JP2018126906A - Release sheet, transfer sheet, and method of manufacturing decorative molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release sheet capable of realizing a decorative molding excellent in designability and good in yield.SOLUTION: A release sheet 10 includes an irregularity layer 12 and a release layer 13 on a support medium 11. In the release sheet 10, a maximum height Ry measured in accordance with JIS B0601:1994 at a cutoff value 0.8 mm of the irregularity layer, arithmetic average roughness Ra measured in accordance with JIS B0601:1994 at a cutoff value 0.8 mm of the irregularity layer, ten-point average roughness Rz measured in accordance with JIS B0601:1994 at a cutoff value 0.8 mm of the irregularity layer, and a thickness T of the release layer satisfy following conditions (1) and (2): 3.0≤Ry/Ra (1); and T/Rz≤0.50 (2).SELECTED DRAWING: Figure 1

Description

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

  Conventionally, in the fields of household electrical appliances, automobile interior parts, and miscellaneous goods, it is possible to achieve high functionality and design by creating decorative molded products with decorations such as letters and pictures on the surface of the transfer object. Has been expressed.

  There is a transfer method as a method for obtaining a decorative molded product that decorates the surface of the transfer object. The transfer method uses a transfer sheet in which a transfer layer composed of a release layer, a design layer, an adhesive layer, etc. is formed on a support, heat-presses the transfer layer in close contact with the transfer object, This is a method of performing decoration by peeling and transferring only the transfer layer onto the surface of the transfer object.

  For example, Patent Document 1 discloses a release layer containing a matting agent entirely on a base sheet, a mask layer partially containing an active energy ray-curable resin, a release layer and a design layer as a transfer layer. A partially uneven transfer sheet characterized in that is formed is disclosed.

Japanese Patent No. 5095598

  However, the transfer layer transferred by the partial mat transfer sheet of Patent Document 1 has an in-plane portion where the uneven portion is distorted and viewed when viewed from an oblique direction, even when the defect is not viewed when viewed from the front. Occasionally, the design was not sufficient. A decrease in designability also leads to a decrease in the yield of decorative molded products.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the release sheet and transfer sheet from which the decorative molded product excellent in the designability and the yield is obtained. Moreover, this invention makes it a subject to provide the manufacturing method of the decorative molded product using this transfer sheet.

In order to solve the above problems, the present invention provides the following [1] to [3].
[1] A release sheet having a concavo-convex layer and a release layer on a support, wherein the concavo-convex layer has a maximum height Ry at a cut-off value of 0.8 mm measured according to JIS B0601: 1994, JIS B0601: The arithmetic mean roughness Ra at the cut-off value of 0.8 mm measured according to 1994, and the cut-off value at the cut-off value of 0.8 mm measured according to JIS B0601: 1994 A release sheet in which the point average roughness Rz and the thickness T of the release layer satisfy the following conditions (1) and (2).
3.0 ≦ Ry / Ra (1)
T / Rz ≦ 0.50 (2)
[2] A transfer sheet having a transfer layer on the release sheet according to [1].
[3] A method for producing a decorative molded product, comprising: a step of transferring the transfer layer of the transfer sheet according to the above [2] to a transfer target; and a step of peeling the release sheet of the transfer sheet.

  ADVANTAGE OF THE INVENTION According to this invention, the release sheet and transfer sheet from which the decorative molded product excellent in the designability and the yield can be obtained can be provided. Moreover, according to this invention, the decorative molded product excellent in the designability and the yield can be manufactured easily.

It is sectional drawing which shows an example of the release sheet of this invention. It is sectional drawing which shows an example of the release sheet of a comparative example.

[Release sheet]
The release sheet of the present invention has a concavo-convex layer and a release layer on a support, and the maximum height Ry at a cut-off value of 0.8 mm of the concavo-convex layer measured according to JIS B0601: 1994. , Arithmetic mean roughness Ra at a cut-off value of 0.8 mm of the concavo-convex layer measured according to JIS B0601: 1994, cut-off value of the concavo-convex layer measured according to JIS B0601: 1994 at 0.8 mm The ten-point average roughness Rz and the thickness T of the release layer satisfy the following conditions (1) and (2).
3.0 ≦ Ry / Ra (1)
T / Rz ≦ 0.50 (2)

  The release sheet is used as a release sheet for the transfer sheet of the present invention described later. The release sheet is peeled off after the transfer layer is transferred to a transfer object such as a resin molded body.

