transfer sheet to a preformed object to be transferred, transferring the transfer layer of the transfer sheet, and then peeling off the release sheet of the transfer sheet, (ii) a flat plate-shaped cover. A method of attaching a transfer sheet to a transfer product, transferring the transfer layer of the transfer sheet, peeling off the release sheet of the transfer sheet, and then molding the transferred product on which the transfer layer is laminated, (iii). ) A method of integrating the transfer material with the transfer sheet at the time of injection molding and then peeling off the release sheet of the transfer sheet [in-mold molding (injection molding simultaneous transfer decoration method)] and the like can be mentioned. Above all, according to in-mold molding (injection molding simultaneous transfer decoration method), it is possible to perform decoration molding on a resin molded body having a complicated surface shape such as a three-dimensional curved surface.

As one embodiment of the method for manufacturing a decorative molded product using the transfer sheet of the present invention by in-mold molding, (1) the transfer layer side of the transfer sheet is arranged toward the inside of the in-mold molding mold. The process and (2) the process of injecting resin into the in-mold molding die.
(3) A step of integrating the transfer sheet and the resin to transfer the transfer layer of the transfer sheet onto the surface of the resin molded body (transferred product), and (4) the resin molded body (transferred). A thing having a step of peeling off the release sheet of the transfer sheet after taking out the thing) from a mold.
(1) If the second region R ₂ remains at the time of arranging the steps, the transfer sheet is arranged at an accurate position of the mold by using the alignment pattern portion of the second region R _2. be able to.
After the step (4), it is preferable to trim (remove) unnecessary portions as necessary. (4) When the second region R ₂ remains after the step, it is preferable to trim (remove) the region.

(Resin molded product)
As the resin molded body, it is preferable to use an injection-moldable thermoplastic resin or a thermosetting resin, and various known resins can be used.
When the decorative molded product according to the present invention is manufactured by in-mold molding, it is preferable to use a thermoplastic resin. Examples of such thermoplastic resins include polystyrene-based resins, polyolefin-based resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide-based resins, polycarbonate-based resins, polyacetal-based resins, and acrylic-based resins. Examples thereof include polyethylene terephthalate resin, polybutylene tephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

[Measurement and evaluation]
The transfer sheets prepared in Examples and Comparative Examples were measured and evaluated as follows. The results are shown in Table 1.

<Evaluation of foil dust>
The size and number of foil dusts generated when the transfer sheets were cut into 10 cm squares were evaluated so as to cut the alignment marks of the transfer sheets produced in Examples and Comparative Examples. When 10 places were cut out, the average number of foil dusts of 2 cm square or more was calculated.
A: Less than 0.5 B: 0.5 or more and less than 2.0 C: 2.0 or more

<Adhesion 1>
After attaching a plant-based cellophane tape (manufactured by Nichiban Co., Ltd., width 25 mm) to the release sheet of the transfer sheet produced in Examples and Comparative Examples, hold the tip of the cellophane tape and hold the tip of the cellophane tape at an angle of 45 degrees to 0. It was pulled off in 5 seconds and the adhesion was evaluated.
A: Peeled at the interface between the release sheet and the transfer layer C: Peeled at a place other than the interface between the release sheet and the transfer layer

<Adhesion 2>
After attaching a plant-based cellophane tape (manufactured by Nichiban Co., Ltd., width 25 mm) to the release sheet of the transfer sheet produced in Examples and Comparative Examples, hold the tip of the cellophane tape and hold an angle of 180 degrees. It was pulled off in seconds and the adhesion was evaluated.
A: Peeled at the interface between the release sheet and the transfer layer C: Peeled at a place other than the interface between the release sheet and the transfer layer

<Clarity of alignment pattern>
The alignment patterns of the transfer sheets prepared in Examples and Comparative Examples were photographed with micrographs, and the sharpness of the alignment patterns was evaluated. Regarding the sharpness, the line widths of the colored layers at 10 points were measured, and the following evaluations were made.
A: The variation of the line width of the colored layer when the transfer sheet is observed from the plane direction is within 5% B: The variation of the line width of the colored layer when the transfer sheet is observed from the plane direction is within 10% C: The transfer sheet The variation of the line width of the colored layer when observing from the plane direction exceeds 10%.

