JP6743423B2 - Transfer sheet, method of manufacturing transfer sheet, and method of manufacturing decorative molded article using transfer sheet - Google Patents

Description

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

2. Description of the Related Art Conventionally, in the fields of household electric appliances, automobile interior parts, sundries, and the like, high functionality and design have been developed by decorating the surface of the transferred material with characters and pictures. As a method of decorating the surface of the transferred material, there is a transfer method. The transfer method uses a transfer sheet in which a transfer layer including a release layer, a pattern layer, and an adhesive layer is formed on a base material, and heat and pressure are applied to bring the transfer layer into close contact with an object to be transferred. It is a method of peeling and transferring only the transfer layer to the surface of the transferred object for decoration.

In addition, depending on the use, the surface of the transferred material may be required to have a high-quality appearance and excellent designability such as a different texture such as gloss and matte.
For example, in Patent Document 1, a release layer entirely containing a matting agent on a base sheet, a mask layer partially containing an active energy ray-curable resin, a release layer as a transfer layer, and a pattern layer. Is disclosed, a partial mat transfer sheet is disclosed.

Japanese Patent No. 5095598

In the partial mat transfer sheet described in Patent Document 1, after the transfer layer is adhered to the surface of the transferred material, the base sheet, the release layer, and the mask layer are peeled off to transfer the transfer layer to the surface of the transferred material. .. However, in the matte portion on the surface of the transfer layer after the transfer, the characters or the like of the transfer target may be whitish and the contrast may be low.

The present invention has been made in view of such circumstances, and uses a transfer sheet having a high contrast and a decorative molded article excellent in designability, a method for producing the transfer sheet, and the transfer sheet. It is an object of the present invention to provide a method for manufacturing a decorative molded product.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by forming a first release layer on the uneven shape of the uneven layer.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [8].
[1] A base material having a first region and a second region adjacent to the first region, a concavo-convex layer having a concavo-convex shape provided on the first region of the base material, and the concavo-convex layer described above. A first release layer formed on the uneven shape, a second release layer provided on the second region of the base material, the first release layer, and the second release layer. A transfer sheet having a protective layer formed on.
[2] The ratio between the thickness _{T 2} of the said the thickness _{T 1} of the said uneven layer first releasing layer _(T 1 / _{T 2)} is a 0.2 to 200, transfer sheet according to the above [1] ..
[3] The transfer sheet according to the above [1] or [2], which has an uneven layer between the base material in the second region and the second release layer.
[4] The transfer sheet according to the above [3], further including a relaxation layer between the uneven layer provided on the second region of the base material and the second release layer.
[5] A step (1) of forming a concavo-convex layer having a concavo-convex shape on a first region of a base material having a first region and a second region adjacent to the first region, and the concavo-convex pattern of the concavo-convex layer. A step (2) of forming a first release layer on the shape; a step (3) of forming a second release layer on the second region of the substrate; the first release layer; A step (4) of forming a protective layer on the second release layer.
[6] The method for producing a transfer sheet according to the above [5], wherein in the step (1), the uneven layer is formed on the second region of the base material.
[7] The method for producing a transfer sheet according to the above [6], wherein before the step (2), a relaxation layer is formed on the uneven layer provided on the second region of the base material.
[8] A step of transferring the protective layer of the transfer sheet according to any one of the above [1] to [4] to a transfer target, a base material of the transfer sheet, an uneven layer, a first release layer, And a step of peeling off the second release layer, the method for producing a decorated molded article.

According to the present invention, there is provided a transfer sheet having a high contrast and a decorative molded product excellent in designability, a method for manufacturing the transfer sheet, and a method for manufacturing a decorative molded product using the transfer sheet. You can

It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the decorative molded product obtained using the transfer sheet of this invention. FIG. 3 is a plan view of the decorative molded product according to the present invention viewed from the protective layer side.

[Transfer sheet]
The transfer sheet of the present invention comprises a base material having a first area and a second area adjacent to the first area, and an uneven layer having an uneven shape provided on the first area of the base material, A first release layer formed on the uneven shape of the uneven layer, a second release layer provided on the second region of the base material, the first release layer, and the second release layer. A protective layer formed on the layer.

1 to 3 are sectional views showing an embodiment of the transfer sheet of the present invention. The transfer sheet 10 of FIG. 1 has a base material 1 having a first region P and a second region Q adjacent to the first region P. The uneven layer 2 having an uneven shape is provided on the first region P of the base material 1, and the first release layer 3 is provided on the uneven shape of the uneven layer 2. Further, the second release layer 4 is provided on the second region Q of the base material 1. Further, a protective layer 5 is provided on the first release layer 3 and the second release layer 4.

Further, as shown in FIG. 2, the transfer sheet 20 of the present invention may have the uneven layer 12 formed on the second region Q of the base material 1. In this case, the relaxation layer 16 is provided on the uneven layer 12 formed on the second region Q of the base material 1, and the second release layer 14 is provided on the relaxation layer 16. Further, the anchor layer 17, the print layer 18, and the adhesive layer 19 may be provided on the protective layer 15. As described above, the transfer sheet 20 includes the release sheet X having the base material 11, the uneven layer 12, the first release layer 13, the second release layer 14, and the relaxation layer 16, the protective layer 15, and the anchor layer 17. , A print layer 18, and a transfer layer Y having an adhesive layer 19.
The positions of the first region P and the second region Q are not particularly limited, and the first region P may be arranged between the second regions Q or inside the second region Q as shown in FIG. 2. However, as shown in FIG. 3, the second regions Q may be arranged between the first regions P or inside the first regions P.
Hereinafter, each layer constituting the transfer sheet of the present invention will be specifically described.

(Base material)
The substrate used for the transfer sheet of the present invention is a polyolefin resin such as polyethylene or polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl acetate copolymer, ethylene/vinyl alcohol copolymer, or other vinyl. -Based resins, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as methyl poly(meth)acrylate and ethyl poly(meth)acrylate, styrene resins such as polystyrene, nylon 6 or A resin such as a polyamide resin represented by nylon 66 is used. Of these, the base material is selected according to the usage conditions. For example, polyethylene terephthalate or the like can be used from the viewpoint of heat resistance, and nylon or the like can be used from the viewpoint of conformability to the surface shape of the transferred object such as a curved shape.

The thickness of the base material is preferably in the range of 25 to 150 μm, more preferably in the range of 30 to 100 μm, from the viewpoints of moldability, shape conformability and easy handling.
Further, on the surface of the substrate, physical treatment such as corona discharge treatment or oxidation treatment, or application of a coating material called an anchor agent or a primer may be performed in advance in order to enhance adhesion with the uneven layer or the like. ..
In the present specification, “AA to BB” means “AA or more and BB or less”. The same applies below.

(Uneven layer)
The uneven layer is a layer having an uneven shape, and is formed on the first region of the base material.
The concavo-convex layer forms a concavo-convex shape by phase separation using a method of forming a concavo-convex shape using a resin composition mainly composed of a filler and a binder resin, or a resin composition containing only a resin or the like without a filler. It can be formed by a method or a method of forming a concavo-convex shape by transferring a resin composition containing only a resin or the like without a filler to a mold. In the present invention, the uneven layer is preferably formed of a resin composition mainly containing a filler and a binder resin. By using the resin composition, the surface of the concavo-convex layer in contact with the protective layer can be formed into a concavo-convex shape. Examples of the binder resin include thermoplastic resins and curable resins, and curable resins are preferable from the viewpoint of film strength.

The curable resin can be selected from thermosetting resins and ionizing radiation curable resins such as photocurable resins and electron beam curable resins. As the thermosetting resin, it is possible to apply a resin generally known as a resin that is cured (insolubilized) when heated. Examples thereof include phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, resin obtained by curing acrylic polyol with isocyanate, resin obtained by curing polyester polyol with melamine, and resin obtained by curing acrylic acid with melamine. To be Moreover, you may use combining the monomer which is a structural component of thermosetting resin.

In addition to the above, it is preferable to use, for example, a thermosetting acrylic resin. The thermosetting acrylic resin is obtained by crosslinking at least one acrylic monomer or a copolymer obtained by polymerizing an acrylic monomer and a styrene monomer with a melamine compound or an isocyanate compound. It is a thing.