FIG. 1 is a cross-sectional view showing an embodiment of a release sheet of the present invention. The release sheet 10 of FIG. 1 has a configuration having an uneven layer 12 and a release layer 13 on a support 11.
The structure of a release sheet is not limited to the structure of FIG. 1, You may have layers other than a support body, an uneven | corrugated layer, and a release layer.

<Condition (1) and Condition (2)>
The release sheet of the present invention satisfies the above conditions (1) and (2).
In condition (1), the maximum height Ry at a cut-off value of 0.8 mm of the uneven layer measured according to JIS B0601: 1994, and the cut-off value of the uneven layer measured according to JIS B0601: 1994 is 0. The ratio [Ry / Ra] with the arithmetic average roughness Ra at 0.8 mm is required to be 3.0 or more.
Ry is the maximum height of the roughness curve and Ra is the arithmetic mean of the roughness curve. That is, Ry / Ra of the condition (1) indicates a specific level of unevenness existing in the uneven layer. Specifically, Ry / Ra of 3.0 or more in the condition (1) indicates that there are specific irregularities exceeding 3.0 times the average irregularities.

When the transfer layer of a transfer sheet having a transfer layer on a release sheet having Ry / Ra of 3.0 or more is transferred to a transfer target, defects may be visually recognized on the surface of the transfer layer. Specifically, even if no defects are visible on the transfer layer when viewed from the front, the areas where the transfer layer is distorted and viewed due to specific irregularities when viewed from an oblique direction are in-plane. May be found in
However, even if the release sheet of the present invention has specific irregularities with Ry / Ra of 3.0 or more, the transfer layer is distorted when viewed obliquely by satisfying the condition (2). It is possible to suppress visual recognition.

Under the condition (2), the ten-point average roughness Rz at the cut-off value of 0.8 mm of the concavo-convex layer measured according to JIS B0601: 1994 and the thickness T of the release layer are T / Rz ≦ 0. .50.
Rz is a parameter serving as an index of the randomness of the unevenness. Therefore, when Rz is large, even if specific irregularities exist in the transferred layer after transfer, it tends to be easy to suppress the vicinity of the specific irregularities from being distorted. However, when the release layer is formed on the uneven layer, the randomness of the unevenness on the surface of the release sheet is alleviated.
In the condition (2), T / Rz being 0.50 or less means that the randomness of the unevenness on the surface of the release sheet is not alleviated too much by the release layer, as shown in FIG. Therefore, even if there are specific irregularities that satisfy the condition (1), by satisfying the condition (2), it is possible to suppress the specific irregularities of the transfer layer after transfer from being visually recognized. , Designability and yield can be improved.
On the other hand, when T / Rz exceeds 0.50, as shown in FIG. 2, the randomness of the unevenness on the surface of the release layer is excessively relaxed, and the specific unevenness of the transfer layer after transfer is visually recognized. The transfer layer is distorted and visually recognized.

When Ry / Ra is large, blocking tends to be suppressed, and when Ry / Ra is too large, the transferred layer tends to be whitened.
For this reason, Ry / Ra in the condition (1) is preferably 3.0 to 15.0, more preferably 5.0 to 12.0, and 6.0 to 10.0. Is more preferable.
In the present specification, “AA to BB” means “AA to BB”. The same applies hereinafter.

In addition, as T / Rz is smaller, it is easier to suppress the transfer layer from being distorted and viewed when viewed from an oblique direction. However, if T / Rz is too small, the uneven layer after transfer is likely to be whitened. In addition, when the transfer object is used on the front surface of a display element such as a liquid crystal display element, if T / Rz is too small, glare is likely to occur. “Glitter” refers to a phenomenon in which minute brightness variations are seen in image light due to the uneven structure.
For this reason, T / Rz of condition (2) is preferably 0.10 to 0.50, more preferably 0.12 to 0.48, and 0.15 to 0.45. Is more preferable.

In the present invention, Ry, Ra, and Rz, and Sm described later, are samples of 5.5 cm × 5.5 cm from the central portion of the release sheet intermediate (laminated body having a concavo-convex layer on the support). Cut out, measure 10 points in the vertical direction of the sample at intervals of 0.5 cm, and measure 10 points in the horizontal direction of the sample at intervals of 0.5 cm to obtain an average value of the measured values of a total of 20 points.
In the present invention, the thickness T of the release layer is taken as a cross-sectional photograph of a cross-section obtained by cutting the central portion of the release sheet in the vertical direction, and the thickness of the release layer is at least 20 at intervals of 500 μm from the cross-sectional photograph. The average value when calculated.