(Example 1)
1. 1. Preparation of Release Sheet A resin layer forming ink of the following formulation was applied onto a polyethylene terephthalate film having a thickness of 75 μm and dried to form an uncured resin layer having a thickness of 8.0 μm.
<Ink for forming resin layer>
40 parts by mass of ionizing radiation curable resin composition (Acrylic resin manufactured by Kyoei Chemical Co., Ltd.)
・ Photopolymerization initiator 3 parts by mass ・ Methyl ethyl ketone 60 parts by mass ・ Silicone leveling agent 0.5 parts by mass

Next, using a plate having a shape complementary to the following first region R ₁ and second region R ₂ , the uncured resin layer is formed, and at the same time, ionizing radiation is irradiated from the polyethylene terephthalate film side. The shaped resin layer was cured.
<First region _{R 1} and the complementary shapes>
-Smooth <shape complementary to the second region R ₂ >
-Groove portion having a shape complementary to the convex portion: width 0.2 mm, depth 7.0 μm
・ Spacing between the ends of the groove: 0.6 mm
-Number of grooves: 25 <Shape of shaped resin layer>
-Convex: width 0.2 mm, height 5.0 μm
・ Spacing between the ends of the convex parts: 0.6 mm
・ Number of grooves: 24

Next, the mold release layer forming ink of the following formulation was applied to the entire surface of the obtained resin layer, and then dried at 40 ° C. for 72 hours to form a release layer having a thickness of 0.5 μm to form a release sheet. Got
<Ink for mold release layer formation>
-Acrylic polyol 70 parts by mass (manufactured by Soken Chemical Co., Ltd., product name: Thermolac SU100A)
25 parts by mass of isocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D-110N)
-Ethyl acetate 161 parts by mass-Methyl isobutyl ketone 56 parts by mass

2. 2. Preparation of Transfer Layer A coating film is formed by applying the protective layer forming ink of the following formulation to the release sheet obtained in "1" above so that the adhesion amount after drying is 5.0 g / m ^2. After that, the light source was irradiated with an H bulb, a transport speed of 20 m / min, and an output of 40% using a fusion UV lamp system to semi-cure the protective layer. The integrated light intensity at this time was measured with an illuminance meter (trade name: UVPF-A1) manufactured by Eye Graphics Co., Ltd. and found to be 15 mJ / m ² .
<Ink for forming protective layer>
-Urethane acrylate-based UV curable resin composition 70 parts by mass (manufactured by Dainichiseika Co., Ltd., trade name: Seika Beam HT-X)
(Solid content 35%, toluene / ethyl acetate mixed solvent)
-Urethane acrylate-based UV curable resin composition 30 parts by mass (manufactured by Dainichiseika Co., Ltd., trade name: Seika Beam EXF-HT-1)
(Solid content 40%, toluene / methyl ethyl ketone mixed solvent)

Next, the anchor layer forming ink of the following formulation is applied onto the protective layer so that the adhesion amount after drying is 3.0 g / m ^2, and after forming a coating film, it is dried at 40 ° C. for 72 hours and cured. An anchor layer having a thickness of 2 μm was formed.
<Ink for forming anchor layer>
・ 100 parts by mass of acrylic polyol (manufactured by Dainichiseika Co., Ltd., trade name: TM-VMAC, solid content 25%)
(Toluene / ethyl acetate / methyl ethyl ketone mixed solvent)
・ Xanmethylene diisocyanate 10 parts by mass (manufactured by Dainichiseika Co., Ltd., trade name: PTC-RC3)
(Solid content 75%, solvent: ethyl acetate)
-Solvent 65 parts by mass (methyl ethyl ketone, diluted so that the solid content is 22%)