Examples of the acrylic monomers include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, octyl methacrylate, stearyl methacrylate; ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, etc. Acrylic acid alkyl esters; acrylonitrile; amino group-containing vinyl monomers such as acrylamide, methacrylic acid dimethylaminoethyl ester, methacrylic acid diethylaminoethyl ester, acrylic acid dimethylaminoethyl ester, and dimethylaminopropyl methacrylamide; Further, styrene, α-methylstyrene, vinyltoluene, p-ethylstyrene and the like can be used as the styrene-based monomer.

In addition, as a composition using a photocurable resin, for example, a compound having a reactive double bond such as a vinyl group in the molecule (including not only a low molecular weight compound but also a polymer) and photopolymerization initiation Those containing an agent as a main component are mentioned. Further, examples of the composition using the electron beam curable resin include those containing a compound having a reactive double bond such as a vinyl group in the molecule and, if necessary, a resin. The compound having a reactive double bond in the molecule has a (meth)acryloyl group, for example, methyl (meth)acrylate, ethyl (meth)acrylate benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate. , Monofunctional type such as phenoxydiethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate , Trimethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like. There are also oligomers such as polyester acrylate, polyurethane acrylate, polyepoxy acrylate, polyether acrylate, oligo acrylate, polyalkyd acrylate and polyol acrylate. Further, there are, for example, styrene monomers, α-methylstyrene, divinylbenzene, vinyl acetate, pentene, hexene and unsaturated compounds having a vinyl group or an allyl group.

The photopolymerization initiator is added especially when it is cured by ultraviolet rays. As the photopolymerization initiator, for example, a benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photopolymerization initiator is preferably used. Examples of the benzoin ether type include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether. Examples of the acetophenone type include 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-ter-butyltrichloroacetophenone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the benzophenone series include benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, dibenzosuberenone and the like. Examples of the thioxanthone type include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2-ethylanthraquinone.
The photopolymerization initiator is preferably added in an amount of 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the compound having a reactive double bond. Further, the photopolymerization initiator is not limited to one type, and two or more types may be used in combination.

By using the above-mentioned thermosetting resin, photocurable resin, or curable resin such as electron beam curable resin for the concavo-convex layer, the filler is firmly supported and the coating film of the concavo-convex layer is strengthened. In this way, since the filler is firmly supported, peeling (transfer) of the uneven layer due to the removal of the filler does not occur. As a result, fine irregularities are stably formed on the surface of the decorative molded product formed by transferring the transfer layer of the transfer sheet, and uneven portions do not occur.

The filler contained in the uneven layer preferably has an average particle size of 0.5 to 10 μm, and an organic filler or an inorganic filler can be used. Here, in the present invention, the “equivalent spherical diameter” of the filler at the 50 mass% point of all the fillers determined by the light transmission centrifugal sedimentation method is defined as the average particle diameter of the filler. By setting the average particle diameter to 0.5 μm or more, sufficient fine irregularities can be provided on the surface of the decorative molded product, and a sufficient matt feeling can be obtained. By setting the average particle diameter to 10 μm or less, a sufficient matt feeling can be obtained without adding a large amount of filler, and the release sheet can be easily peeled off at the interface with the protective layer.

Examples of the inorganic filler include fillers such as silica, alumina, clay, talc, diatomaceous earth, zeolite, calcium carbonate, barium sulfate, zinc oxide, titanium oxide and glass beads. Examples of the organic filler include various synthetic resin particles, for example, melamine resin, benzoguanamine resin, benzoguanamine/melamine/formalin condensate, acrylic resin, urethane resin, styrene resin, and the like. It can also be used as a mixture. In particular, the organic filler of a condensate of melamine and formaldehyde or a condensate of benzoguanamine and formaldehyde improves the matte feeling of the surface of the decorative molded product and enhances the antireflection effect, or It is preferable in terms of stability.

The above filler is preferably contained in an amount of 0.5 to 30 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the binder resin. When the amount is 0.5 parts by mass or more, an appropriate fine uneven shape can be formed on the surface of the uneven layer, and when the amount is 30 parts by mass or less, a decrease in film strength of the uneven layer is suppressed, and a release sheet. Can be easily peeled off at the interface with the protective layer.

The concavo-convex layer is prepared by adding an additive to the above-mentioned filler and binder resin, if necessary, and dissolving or dispersing it in a suitable solvent to prepare a concavo-convex layer coating solution. It can be formed by applying by means of a printing method, a screen printing method, a slit reverse method, a reverse coating method using a gravure plate, etc., drying, and curing if necessary.

The thickness T ₁ of the uneven layer after drying (hereinafter referred to as the thickness T _{1 of the} uneven layer) is preferably 0.5 to 10 μm, more preferably ₁ to 8 μm. In addition, the thickness T ₁ of the uneven layer refers to the thickness from the base to the top of the uneven layer.

(First release layer)
The first release layer is a layer provided to easily peel the transfer layer from the base material and to improve the contrast of the decorative molded product, and is formed on the uneven shape of the uneven layer described above. By providing the first release layer on the uneven shape of the uneven layer, the transfer layer can be reliably and easily transferred from the transfer sheet to the transfer target, and the release sheet can be reliably peeled off. Further, by providing the first release layer on the uneven shape of the uneven layer, the uneven shape is relaxed, the high frequency component of the uneven shape on the first release layer is reduced, and the transfer layer of the transfer sheet is transferred. When transferred to the body, the surface of the decorative molded product has an uneven shape with few high-frequency components. Since the unevenness of the high frequency component has a larger inclination angle than the unevenness of the low frequency component, the diffusion is strong and whitening is likely to occur. Therefore, by forming the first release layer on the concavo-convex layer, the contrast can be improved and the designability can be improved. In addition, glare on the surface can be suppressed. Here, “glare” refers to a phenomenon in which a minute variation in luminance is visible in the image light due to the uneven structure on the surface. Furthermore, since the unevenness of the low frequency component remains in the uneven shape on the first release layer, the antiglare property can be imparted based on the unevenness of the low frequency component, and the designability can be improved. Further, since the unevenness of the low frequency component provides a sufficient matte feeling, a texture different from the surface shape of the second release layer on the second region of the base material can be expressed.

Uneven layer thickness T ₁ and the first release layer after drying a thickness T ₂ ratio _{(hereinafter,} the first release layer is referred to as the thickness T ₂ of _{the) (T} 1 _/ T 2) is preferably 0. 2 to 200, more preferably 1.0 to 100, still more preferably 2.0 to 50, still more preferably 3.0 to 10. When it is 0.2 or more, it is possible to easily impart the antiglare property due to the unevenness of the low frequency component, and when it is 200 or less, the contrast of the decorative molded product is improved and the glare is suppressed, The designability can be improved.
The thickness T ₂ of the uneven layer thickness T ₁ and the first release layer, for example, from the captured cross-sectional image using a scanning transmission electron microscope (STEM) of 20 points thickness was measured, and the 20 locations It can be calculated from the average value. The accelerating voltage of STEM is preferably 10 kv to 30 kV. The STEM magnification is preferably 1000 to 7,000 times when the measured film thickness is on the micron order, and is preferably 50,000 to 300,000 times when the measured film thickness is on the nano order.

In the present invention, on the surface of the first release layer, the arithmetic mean roughness (Ra _x11 ) of JIS B0601:2001 when the cutoff value is 0.8 mm and the cutoff value is 0.08 mm It is preferable that the arithmetic mean roughness (Ra _y11 ) of JIS B0601:2001 satisfies the following condition (1)′.
0.45≦(Ra _x11 −Ra _y11 )/Ray _y11 (1)′

By satisfying the above condition (1)', the protective layer of the decorative molded product obtained by using the transfer sheet of the present invention can satisfy the condition (1) described later and suppress whitening.

(Ra _x11 -Ra _y11 )/Ra _y11 is more preferably 0.50 or more.
_The upper limit of _{(Ra x11 -Ra y11) / Ra} y11 is preferably less than 0.90, more preferably 0.80 or less, more preferably 0.70 or less.

Ra _x11 is preferably 0.12 to 0.20, more preferably 0.12 to 0.18. Moreover, _Ray11 is preferably 0.05 to 0.10, and more preferably 0.06 to 0.09.
The values of Ra _x11 and Ra _y11 are calculated by measuring 20 points and averaging the measured 20 points.