<Surface shape of other uneven layers>
The maximum height Ry of the concavo-convex layer is preferably 0.7 to 7.0 μm, more preferably 1.0 to 6.0 μm, and further preferably 1.5 to 5.0 μm.
When Ry is 0.7 μm or more, blocking can be easily suppressed, and when Ry is 7.0 μm or less, whitening of the transfer layer after transfer can be easily suppressed.

The arithmetic average roughness Ra of the concavo-convex layer is preferably 0.05 to 2.00 μm, more preferably 0.10 to 1.00 μm, and further preferably 0.20 to 0.50 μm. .
By setting Ra to 0.05 μm or more, it is possible to easily impart antiglare properties to the transferred layer after transfer, and by setting Ra to 2.00 μm or less, it is possible to easily suppress whitening of the transferred layer after transfer. .

The ten-point average roughness Rz of the concavo-convex layer is preferably 0.20 to 5.00 μm, more preferably 0.30 to 4.00 μm, and further preferably 0.50 to 2.80 μm. preferable.
By setting Rz to 0.20 μm or more, defects in the transfer layer after transfer can be made inconspicuous. Further, by setting Rz to 5.00 μm or less, whitening of the transfer layer after transfer can be easily suppressed. When Rz is 5.00 μm or less, glare can be easily suppressed when the transfer object is used on the front surface of a display element such as a liquid crystal display element.

In the concavo-convex layer, it is preferable that the ten-point average roughness Rz when the concavo-convex layer has a cut-off value of 0.8 mm and the arithmetic average roughness Ra of the concavo-convex layer satisfy the relationship of Rz / Ra ≦ 10.0.
Rz / Ra is a parameter that more accurately indicates the randomness of the unevenness. When Rz / Ra is 10.0 or less, the randomness of the unevenness layer is weak. By setting Rz / Ra to 10.0 or less, the unevenness of the transfer layer after transfer can be homogenized and the design can be improved.
Rz / Ra is more preferably from 3.0 to 8.0, and even more preferably from 4.0 to 7.0, from the viewpoint of the balance between the design properties and the conspicuousness of defects.

  The concavo-convex layer preferably has an concavo-convex average interval Sm of 10 to 200 μm, more preferably 20 to 100 μm, measured according to JIS B0601: 1994. More preferably, it is 30-80 micrometers.

<Support>
As the support constituting the release sheet, polyolefin resins such as polyethylene and polypropylene, vinyl chloride such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, etc. Resins, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, nylon 6 or nylon Examples thereof include a plastic film made of a resin such as polyamide resin represented by No. 66 and the like.
Among these plastic films, a biaxially stretched polyester film that is excellent in heat resistance and dimensional stability and excellent in alignment at the time of transfer is preferable.

The thickness of the support is preferably 12 to 150 μm, more preferably 25 to 100 μm, from the viewpoints of moldability, shape followability, and handling.
Further, in order to enhance the adhesion to the resin layer or the like, the surface of the support may be subjected in advance to a physical treatment such as corona discharge treatment or oxidation treatment, or application of a paint called an anchor agent or a primer. .

<Uneven layer>
The uneven shape of the uneven layer is a shape close to the uneven shape formed on the surface of the transfer object after the transfer layer is transferred to the transfer object. That is, after transferring the transfer layer to the transfer object, a shape close to the uneven shape of the uneven layer is formed on the surface of the transfer object. Thus, by forming unevenness on the transferred object, the design of the transferred object can be improved, or the antiglare property can be imparted to the transferred object.

The uneven layer constituting the release sheet preferably contains a resin component such as a thermoplastic resin, a cured product of a thermosetting resin composition, 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 uneven layer, and the ratio is preferably 70% by mass or more, and more preferably 90% by mass or more.
Among the above resin components, a cured product of an ionizing radiation curable resin composition that is excellent in strength and capable of giving an accurate and precise shape because it is instantly cured is preferable. In addition, from the viewpoint of easily obtaining the effect of the ionizing radiation curable resin composition, it is preferable that 70% by mass or more of the cured product of the ionizing radiation curable resin composition is included among all the resin components constituting the uneven layer. More preferably, it is contained more than 95 mass%, more preferably more than 95 mass%, and still more preferably 100 mass%.