Next, the adhesive layer forming ink of the following formulation was applied onto the anchor layer so that the adhesion amount after drying was 2.5 g / m ^2, and a coating film was formed. The coating film was dried to form an adhesive layer having a thickness of 2 μm, and a transfer sheet was obtained.
<Ink for forming adhesive layer>
-Acrylic resin 100 parts by mass (manufactured by Dainichiseika Co., Ltd., product name: TM-R600, solid content 20%)
(Ethyl acetate / acetic acid-n-propyl / methyl ethyl ketone mixed solvent)
-Methylethylketone 40 parts by mass-Hydroxyphenyl triazine-based UV absorber 1.28 parts by mass (manufactured by BASF, trade name: Tinuvin479)

<Shape of protrusion formed on the adhesive layer>
・ Height of protrusion: 4.5 μm
・ Spacing between the ends of the protrusions: 0.5 mm

Next, the colored layer forming ink 1 of the following formulation is applied onto the protruding portion of the adhesive layer by a gravure reverse printing method so that the adhesion amount after drying is 1 g / m ² , dried, and the colored layer is formed. Was formed to obtain a transfer sheet of Example 1. The evaluation results of the obtained transfer sheet are shown in Table 1.
<Ink 1 for forming a colored layer>
・ Black pigment (carbon black) 4.3 parts by mass ・ Copolymer of vinyl chloride resin and vinyl acetate resin 1.3 parts by mass ・ Acrylic resin 5.4 parts by mass ・ Polymethyl methacrylate resin 7.0 parts by mass Parts / solvent 82 parts by mass (methyl ethyl ketone / ethyl acetate / methyl isobutyl ketone mixed solvent)
(Mixing ratio 4/4/2)

(Example 2)
In Example 1, the method for forming the colored layer was the same except that the method was melt thermal transfer using a thermal transfer sheet, and the transfer sheet of Example 2 was obtained. The evaluation results of the obtained transfer sheet are shown in Table 1.

As a method for producing the thermal transfer sheet used in Example 2, first, a heat-sensitive adhesive having the following composition is dissolved in xylene on art paper having a thickness of 70 μm and gravure-coated at a ratio of 20 g / m ^{2 based} on the solid content. , A thermal transfer image receiving sheet was prepared. Next, a gravure reverse printing method is performed on the surface of a polyester film having a thickness of 6 μm in which a heat-resistant layer is formed on the back surface so that the amount of the colored layer forming ink 2 of the following formulation after drying is 1.5 g / m ^2. And dried to prepare a heat transfer sheet.
<Heat-sensitive adhesive>
-Styrene-butadiene rubber 2.4 parts by mass (Asahi Kasei, trade name: Solpren 1204)
-2.0 parts by mass of chlorinated polypropylene (manufactured by Sanyo Kokusaku Pulp, trade name: Supercron 907LL)
-Vinyl chloride / vinyl acetate copolymer 10.0 parts by mass (manufactured by Sumitomo Chemical, trade name: Sumitate KC10)
-Petroleum resin 5.0 parts by mass (manufactured by Nippon Oil, trade name: Neopolymer 130)
-Microsilica 0.4 parts by mass (made by Degussa, trade name: Erosil OK-412)
-Polyethylene wax 1.5 parts by mass (manufactured by Goodyear, trade name: Microfine SF Gold)
-Amide wax 1.5 parts by mass (made by Denka Polymer, trade name: AP65)
・ Toluene 80.0 parts by mass <Ink for forming colored layer 2>
-Black pigment (carbon black) 4.3 parts by mass-Polymer of vinyl chloride resin and vinyl acetate resin 1.3 parts by mass-Acrylic resin 5.4 parts by mass-Polymethyl methacrylate resin 7.0 parts by mass- Polyethylene wax 0.8 parts by mass (made by BASF, trade name: A wax)
-Solvent 81.2 parts by mass (mixed solvent of methyl ethyl ketone / ethyl acetate / methyl isobutyl ketone)
(Mixing ratio 4/4/2)

(Comparative Example 1)
1. 1. Preparation of Release Sheet A melt thermal transfer method using the thermal transfer sheet obtained in Example 2 on a convex portion provided in a second region of the resin layer of the release sheet obtained in "1" of Example 1. To form a colored layer. Other than that, a release sheet was prepared in the same manner as in Example 1.