The first release layer is not particularly limited as long as it has a low adhesive force with the protective layer and can easily peel off the transfer layer from the base material, and examples thereof include a fluororesin and an acrylic resin (for example, acrylic- Melamine-based resins are included), polyester-based resins, polyolefin-based resins, polystyrene-based resins, polyurethane-based resins, cellulose-based resins, vinyl chloride-vinyl acetate-based copolymer resins, thermoplastic resins such as nitrified cotton, and the like. A copolymer of monomers forming a plastic resin, or a resin obtained by modifying these resins with (meth)acrylic acid or urethane can be used alone or as a mixture of a plurality of resin compositions.
In the present invention, it is particularly preferable to use an ester group-containing curable resin. As the ester group-containing curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. The ionizing radiation curable resin may be any ionizing radiation curable resin having an ester group in its side chain, such as acryl (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate having an ester group in its side chain. And polyether (meth)acrylates. The thermosetting resin may be a resin obtained by reacting a polymer having an ester group and a hydroxyl group in the side chain with an isocyanate, for example, an acrylic resin having an ester group and a hydroxyl group in the side chain, an epoxy resin, and A resin obtained by reacting a phenol resin with an isocyanate can be used, and it is particularly preferable to use a resin obtained by reacting an acrylic polyol with an isocyanate.

The first release layer preferably does not contain a filler having an average particle size of 0.5 μm or more, and more preferably does not contain a filler having an average particle size of 0.2 μm or more. Since the first release layer does not contain a filler having an average particle diameter of 0.5 μm or more, the high frequency component of the unevenness on the first release layer can be reduced. Therefore, the decorative molded article obtained by using the transfer sheet of the present invention has an uneven shape in which the unevenness of the high frequency component of the uneven layer is relaxed by the first release layer (the unevenness of the surface of the first release layer). By forming the (shape), the contrast of the concavo-convex portion can be improved and the designability can be improved. Further, it is possible to suppress glare in the uneven portion.

The first release layer may add a filler of less than 0.5 μm in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing the unevenness of the high frequency component, the average particle diameter of the filler is preferably less than 0.2 μm, and the content thereof is preferably 10 parts by mass or less based on 100 parts by mass of the resin component. ..

The first release layer is prepared by preparing a coating solution for the first release layer containing a resin that constitutes the first release layer, an appropriate solvent, etc., and applying the coating solution onto the uneven shape of the uneven layer by the gravure printing method. It can be formed by coating and drying by means such as a screen printing method, a slit reverse method or a reverse coating method using a gravure plate.

The thickness T ₂ of the first release layer is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm.

(Second release layer)
The second release layer is a layer provided to easily peel the transfer layer from the base material, and is provided on the second region of the base material.
In the present invention, on the surface of the second release layer, the arithmetic mean roughness (Ra _x22 ) of JIS B0601:2001 when the cutoff value is 0.8 mm, and the cutoff value when 0.08 mm It is preferable that the arithmetic average roughness ( _{Ray 22} ) of JIS B0601:2001 satisfies the following condition (2)′.
0.90≦(Ra _x22 −Ray ₂₂ )/ _{Ray 22} (2)′

By satisfying the above condition (2)', the protective layer of the decorative molded product obtained by using the transfer sheet of the present invention can satisfy the following condition (2).
(Ra _x22 -Ra _y22 )/Ra _y22 is more preferably 1.20 or more, _still more preferably 1.50 or more.
_{Further, (Ra x22} -Ra y22) _/ the upper limit of _{Ra y22} is not particularly limited, but is preferably 2.50 or less, more preferably 2.00 or less.

Ra _x22 is preferably 0.10 to 0.17, more preferably 0.11 to 0.16. Moreover, _Ray22 is preferably 0.03 to 0.06, and more preferably 0.04 to 0.06.

The ratio [(Ra _x11 -Ra _y11 )/Ra _y11 ]/[(Ra _x22 -Ra _y22 )/Ra _y22 ] of (Ra _x11 -Ra _y11 )/Ra _y11 and (Ra _x22 -Ra _y22 )/Ra _y2 is , Preferably 0.56 or less, more preferably 0.50 or less. By setting the ratio to 0.56 or less, the second region of the protective layer of the decorative molded article obtained by using the transfer sheet of the present invention can obtain a glossy feeling, a matte feeling, a texture and the like different from those of the first region. it can.

_{Further, by} setting {(Ra _x22 -Ra _y22 )/Ra _y22 }-{(Ra _x11 -Ra _y11 )/Ra _y11 }>0.30, a decorative molded article obtained by using the transfer sheet of the present invention The second area of the protective layer is preferable because it can provide a glossy feeling, a matte feeling, a texture, and the like different from those of the first area. From the viewpoint of making the contrast between the first region and the second region clear, it is more preferably 0.40 or more, still more preferably 0.60 or more.
_The value of _{Ra x22,} and _{Ra y22} are each measured 20 points, and calculates an average of the measured 20 points.

The second release layer is not particularly limited as long as it has a low adhesive force with the protective layer and can easily peel off the transfer layer from the base material. For example, the resin exemplified in the section of the first release layer is used. It can be formed by using the same, and may be the same as or different from the resin composition used for the first release layer.

The second release layer preferably does not contain a filler having an average particle diameter of 0.5 μm or more, and more preferably does not contain a filler having an average particle diameter of 0.2 μm or more. Since the second release layer does not contain a filler having an average particle size of 0.5 μm or more, the smoothness of the surface of the second release layer is improved, whereby the protective layer provided on the second release layer. The smoothness of the surface can be improved. As a result, when the transfer layer having the protective layer is transferred to the transfer target, a smooth surface of the protective layer is formed on the surface of the decorative molded product, so that it is formed by the uneven layer and the first release layer. It is possible to express a texture different from the uneven shape.

The second release layer may add a filler of less than 0.5 μm in order to impart thixotropy to the coating liquid. However, from the viewpoint of reducing the unevenness of the high frequency component, the average particle diameter of the filler is preferably less than 0.2 μm, and the content thereof is preferably 10 parts by mass or less based on 100 parts by mass of the resin component. ..

The second release layer is prepared by preparing a coating solution for the second release layer containing the above-mentioned resin and a suitable solvent and the like, and applying this to a substrate by gravure printing method, screen printing method, slit reverse method or gravure method. It can be formed by coating and drying by means such as a reverse coating method using a plate.

The thickness T ₃ after drying of the second release layer when the uneven layer is not provided on the second region of the base material and when the uneven layer and the relaxation layer are provided on the second region of the base material (hereinafter, referred to as the The thickness of the second release layer, which is referred to as T ₃ , is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. Further, the thickness T ₃ of the second release layer in the case of having the uneven layer on the second region of the base material and not having the relaxation layer is preferably 0.05 to 10 μm, and more preferably 0.1 to 10. It is 5 μm.

(Relaxation layer)
In the transfer sheet of the present invention, when the uneven layer is formed on the second region of the base material, in order to make the uneven shape of the uneven layer smoother, the transfer sheet is provided between the uneven layer and the second release layer. In addition, it is preferable to further provide a relaxation layer.
The relaxation layer may be formed only from a resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and these resins are used as a binder, and a pigment or dye of an appropriate color is used. You may form with the coloring ink which contains a as a coloring agent. When the relaxing layer contains the colorant, a marker for aligning the pattern when printing the pattern on the transfer layer and for aligning with the transfer target can be formed simultaneously with the formation of the relaxing layer. In this case, the color is not limited to a color that a person can feel, but includes a color that can be mechanically detected such as infrared rays. Above all, the relaxation layer is preferably black from the viewpoint of being reliably detected regardless of the type of light source of the photoelectric tube. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing, sublimation transfer printing, and inkjet printing. Incidentally, by containing a colorant in the relaxation layer without containing a colorant in the second release layer, it is possible to make it difficult to form irregularities due to the colorant on the surface of the second release layer, The peelability between the mold layer and the protective layer can be easily improved.

The thickness of the relaxing layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. The average particle diameter of the colorant is preferably 5 nm to 500 nm from the viewpoint of alleviating irregularities. Here, the average particle size is a 50% particle size (d50: median size) when the colorant in a solution is measured by a dynamic light scattering method and the particle size distribution is represented by a cumulative distribution. It can be measured using an analyzer (manufactured by Nikkiso Co., Ltd.).

Ratio of the thickness of the concavo-convex layer when the concavo-convex layer is formed on the second region of the base material and the total thickness of the layers constituting the release sheet existing on the concavo-convex layer [thickness of concavo-convex layer/ The total thickness of the layers constituting the release sheet present] is preferably 0.01 to 70, more preferably 0.1 to 15.