The uneven layer may be formed by coating, but from the viewpoint of forming an accurate and precise shape, the uneven layer is preferably formed by printing using a plate having a shape complementary to the shape of the uneven layer. Details of the method for forming the concavo-convex layer using a plate will be described later.
In addition, the uneven | corrugated layer by a coating method is formed by apply | coating and drying the coating liquid containing particle | grains on a support body. The coating method is not preferable as a means for forming a concavo-convex layer because Ry, Ry / Ra, Rz / Ra, etc. tend to become extremely large due to particle aggregation.

  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, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

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 bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, 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 a transfer sheet, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups, and in particular, an ethylenically unsaturated group. A polyfunctional (meth) acrylate compound having two or more saturated bonding groups is more preferable. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

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

Moreover, examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth) acrylate, for example.
A preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting (meth) acrylic acid with a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like. (Meth) acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like with polybasic acids and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resins, It is a (meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with a phenol and (meth) acrylic acid.
The ionizing radiation curable resin can be used alone or in combination of two or more.

When the ionizing radiation curable resin is an ultraviolet curable resin, the uneven 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's ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be mentioned.

The thickness of the concavo-convex layer is not particularly limited, but if the concavo-convex layer is too thick, cracks are likely to occur in the concavo-convex layer during transfer. For this reason, the thickness of the uneven layer is preferably 20.0 μm or less, more preferably 18.0 μm or less, and even more preferably 15.0 μm or less.
In order to suppress the exposure of the support, the [thickness of the uneven layer−Ry of the uneven layer] is preferably more than 0 μm, more preferably 0.5 μm or more, and 1.0 μm or more. Further preferred.
The thickness of the concavo-convex layer is such that a 5.5 cm × 5.5 cm sample is cut out from the center part of the intermediate of the release sheet (laminate having the concavo-convex layer on the support), and 1 cm intervals from the center of the sample. It is set as the average value of the thickness of the uneven | corrugated layer measured 25 places in a grid | lattice form. The thickness of the concavo-convex layer is determined by measuring the total thickness of the sample (for example, the total thickness of the support and the concavo-convex layer) using, for example, a contact-type film thickness measuring instrument, and calculating the support thickness from the total thickness. It can be calculated by subtracting.

  From the viewpoint of improving the releasability between the release sheet and the transfer layer, it is preferable that the uneven layer contains substantially no particles. Specifically, the content of the particles in the uneven layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, further preferably less than 0.01% by mass, More preferably, it is 0 mass%.

<Release layer>
The release layer has a role of improving the release property of the transfer layer. Further, by forming the release layer on the concavo-convex layer, the high-frequency component of the concavo-convex shape of the concavo-convex layer can be reduced, and whitening and glare of the transfer object can be easily suppressed.

The release layer is preferably mainly composed of a resin.
The resin of the release layer is not particularly limited as long as it has a predetermined film strength and has a low adhesive strength with the transfer layer. General-purpose thermoplastic resin, cured product of thermosetting resin composition, ionizing radiation Examples include cured products of curable resin compositions. Specifically, fluorine resin, silicone resin, acrylic resin, polyester resin, polyolefin resin, polystyrene resin, polyurethane resin, cellulose resin, vinyl chloride-vinyl acetate copolymer resin, nitrified cotton Etc.
Among these, the hardened | cured material of a thermosetting resin composition is preferable, and the thermosetting resin composition containing an acrylic polyol and isocyanate is more preferable.

  The release layer 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 washes. The synthetic wax is preferably a polyolefin wax such as polyethylene wax or polypropylene wax.

The thickness T of the release layer is not particularly limited as long as the condition (2) is satisfied. Note that if the thickness of the release layer is too large, the “irregularities of the high-frequency component of the concavo-convex layer” that may contribute to the invisible appearance of defects in the concavo-convex layer after transfer may be excessively reduced. On the other hand, if the thickness of the release layer is too small, the concavo-convex layer after transfer is likely to be whitened or glaring is likely to occur.
For this reason, the thickness T of the release layer is preferably less than 1.0 μm, more preferably 0.1 μm or more and less than 1.0 μm, and further preferably 0.2 to 0.8 μm.

The release sheet may have other layers.
Examples of other layers include an antistatic layer. By having the antistatic layer, it is possible to suppress the peeling electrification when peeling the release sheet, and to improve the transfer workability.