2. 2. Preparation of Transfer Layer A transfer layer was prepared by laminating the protective layer, the anchor layer, and the adhesive layer shown in Example 1 in this order on the release sheet and the colored layer obtained in "1" above.
Through the above steps, a transfer sheet of Comparative Example 1 was obtained. The evaluation results of the obtained transfer sheet are shown in Table 1.

<Shape of protrusion formed on the adhesive layer>
・ Height of protrusion: 4.7 μm
・ Spacing between the ends of the protrusions: 0.5 mm

The transfer sheet of the present invention can be suitably used for manufacturing communication devices such as mobile phones, information devices inside automobiles, and decorative molded products such as home appliances.

1: Support 2: Resin layer 3: Release layer 4: Convex part 5: Concavo-convex part 10: Release sheet 20: Transfer layer 21: Protective layer 22: Adhesive layer 23: Projection part 30: Colored layer 100: Transfer Sheet

Claims (12)

A transfer sheet having a transfer layer on a release sheet.
The release sheet has a first region for transferring to a transfer material and a second region for providing an alignment pattern, and the second region has a convex portion on the surface side of the transfer layer side. Have and
The transfer layer is provided with a positioning pattern portion having a protrusion based on the convex portion on the surface opposite to the surface on which the release sheet is provided, and has a colored layer on the protrusion. Sheet. The transfer sheet according to claim 1, wherein the height of the protruding portion is 1.0 μm or more. The transfer sheet according to claim 1 or 2, wherein the distance between the ends of the protruding portions is 0.05 to 3.0 mm. The transfer according to any one of claims 1 to 3, wherein the colored layer has a line-like pattern having an average line width of 0.01 to 4.0 mm, and the variation of the line width is within 10%. Sheet. The transfer sheet according to any one of claims 1 to 4, wherein the thickness of the colored layer is 0.3 to 5.0 μm. The transfer sheet according to any one of claims 1 to 5, wherein the release sheet has a release layer on at least a part of a surface on the side in contact with the transfer layer. The transfer sheet according to any one of claims 1 to 6, wherein the transfer layer has a protective layer on the release sheet side. The transfer sheet according to claim 7, wherein the protective layer contains a cured product of an ionizing radiation curable resin composition. A step of applying an ink for forming a resin layer containing an ionizing radiation curable resin composition on a support to form an uncured resin layer, and
Using a plate having a shape complementary to the first region and the second region, the uncured resin layer is shaped, and at the same time, ionizing radiation is irradiated to cure the shaped resin layer.
A step of applying an ink for forming a release layer on the cured resin layer to form a release layer, and
A step of applying a protective layer forming ink containing an ionizing radiation curable resin composition onto the release layer to form a protective layer, and
A step of applying an adhesive layer forming ink on the protective layer to form an adhesive layer, and
The transfer sheet according to claim 1, further comprising a step of applying an ink for forming a colored layer on a protruding portion formed at a position corresponding to the second region of the adhesive layer to form a colored layer. Production method. The method for producing a transfer sheet according to claim 9, wherein the step of forming the colored layer is formed by a transfer method. The method for producing a transfer sheet according to claim 9, wherein the step of forming the colored layer is formed by a printing method. Manufacture of a decorative molded product comprising a step of transferring the transfer layer of the transfer sheet according to any one of claims 1 to 8 to an object to be transferred and a step of peeling off the release sheet of the transfer sheet. Method.