(Protective layer)
The protective layer is a layer for protecting the decorative molded product from abrasion, light, chemicals and the like after the transfer layer is transferred from the transfer sheet to the transfer target. The surface shape of the protective layer is a shape complementary to the surface shapes of the first release layer and the second release layer. Further, in the part corresponding to the first release layer of the protective layer, antiglare property is imparted while suppressing the decrease in contrast, and a sufficient matt feeling is obtained, and in the part corresponding to the second release layer. Provides a glossy feeling and a matte feeling different from those of the first release layer.
The protective layer is preferably formed using a curable resin such as an ionizing radiation curable resin, a thermosetting resin, or a thermoplastic resin. Ionizing radiation curable has an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, it is excited by irradiation of ultraviolet rays or electron beams to cause a polymerization reaction to cause crosslinking/polymerization. It is the ability to cure. The ionizing radiation-curable functional group is a functional group capable of exhibiting the above-mentioned ionizing radiation-curable property, and is at least selected from the group consisting of vinyl group, (meth)acryloyl group, allyl group, and epoxy group. It is one kind.

The protective layer is preferably formed from an ink composition containing an ionizing radiation curable resin, and further, an ink composition containing a reactive inorganic particle having a reactive functional group on the surface of the inorganic particle and a polyfunctional isocyanate. Is more preferably formed from This ink can be formed by applying and drying it by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.

Examples of the polymer having an ionizing radiation-curable functional group include acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate, and particularly, Urethane (meth)acrylate is preferred. In the present invention, these polymers may be used alone or in combination of two or more.

The weight average molecular weight of the polymer having an ionizing radiation-curable functional group is preferably about 5,000 to 150,000, more preferably 20,000 to 100,000. When the number average molecular weight is within the above range, the thixotropy of the ink composition is obtained, and good moldability is also obtained. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC), and is a value measured under the condition that polystyrene is used as a standard sample. From the viewpoint of obtaining excellent high hardness and scratch resistance, the double bond equivalent of the polymer is 50 to 1000, preferably 100 to 1000, and more preferably 100 to 500. Here, the double bond equivalent means a molecular weight per one ionizing radiation-curable functional group.

The reactive inorganic particles have a reactive functional group on the surface of the inorganic particles. The reactive functional group is preferably a vinyl group, a (meth)acryloyl group, an allyl group, an epoxy group, a silanol group, or the like. From the viewpoint of improving high hardness and scratch resistance, a vinyl group, (meth) An acryloyl group and an allyl group are more preferable.

As the inorganic particles, metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitable silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles and the like are preferably mentioned, which have high hardness and scratch resistance. From the viewpoint of improving the property, silica particles are preferable.

Examples of the shape of the inorganic particles include spheres, ellipsoids, polyhedra, and scaly shapes, and these shapes are uniform and preferably sized, and the inorganic particles have a weak interaction between particles, and are simple particles. It is preferably monodispersed particles. The average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer formed by the ink composition, but is usually preferably 0.05 to 5.0 μm, more preferably 0.1 to 0.5 μm. Here, the average particle size is a 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 represented by a cumulative distribution. It can be measured using a meter (manufactured by Nikkiso Co., Ltd.).

Further, among the inorganic particles, irregularly shaped inorganic particles are preferable from the viewpoint of high hardness. The irregularly shaped inorganic particles are composed of a group of inorganic particles in which the inorganic particles are connected and aggregated with an average number of connected particles of 2 to 40, and are included in the inorganic particles in the present invention. Tethered aggregation may be regular or irregular. As the inorganic particles forming the group of inorganic particles, silica (colloidal silica, fumed silica, precipitable silica, etc.), alumina, zirconia, titania, inorganic particles composed of metal oxides such as zinc oxide are preferably mentioned. From the viewpoint of improving hardness and scratch resistance, inorganic particles made of silica are preferable. That is, it is preferable that the irregular-shaped inorganic particles include a group of silica particles in which the silica particles are connected and aggregated with an average number of connected particles of 2 to 40.

Preferred examples of such reactive irregularly shaped inorganic particles include irregularly shaped inorganic particles whose surface is decorated with a silane coupling agent. Examples of the silane coupling agent include known silane coupling agents having an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group, and the like, and more specifically, γ-aminopropyltriethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropyldimethylethoxysilane , Vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like are preferable, and more preferable are γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. , Γ-methacryloxypropyl dimethylmethoxysilane.

The method of surface-modifying the irregular-shaped inorganic particles with a silane coupling agent may be any known method without particular limitation, such as a dry method of spraying a silane coupling agent or a silane after dispersing the irregular-shaped inorganic particles in a solvent. A wet method in which a coupling agent is added and a reaction is performed can be used.

The polyfunctional isocyanate is a compound having two or more isocyanate groups. Examples of polyfunctional isocyanates include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate ( HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and other polyisocyanates such as aliphatic (or alicyclic) isocyanate. In addition, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimer, and the like, blocked isocyanate compounds, and the like can also be mentioned.

Further, among the polyfunctional isocyanates, those having at least one selected from a vinyl group, a (meth)acryloyl group, an allyl group and an epoxy group as an ionizing radiation curable functional group are particularly preferable from the viewpoint of high hardness. Specifically, a polyfunctional isocyanate having at least one functional group having an ethylenically unsaturated bond and two or more isocyanate groups such as "Laromer LR9000 (trade name)" (manufactured by BASF) is preferable.

The content of the reactive inorganic particles and/or the reactive irregular-shaped inorganic particles in the above ink composition is preferably 15 to 60% by mass, more preferably 20 to 50% by mass. Here, the content of the reactive inorganic particles and/or the reactive irregular-shaped inorganic particles in the ink composition is the amount of the reactive inorganic particles and/or the reactive inorganic particles based on the total amount of the polymer and the reactive inorganic particles and/or the reactive irregular-shaped inorganic particles. Means the content of sexually modified inorganic particles, and the polymer is solid. When the content of the reactive inorganic particles is within the above range, excellent high hardness and scratch resistance can be obtained.

The above ink composition may contain a solvent for the purpose of adjusting the viscosity. As the solvent, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl Ketones, cyclohexanone, diacetone alcohol, and other ketones; methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate, and other esters; nitromethane, N-methylpyrrolidone, N,N-dimethylformamide, and other nitrogen-containing compounds; Ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dioxolane; halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, tetrachloroethane; other substances such as dimethyl sulfoxide, propylene carbonate; or mixtures thereof. Are preferred. More preferable solvents include methyl ethyl ketone and methyl isobutyl ketone.

The amount of the solvent in the ink composition may be appropriately selected according to the viscosity of the composition, but the solid content of the polymer, the reactive inorganic particles or the reactive irregular-shaped inorganic particles and other photopolymerization initiators described later The content of the solid content of the above is usually about 10 to 50% by mass, preferably 20 to 40% by mass.

The above-mentioned ink composition may contain a photopolymerization initiator. Examples of the photopolymerization initiator include those described in the section of the uneven layer.
The content of the photopolymerization initiator is preferably about 0.5 to 10% by mass, more preferably 1 to 8% by mass, further preferably 3 to 8%, based on the total amount of the above-mentioned polymer and inorganic particles. % By mass, the polymer and inorganic particles are based on solids.

The above ink composition may contain various additives depending on desired physical properties to be obtained. Examples of the additives include ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, defoamers. Agents, fillers and the like.

When the protective layer is composed of a thermosetting resin, the thermosetting resin may be a phenol-formaldehyde resin, a urea/formaldehyde resin, a melamine/formaldehyde resin, a resin obtained by curing an acrylic polyol with an isocyanate, or a polyester polyol. A resin cured with isocyanate, a resin cured with acrylic acid with melamine, or the like can be used. Furthermore, when the protective layer is composed of a thermosetting resin, inorganic particles may be added to the thermosetting resin. As the inorganic particles to be added to the thermosetting resin, the above-mentioned inorganic particles can be used as in the case where the protective layer is composed of the ionizing radiation curable resin.

When the protective layer is made of a thermoplastic resin, acrylic resin, vinyl resin, polyester resin or the like can be used as the thermoplastic resin. Furthermore, when the protective layer is made of a thermoplastic resin, inorganic particles may be added to the thermoplastic resin. As the inorganic particles to be added to the thermoplastic resin, the above-mentioned inorganic particles can be used as in the case where the protective layer is composed of an ionizing radiation curable resin.

The protective layer is prepared by preparing a protective layer coating solution containing the above-mentioned resin and a suitable solvent and the like, and gravure printing method, screen printing method, slit reverse method on the first release layer and the second release layer. Method or a reverse coating method using a gravure plate, and the like can be applied and dried.

Usually, the thickness T ₄ of the protective layer after drying (hereinafter referred to as the thickness T _{4 of the} protective layer) is preferably in the range of 0.5 to 30 μm, and more preferably in the range of 1 to 15 μm. preferable. When the thickness of the protective layer is within the above range, excellent physical properties such as high hardness, scratch resistance, chemical resistance, and stain resistance can be obtained, and further excellent moldability and shape followability can be obtained. be able to. Both the first region and the second region are preferably within the above range. The thickness of the protective layer is the thickness from the base to the top, and, for example, the thickness of 20 points is measured from an image of a cross section taken using a scanning transmission electron microscope (STEM), and the average value of the 20 points is measured. Can be calculated from The accelerating voltage of STEM is preferably 10 kv to 30 kV. The STEM magnification is preferably 1000 to 7,000 times when the measured film thickness is on the micron order, and is preferably 50,000 to 300,000 times when the measured film thickness is on the nano order.

(Peeling layer)
The transfer sheet of the present invention may further include a release layer between the protective layer and the first release layer and the second release layer. By providing the release layer, the release sheet can be released from the transfer sheet, and the transfer layer including the release layer can be reliably and easily transferred to the transfer target.

The release layer contains an acrylic resin, and may further contain at least one selected from the group consisting of a vinyl resin and a polyester resin. Examples of acrylic resins include methyl poly(meth)acrylate, ethyl poly(meth)acrylate, and butyl poly(meth)acrylate. Examples of vinyl resins include polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, and polyvinyl butyral. By including the acrylic resin in combination with the vinyl resin and/or the polyester resin, the release layer can improve the adhesion strength with the release layer.

The release layer may further include a release agent. Examples of the release agent include waxes such as synthetic wax and natural washes. The synthetic wax is preferably a polyolefin wax such as polyethylene wax or polypropylene wax. The release layer can improve releasability by containing a release agent.

The transfer sheet of the present invention may further have functional layers such as an anchor layer, a printing layer, and an adhesive layer on the surface of the protective layer opposite to the substrate.

(Anchor layer)
The anchor layer is a layer provided to improve heat resistance when placed in a high temperature environment such as in-mold molding, and is formed using a curable resin. As the curable resin, an ionizing radiation curable resin or a thermosetting resin can be used. As the ionizing radiation curable resin, a polymer having at least one ionizing radiation curable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, and an epoxy group can be used. For example, acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate can be mentioned, and urethane (meth)acrylate is particularly preferable. Thermosetting resins include phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, acrylic polyol cured with isocyanate resin, polyester polyol cured with isocyanate resin, and acrylic acid cured with melamine. Resin.

Further, the anchor layer preferably contains a resin formed by reacting an acrylic polyol and an isocyanate. When the anchor layer contains a resin obtained by reacting an acrylic polyol with an isocyanate and the printing layer or the adhesive layer contains an acrylic polyol, the adhesion of the printing layer or the adhesive layer can be improved. Further, the affinity between the resin of the protective layer and the resin obtained by reacting the acrylic polyol and the isocyanate of the anchor layer can improve the adhesion between the protective layer, the anchor layer, and the printing layer or the adhesive layer. it can.

Further, the anchor layer is a coating solution for an anchor layer prepared by dissolving or dispersing the above resin with necessary additives added thereto, a gravure coating method, a roll coating method, a comma coating method, It can be formed by coating and drying by a known means such as a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the anchor layer is preferably in the range of 0.1 to 6 μm, more preferably in the range of 1 to 5 μm.

(Print layer)
The print layer is a layer for imparting a desired design property to the decorative molded product, and is a layer provided as desired. Although the design of the print layer is arbitrary, for example, a design composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters and the like can be mentioned. In addition, the print layer can be provided with a pattern pattern layer expressing the above-mentioned pattern and an entire solid layer alone or in combination, and the entire solid layer is usually used as a hiding layer, a coloring layer, a colored hiding layer or the like.

The printing layer is usually a resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin as a binder on the protective layer or the anchor layer, and a pigment of an appropriate color or It is formed by printing with a printing ink containing a dye as a colorant. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing, sublimation transfer printing, and inkjet printing.
The thickness of the printed layer is preferably 0.5 to 40 μm, more preferably 1 to 30 μm from the viewpoint of designability.
By referring to the marker formed at the same time as the colored relaxing layer described above, it is possible to adjust the positional relationship between the pattern of the printed layer and the pattern of the first region and the second region.

(Adhesive layer)
The adhesive layer is a layer formed in order to transfer the transfer layer to the transfer target (resin molding) with good adhesiveness. For this adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the resin molded body is appropriately used. For example, when the material of the resin molded body is acrylic resin, it is preferable to use acrylic resin. When the material of the resin molding is polyphenylene oxide/polystyrene resin, polycarbonate resin, or styrene resin, use acrylic resin, polystyrene resin, polyamide resin, etc. that have affinity with these resins. Is preferred. Furthermore, when the material of the resin molding is polypropylene resin, it is preferable to use chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin.
You may mix|blend additives, such as an ultraviolet absorber and an infrared absorber, with the said resin.

As a method for forming the adhesive layer, there are a coating method such as a gravure coating method and a roll coating method, and a printing method such as a gravure printing method and a screen printing method. If the printed layer has sufficient adhesiveness to the resin molded body, the adhesive layer may not be provided.
Generally, the thickness of the adhesive layer is preferably about 0.1 to 5 μm.

(Antistatic layer)
The transfer sheet of the present invention can be provided with an antistatic layer. The antistatic layer is a layer that is preferably provided in order to prevent foreign matter from adhering to the transfer sheet or the decorative molded product, and is provided on the surface of the base material opposite to the surface on which the release layer is provided.
Examples of the antistatic agent used in the antistatic layer include carboxylic acid-based, sulfonic acid-based, and phosphoric acid-based anionic surfactants; quaternary ammonium-based cationic surfactants; alkylbetaine-based and alkylimidazoline-based surfactants. -Based, alkylalanine-based amphoteric surfactants; alkylene oxide polymers, alkylene oxide copolymers, nonionic surfactants such as aliphatic alcohol-alkylene oxide adducts; carbon, gold, platinum, silver, copper, Inorganic conductive substances such as various metal powders of aluminum, nickel, titanium, molybdenum, etc.; polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyphenylenevinylene, polyvinylcarbazole, or poly containing aminocarboxylic acid, dicarboxylic acid and polyethylene glycol. Preferable examples include conductive polymers such as ether ester amide resins.

The antistatic layer is formed by a coating method such as a gravure coating method or a roll coating method, or a printing method such as a gravure printing method or a screen printing method using a coating material containing the above-mentioned antistatic agent and an organic solvent. The thickness of the antistatic layer thus formed is usually preferably 0.1 to 5 μm. When the thickness of the antistatic layer is within the above range, excellent antistatic performance can be efficiently obtained.
The surface resistance value of the antistatic layer is preferably 10 ⁻⁹ to 10 ⁻¹² Ω/□.

[Transfer sheet manufacturing method]
The transfer sheet of the present invention comprises a step (1) of forming a concavo-convex layer having a concavo-convex shape on a first region of a substrate having a first region and a second region adjacent to the first region,
A step (2) of forming a first release layer on the uneven shape of the uneven layer;
A step (3) of forming a second release layer on the second region of the substrate,
The method includes the step (4) of forming a protective layer on the first release layer and the second release layer.

First, in step (1), an uneven layer having an uneven shape is formed on the first region of the base material.
The uneven layer is prepared by preparing the uneven layer composition described in the section of the transfer sheet, applying the composition on the first region of the substrate by a gravure printing method, a slit reverse method, or the like, and drying, and if necessary, curing. Can be formed. The uneven layer may be formed on the second region of the base material, that is, on the entire surface of the base material from the viewpoint of manufacturing efficiency. When the uneven layer is formed on the second region of the base material, the uneven layer is formed on the uneven layer between the step (1) and the step (2) or between the step (2) and the step (3). It is preferable that a relief layer is provided so that the relief layer is smoother than the relief layer formed on the first region of the substrate.

Next, in step (2), a first release layer is formed on the uneven shape of the uneven layer.
The first release layer is formed by preparing the composition for the first release layer described in the section of the transfer sheet, applying the composition on the uneven shape of the uneven layer by a gravure printing method, and drying. You can

Next, in step (3), a second release layer is formed on the second region of the base material. The second release layer is formed by preparing the composition for the second release layer described in the section of the transfer sheet, applying the composition on the second region of the substrate by a gravure printing method, etc., and drying. You can
Incidentally, the composition for the second release layer, it is possible to use the same composition for the first release layer, from the viewpoint of production efficiency, the first release layer and the second release layer, It is preferable to simultaneously apply, dry, and form. That is, it is preferable to perform the steps (2) and (3) at the same time.

Next, in step (4), a protective layer is formed on the first release layer and the second release layer. The protective layer can be formed by preparing the ink composition described in the section of the transfer sheet, applying the composition on the first release layer and the second release layer, and drying the composition. When the ink composition contains an ionizing radiation-curable resin, the ink composition may be applied on the release layer and then irradiated with ultraviolet rays to be semi-cured or sufficiently cured.

By using the transfer sheet thus obtained, the surface of the obtained decorative molded article has a surface shape (uneven shape) formed by the uneven layer and the first release layer, and a surface shape formed by the second release layer. Is formed. By making the surface shape of the uneven layer and the surface shape of the first release layer different from the surface shape of the second release layer, different textures can be expressed on the surface of the decorative molded product, and the designability can be improved. it can. Further, in the uneven portion formed by the uneven layer and the first release layer, the high frequency component of the unevenness is reduced, so that the contrast is improved and the glare can be suppressed. As a result, the visibility of an image or the like can be improved by applying the uneven portion to a display of a communication device such as a mobile phone or an information device inside a car.

[Method for manufacturing decorative molded products]
The method for producing a decorative molded product of the present invention includes a step of transferring the protective layer of the transfer sheet to a transfer target (resin molded body), and a release sheet (base material, uneven layer, first layer) of the transfer sheet. And a step of peeling the release layer and the second release layer).
A known transfer method can be used for the method for producing the decorated molded product. For example, (i) a method in which a transfer sheet is attached to a pre-transferred body (resin molded body), the transfer layer of the transfer sheet is transferred, and then the release sheet of the transfer sheet is peeled off. ) A transfer sheet is attached to a plate-shaped transfer target (resin molding), the transfer layer of the transfer sheet is transferred, the release sheet of the transfer sheet is peeled off, and then the transfer layer is transferred to the resin molding. And (iii) a method of performing bending processing on a laminated body in which is laminated, and (iii) a method of integrating the transferred sheet (resin molding) with a transfer sheet when injection-molding, and then peeling the release sheet of the transfer sheet [ In-mold molding (injection molding simultaneous transfer decoration method)] and the like. Among them, according to in-mold molding (injection molding simultaneous transfer decoration method), it is possible to carry out decoration molding on a resin molded body having a complicated surface shape such as a three-dimensional curved surface.

As an embodiment of a method for producing a decorated molded product using the transfer sheet of the present invention by in-mold molding,
(A) a step of arranging the transfer layer side of the transfer sheet so as to face the inside of the in-mold molding die;
(B) a step of injecting a resin into the in-mold molding die,
(C) a step of integrating the transfer sheet and the resin, and transferring the transfer layer of the transfer sheet onto the surface of a resin molding (transfer target).
(D) A step of removing the release sheet of the transfer sheet after taking out the resin molded body (transferred body) from the mold.
By manufacturing a decorative molded product by such a manufacturing process, a complicated design can be expressed on the surface of the resin molded body. Further, since the uneven shape of the transfer sheet of the present invention is formed on the surface of the obtained decorative molded product, the contrast is improved, the design is excellent, and the glare on the surface is suppressed.

(Resin molding)
As the resin molded body, it is preferable to use an injection-moldable thermoplastic resin or 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 a thermoplastic resin include polystyrene resin, polyolefin resin, ABS resin (including heat resistant ABS resin), AS resin, AN resin, polyphenylene oxide resin, polycarbonate resin, polyacetal resin, acrylic resin, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

FIG. 4 is a sectional view showing an embodiment of the decorative molded product according to the present invention. The decorative molded product 40 is one in which an adhesive layer 34, a printing layer 33, an anchor layer 32, and a protective layer 31 are sequentially laminated on one surface of a resin molded body (transferred body) 35.

FIG. 5 is a plan view of the decorative molded article according to the present invention shown in FIG. 4 as seen from the protective layer side. The first area 311 is an area in which the uneven shapes of the uneven layer and the first release layer on the first area of the transfer sheet of the present invention are transferred. The first region 311 has an uneven shape (uneven shape on the surface of the first release layer) in which the unevenness of the high-frequency component of the uneven layer is alleviated by the first release layer, so that the contrast of the uneven shape portion is improved. It is possible to improve the design property. Further, it is possible to suppress glare in the uneven portion. Therefore, the first region 311 is preferably applied to the image (moving image). On the other hand, the second area 312 is an area where the shape of the second release layer on the second area of the transfer sheet of the present invention is transferred. The second region 312 has a smooth shape by smoothing the shape of the second release layer, and a sufficient gloss feeling can be obtained.

In the decorative molded product according to the present invention, on the uneven surface on the first region of the protective layer, the arithmetic mean roughness (Ra _x1 ) of JIS B0601:2001 and the cutoff value when the cutoff value is 0.8 mm. It is preferable that the arithmetic average roughness (Ra _y1 ) of JIS B0601:2001 when the thickness is 0.08 mm satisfies the following condition (1).
0.45≦(Ra _x1 −Ra _y1 )/Ra _y1 (1)

Here, the cutoff value is a value indicating the degree to which the low frequency component is cut from the cross-sectional curve formed of the high frequency component (roughness component) and the low frequency component (waviness component). Therefore, when the cutoff value (reference length) is 0.08 mm, the low-frequency component of the roughness curve is more greatly cut than when the cutoff value (reference length) is 0.8 mm. Become. That is, the value of Ra _y1 can be regarded as a high-frequency component on the uneven surface on the first region of the protective layer, and the value of (Ra _x1 −Ra _y1 ) can be regarded as a low-frequency component on the uneven surface on the first region of the protective layer. .. Therefore, the conditions of (1) _{"(Ra x1 -Ra y1) / Ra} y1 " may be regarded as a ratio of the low-frequency component to the high frequency component of the uneven surface.

In the condition _{(1), (Ra x1 -Ra} y1) / If _{Ra y1} is 0.45 or more, to reduce the high-frequency component of the first region on the irregular surface of the protective layer, or to increase the low-frequency component You can In this way, by forming the unevenness with a few high frequency components on the surface of the protective layer, the diffusion of light on the uneven surface is weakened and whitening can be suppressed. Thereby, the contrast is improved and the designability can be improved. Further, it is possible to suppress glare on the uneven surface. Further, the anti-glare property can be secured by increasing the low frequency component.
(Ra _x1 −Ra _y1 )/Ra _y1 is more preferably 0.50 or more.
Further, the upper limit of (Ra _x1 −Ra _y1 )/Ra _y1 is preferably less than 0.90, more preferably 0.80 or less, still more preferably 0.70 or less.

Ra _x1 is preferably 0.12 to 0.20, more preferably 0.12 to 0.18. Moreover, _Ray1 is preferably 0.05 to 0.10, and more preferably 0.06 to 0.09.

Further, on the surface of the second region of the protective layer, the arithmetic mean roughness (Ra _x2 ) of JIS B0601:2001 when the cutoff value is 0.8 mm, and the JIS when the cutoff value is 0.08 mm The arithmetic average roughness (Ra _y2 ) of B0601:2001 preferably satisfies the following condition (2).
0.90≦(Ra _x2 −Ra _y2 )/Ray _y2 (2)

The condition _(2), if _{(Ra x2 -Ra y2) / Ra} y2 is 0.90 or more, it is possible to reduce a high frequency component of the second region surface.
(Ra _x2- Ra _y2 )/Ra _y2 is more preferably 1.20 or more, still more preferably 1.50 or more.
_The upper limit of _{(Ra x2 -Ra y2) / Ra} y2 is not particularly limited, from the viewpoint of having a moderate frequency and low frequency components, the second region surface is preferably 2.50 or less, more preferably Is 2.00 or less.

Ra _x2 is preferably 0.10 to 0.17, more preferably 0.11 to 0.16. Also, _{Ra y2} is preferably 0.03 to 0.06, more preferably 0.04 to 0.06.

_(Ra x1 _-Ra y1) / ratio _{Ra y1} and _{(Ra x2 -Ra y2) / Ra} y2 _{[(Ra x1 -Ra y1) / Ra} y1 ] / _{[(Ra x2 -Ra y2) / Ra} y2 ] is , Preferably 0.56 or less, more preferably 0.50 or less. By setting the ratio to 0.56 or less, the second region can obtain a glossy feeling, a matte feeling, a texture, and the like different from those of the first region.
Incidentally, than the first region and the second region to the mat, the _{(Ra x1 -Ra y1) / Ra} y1 and _{(Ra x2} -Ra y2) ratio / _{Ra y2 [(Ra x2 -Ra y2) / Ra} y2 ]/[(Ra _x1 −Ra _y1 )/Ra _y1 ] may be 3.0 or less.

In addition, by setting {(Ra _x2- Ra _y2 )/Ra _y2 }-{(Ra _x1- Ra _y1 )/Ra _y1 }>0.30, the second region has a glossiness different from that of the first region. A matt feeling and a texture can be obtained, which is preferable. From the viewpoint of making the contrast between the first region and the second region clear, it is more preferably 0.40 or more, still more preferably 0.60 or more.
Note that the second area may be matted rather than the first area so that {(Ra _x1 -Ra _y1 )/Ra _y1 }-{(Ra _x2- Ra _y2 )/Ra _y2 }<-0.30.

The values of Ra _x1 , Ra _y1 , Ra _x2 , and Ra _y2 are each measured at 20 points and calculated by averaging the measured 20 points.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the form described in the embodiments.

1. Contrast The transparent acrylic sheet side surface of the decorative molded products obtained in Examples and Comparative Examples was bonded to the printed surface of a black acrylic resin plate on which an image was printed. In a bright room with a fluorescent lamp, in the protective layer of the decorative molded product, the uneven portion corresponding to the first region of the transfer sheet was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
○: Good contrast between black background and image ×: Poor contrast between black background and image

2. Glitter The surface of the decorative molded article obtained on the transparent acrylic sheet side in the Examples and Comparative Examples was attached to the screen of the display device, the screen of the display device was visually observed from the front, and evaluated according to the following criteria.
<Evaluation criteria>
◯: There was no minute luminance variation in the image light. ×: There was minute luminance variation in the image light.

3. Designability In the protective layers of the decorative molded articles obtained in Examples and Comparative Examples, the portions corresponding to the first region and the second region of the base material of the transfer sheet were visually observed from the protective layer side, and Was evaluated according to the standard.
<Evaluation criteria>
◯: There is a difference in glossiness between the first area and the second area, and the regular reflection in the first area is not too strong. ×: There is no difference in glossiness between the first area and the second area.

4. Measurement of Arithmetic Average Roughness (Ra) 4-1. Measurement with a cut-off value of 0.8 mm Using a surface roughness measuring instrument (model number: SE-3400/Kosaka Laboratory Ltd.), the decorative molded articles produced in Examples and Comparative Examples under the following measurement conditions. Regarding the surface of each of the first region (the portion corresponding to the first region of the base material of the transfer sheet) and the second region (the portion corresponding to the second region of the base material of the transfer sheet) of the protective layer, JIS B0601:2001 Ra was measured.
[Stylus of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip curvature radius: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness tester]
・Reference length (roughness curve cutoff value λc): 0.8 mm
-Evaluation length (reference length (cutoff value λc) x 5): 4.0 mm
・Feeding speed of stylus: 0.5 mm/s
・Spare length: (cutoff value λc) x 2
・Vertical magnification: 2000 times ・Horizontal magnification: 10 times

4-2. Measurement with a cut-off value of 0.08 mm Using a surface roughness measuring instrument (model number: SE-3400/manufactured by Kosaka Laboratory Ltd.), the decorative molded articles produced in Examples and Comparative Examples under the following measurement conditions. Regarding the surface of each of the first region (the portion corresponding to the first region of the base material of the transfer sheet) and the second region (the portion corresponding to the second region of the base material of the transfer sheet) of the protective layer, JIS B0601:2001 Ra was measured.
[Stylus of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip curvature radius: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness tester]
・Reference length (cutoff value λc of roughness curve): 0.08 mm
-Evaluation length (reference length (cutoff value λc) x 5): 0.4 mm
・Feeding speed of stylus: 0.5 mm/s
・Spare length: (cutoff value λc) x 2
-Longitudinal magnification: 2000 times-Lateral magnification: 10 times Since the second region of the protective layer of the decorative molded product obtained in Example 1 is substantially smooth, the measurement of Ra _x2 and Ra _y2 is omitted. did.

(Example 1)
(1) Production of transfer sheet As a base material, a polyethylene terephthalate (PET) base material (manufactured by Toray Industries, Inc., S105, corona treatment) having a thickness of 50 μm was prepared, and was placed on the first region on one surface of the PET base material. After coating the uneven layer coating liquid having the following formulation so that the coating amount after drying becomes 3.0 g/m ² , a coating film is formed, and then aged at room temperature (25° C.) for 72 hours to pre-cure. The uneven layer thus formed was formed.
<Coating liquid for uneven layer>
-Acrylic polyol (manufactured by Soken Chemical Industry Co., Ltd., trade name: Thermolac SU100A, solid content: 50%, solvent: toluene/ethyl acetate mixed solvent): 40 parts by mass-Filler (manufactured by Nippon Shokubai Co., Ltd., trade name: Eposter S12) , Average particle diameter 1.2 μm): 4 parts by mass, isocyanate (manufactured by Mitsui Chemicals, Inc., trade name: Takenate D-110N solid content: 75% solvent: ethyl acetate) (Takenate is a registered trademark): 14 parts by mass. Ethyl acetate: 40 parts by mass

Then, on the pre-cured concavo-convex layer formed on the first region of the base material, and on the second region of the base material, the coating amount after drying the release layer coating liquid having the following formulation was 0.6 g/ m ² and then aged at 40° C. for 96 hours to be cured to completely cure the pre-cured concavo-convex layer and release layer (the first release layer on the concavo-convex layer (thickness: 0: 0.5 μm) and a second release layer (thickness: 0.5 μm) on the second region). The thickness of the uneven layer after complete curing was 2.5 μm.
The values of Ra ₁₁ and Ra _y11 in the first release layer were substantially the same as the values of Ra ₁ and Ra _y1 shown in Table 1, respectively.
<Release layer coating liquid>
-Acrylic polyol (manufactured by Soken Chemical Industry Co., Ltd., trade name: Thermolac SU100A solid content: 50% solvent: toluene/ethyl acetate mixed solvent): 70 parts by mass-isocyanate (manufactured by Mitsui Chemicals, Inc., Takenate D-110N solid) Min: 75% Solvent: Ethyl acetate) (Takenate is a registered trademark): 25 parts by mass Ethyl acetate: 161 parts by mass Methyl isobutyl ketone: 56 parts by mass

Then, a protective layer coating solution having the following formulation was applied on the first release layer and the second release layer so that the coating amount after drying was 6.5 g/m ² to form a coating film. The fusion UV lamp system was used to irradiate the light source under the conditions of an H bulb, a transportation speed of 20 m/min, and an output of 40% to semi-cure the protective layer. The integrated light amount at this time was 15 mJ/m ² when measured with an illuminometer UVPF-A1 manufactured by Eye Graphics Co., Ltd. The thickness of the protective layer after semi-curing was 6 μm.
<Coating liquid for protective layer>
-Urethane acrylate-based UV curable resin composition (manufactured by Dainichiseika Co., Ltd., trade name: Seika Beam HT-X solid content: 35% solvent: toluene/ethyl acetate mixed solvent): 70 parts by mass-Urethane acrylate-based UV curable resin Composition (manufactured by Dainichiseika Co., Ltd., trade name: SEIKA BEAM EXF-HT-1 Solid content: 40% Solvent: toluene/methyl ethyl ketone mixed solvent): 30 parts by mass

Then, an anchor layer coating solution having the following formulation was applied on the protective layer so that the coating amount after drying was 3.0 g/m ² , a coating film was formed, and then dried at 40° C. for 72 hours, It was cured to form an anchor layer having a thickness of 2 μm.
<Coating liquid for anchor layer>
Acrylic polyol (manufactured by Dainichiseika Co., Ltd., trade name: TM-VMAC solid content 25%, solvent: toluene/ethyl acetate/methylethylketone mixed solvent): 100 parts by mass xanthmethylene diisocyanate (manufactured by Dainichiseika Co., Ltd., Product name: PTC-RC3 Solid content: 75% Solvent: Ethyl acetate): 10 parts by mass

Then, an adhesive layer coating liquid having the following formulation was applied on the anchor layer at a coating amount of 2.5 g/m ² to form a coating film. The coating film was dried to form an adhesive layer having a thickness of 2 μm to obtain a transfer sheet.
<Coating liquid for adhesive layer>
-Acrylic resin (manufactured by Dainichiseika Co., Ltd., trade name: TM-R600, solid content 20%, solvent: ethyl acetate/acetic acid-n-propyl/methyl ethyl ketone mixed solvent): 100 parts by mass-methyl ethyl ketone: 40 parts by mass

(2) Manufacture of decorative molded product The adhesive layer side of the obtained transfer sheet is overlaid on a transparent acrylic sheet (Kuraray Co., Ltd., trade name: Comoglas DK3, thickness 2 mm), and the transfer sheet substrate side. Transferred by heating from. Then, after releasing the release sheet (the substrate, the uneven layer, the first release layer, and the second release layer) of the transfer sheet, the resin molding is irradiated with ultraviolet rays (in the air, H bulb, 800 mJ/cm ^{2 ).} Then, the protective layer (thickness 6 μm) was completely cured to obtain a decorative molded product.

(Example 2)
(1) Production of transfer sheet As a base material, a polyethylene terephthalate (PET) base material (manufactured by Toray Industries, Inc., S105, corona treatment) having a thickness of 50 μm was prepared, and one of the following formulations was prepared on one surface of the PET base material. The uneven layer was pre-cured by applying the coating solution for uneven layer so that the coating amount after drying would be 3.0 g/m ² and forming a coating film, followed by aging at room temperature (25° C.) for 72 hours. Was formed.
<Coating liquid for uneven layer>
-Acrylic polyol (manufactured by Soken Chemical Industry Co., Ltd., trade name: Thermolac SU100A, solid content: 50%, solvent: toluene/ethyl acetate mixed solvent): 40 parts by mass-Filler (manufactured by Nippon Shokubai Co., Ltd., trade name: Eposter S12) , Average particle diameter 1.2 μm): 4 parts by mass, isocyanate (manufactured by Mitsui Chemicals, Inc., Takenate D-110N solid content: 75% solvent: ethyl acetate) (Takenate is a registered trademark): 14 parts by mass, ethyl acetate: 40 parts by mass

Then, the pre-cured concavo-convex layer formed on the second region of the base material was coated with a coating solution for a relaxation layer having the following formulation at a coating amount of 1.0 g/m ² , and the coating film was dried at 80°C. A 0.8 μm thick relaxation layer was formed by gravure printing.
<Relaxing layer coating liquid>
・Black gravure ink (manufactured by Showa Ink Industry Co., Ltd., trade name: EIS(NT) black solid content: 32% methyl ethyl ketone/ethyl acetate/methyl isobutyl ketone mixed solvent): 100 parts by mass ・Methyl ethyl ketone: 65 parts by mass

Then, on the pre-cured concavo-convex layer on the first region of the base material and on the relaxing layer on the second region of the base material, the coating amount after drying the release layer coating solution having the following formulation was 0. After coating so as to be 6 g/m ² , it is aged at 40° C. for 96 hours and cured to completely cure the pre-cured concavo-convex layer, and the release layer (the first release layer on the concavo-convex layer (thickness : 0.5 μm), and a second release layer (thickness: 0.5 μm) on the relaxation layer). The thickness of the uneven layer after complete curing was 2.5 μm.
The values of Ra ₁₁ and Ra _y11 in the first release layer were substantially the same as the values of Ra ₁ and Ra _y1 shown in Table 1, respectively. The values of Ra ₂₂ and Ra _y22 in the second release layer were substantially the same as the values of Ra ₂ and Ra _y2 shown in Table 1, respectively.
<Release layer coating liquid>
-Acrylic polyol (manufactured by Soken Chemical Industry Co., Ltd., trade name: Thermolac SU100A solid content: 50% solvent: toluene/ethyl acetate mixed solvent): 70 parts by mass-isocyanate (manufactured by Mitsui Chemicals, Inc., Takenate D-110N solid) Min: 75% Solvent: Ethyl acetate) (Takenate is a registered trademark): 25 parts by mass Ethyl acetate: 161 parts by mass Methyl isobutyl ketone: 56 parts by mass

Then, in the same manner as in Example 1, a protective layer, an anchor layer, and an adhesive layer were sequentially formed on the first release layer and the second release layer to obtain a transfer sheet.

(2) Manufacture of decorative molded product The surface of the obtained transfer sheet on the side of the adhesive layer is overlaid on a transparent acrylic sheet (Kuraray Co., Ltd., trade name: Comograss DK3, thickness 2 mm) to form a base material for the transfer sheet. Heat transfer was performed from the side. After peeling off the release sheet (base material, uneven layer, relaxing layer, first release layer, and second release layer) of the transfer sheet, the resin molded body is irradiated with ultraviolet rays (in air, H bulb, 800 mJ/cm). ² ) Then, the protective layer (thickness 6 μm) was completely cured to obtain a decorative molded product.

(Comparative Example 1)
(1) Production of Transfer Sheet A transfer sheet was obtained in the same manner as in Example 2 except that the first release layer was not formed on the uneven layer formed on the first region of the base material. ..

(2) Production of decorative molded product A decorative molded product was obtained in the same manner as in Example 2 using the obtained transfer sheet.

(Comparative example 2)
(1) Production of Transfer Sheet In Example 2, the first release layer was not formed on the uneven layer formed on the first region of the base material, and the relaxation layer was not formed on the second region of the base material. A transfer sheet was obtained in the same manner as in Example 2 except for the above.

(2) Production of decorative molded product A decorative molded product was obtained in the same manner as in Example 2 using the obtained transfer sheet.

The transfer sheet of the present invention can be preferably used in the fields of communication devices such as mobile phones, information devices inside automobiles, and home appliances. In particular, since it has a high contrast and is excellent in design and suppresses glare on the surface, it can be suitably used for displays of communication devices such as mobile phones and information devices inside automobiles.

10, 20, 30 Transfer sheet 40 Decorative molded product 1, 11, 21 Base material 2, 12, 22 Concavo-convex layer 3, 13, 23 First release layer 4, 14, 24 Second release layer 5, 15, 25, 31 Protective layer 16, 26 Relaxation layer 17, 27, 32 Anchor layer 18, 28, 33 Printing layer 19, 29, 34 Adhesive layer 35 Resin molded body (transferred body)
311 First area of decorative molded article 312 Second area of decorative molded article P First area Q Second area X Release sheet Y Transfer layer

Claims (8)

A base material having a first region and a second region adjacent to the first region,
An uneven layer having an uneven shape provided on the first region of the substrate,
A first release layer formed on the uneven shape of the uneven layer,
A second release layer provided on the second region of the substrate,
Said first release layer, a protective layer formed on the second release layer possess,
The ratio of the thickness _{T 1} of the uneven layer and the thickness _{T 2} of the said first releasing layer _(T 1 / _{T 2)} is, the transfer sheet is 0.2 to 10. The transfer sheet according to claim 1, wherein the uneven layer contains an ionizing radiation curable resin. The transfer sheet according to claim 1, further comprising an uneven layer between the base material in the second region and the second release layer. The transfer sheet according to claim 3, further comprising a relaxation layer between the uneven layer provided on the second region of the base material and the second release layer. A step (1) of forming a concavo-convex layer having a concavo-convex shape on a first region of a base material having a first region and a second region adjacent to the first region;
A step (2) of forming a first release layer on the uneven shape of the uneven layer;
A step (3) of forming a second release layer on the second region of the substrate,
Possess said first release layer, and a step (4) of forming a protective layer on the second release layer,
Wherein the ratio between the thickness _{T 2} of the uneven layer thickness _{T 1} and the first release layer _(T 1 / _{T 2)} is from 0.2 to 10, a manufacturing method of the transfer sheet. The method for manufacturing a transfer sheet according to claim 5, wherein in the step (1), the uneven layer is formed on the second region of the base material. The method for manufacturing a transfer sheet according to claim 6, wherein, before the step (2), a relaxation layer is formed on the uneven layer provided on the second region of the base material. A step of transferring the protective layer of the transfer sheet according to any one of claims 1 to 4 onto a transfer target;
Base material of the transfer sheet, the uneven layer, and a step of peeling off the first release layer, and a second release layer,
And a method for producing a decorated molded article.