The antistatic layer preferably contains an antistatic agent such as an electron conductive antistatic agent or an ion conductive 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 antistatic layer preferably has a surface resistivity adjusted to a range of 1.0 × 10 ⁻⁹ Ω / □ to 1.0 × 10 ⁻¹² Ω / □.
An antistatic agent may be contained in another layer such as a resin layer to exhibit antistatic properties.

<Haze>
The release sheet preferably has a haze measured according to JIS K7136: 2000 of more than 2.0%, more preferably more than 2.0% and not more than 10.0%, more than 2.5%. More preferably, it is 8.0% or less.
The haze of the release sheet is reflected as the external haze of the decorative molded product. For this reason, the defect of the transfer layer after transfer can be made inconspicuous by setting the haze of the release sheet to more than 2.0%. Moreover, whitening of the transfer layer after transfer can be suppressed by setting the haze of the release sheet to 10.0% or less.

<Method for producing release sheet>
The release sheet can be produced, for example, by the following steps (A1) to (A2).

(A1) The process of apply | coating the uneven | corrugated layer forming ink containing an ionizing radiation curable resin composition on a support body, and forming the layer containing an ionizing radiation curable resin composition.
(A2) A step of forming an uncured uneven layer using a plate having a shape complementary to the shape of the uneven layer, and simultaneously curing the formed uneven layer by irradiating with ionizing radiation.
(A3) A step of forming a release layer on the uneven layer.

When the ionizing radiation curable resin composition contains a solvent, it is preferable to dry the solvent in the step (A1).
In the step (A3), the release layer can be formed, for example, by applying and drying a release layer forming ink on the uneven layer.

  The plate used in the step (A2) can be obtained by engraving the surface of the cylinder into a desired shape by, for example, etching, sandblasting, cutting and laser processing, or a combination thereof. Alternatively, it can be obtained by producing a long male plate (a plate having the same shape as that of the concavo-convex layer) by laser engraving, stereolithography, etc., and wrapping it around the surface of the cylinder. .

Among the plate making means, sand blasting is preferable. When engraving on the cylinder surface with sandblasting, by adjusting the number of collisions of the abrasive with the cylinder surface, it is possible to obtain a shape with moderate randomness while suppressing the formation of extremely specific irregularities. be able to. That is, a plate formed by sandblasting is preferable in that Ry / Ra and Rz / Ra can be easily adjusted to the above-described ranges.
In sandblasting, for example, by adjusting the material of the cylinder surface, the particle diameter of the abrasive, the material of the abrasive, the number of collisions of the abrasive with the cylinder, the distance between the injection nozzle and the cylinder, the injection pressure, the injection frequency, etc. Uneven shape can be adjusted.

  Note that the randomness of the irregularities can be imparted also by etching, cutting and laser processing, but since these means impart artificial randomness by a program or the like, they are inferior to sandblasting.

  The surface of the plate used in the step (A2) is preferably hard-plated with chromium or the like.

Moreover, a release sheet can be manufactured also by the following (B1)-(B3) processes, for example.
(B1) A step of filling an uneven layer forming ink in a plate having a shape complementary to the shape of the uneven layer.
(B2) A step of transferring the concavo-convex layer forming ink filled in the plate onto the support and drying and curing as necessary to form the concavo-convex layer.
(B3) A step of forming a release layer on the uneven layer.

  From the viewpoint of forming an accurate and precise shape, the above-described steps (A1) to (A3) are preferable.

  In the step (A3) and the step (B3), it is preferable to form the release layer thin in order to easily satisfy the condition (2).

[Transfer sheet]
The transfer sheet of the present invention has a transfer layer on the above-described release sheet of the present invention.

<Transfer layer>
The transfer layer is a layer that is transferred to the transfer object. Examples of the transfer layer include a protective layer, an anchor layer, and an adhesive layer in order from the side closer to the release sheet.

<Protective layer>
The protective layer constituting the transfer layer is a layer containing a cured product of the curable resin composition. The protective layer has a role of 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 object.

The protective layer preferably contains a cured product of the 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, more preferably 80% by mass or more, and 90% by mass or more. Even more preferably.
Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition, and among these, a cured product of the ionizing radiation curable resin composition is preferable.
Moreover, although a protective layer may contain a thermoplastic resin, it is preferable that the quantity is a trace amount from a viewpoint of improving abrasion resistance. Specifically, the content of the thermoplastic resin in the protective layer is preferably less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.1% by mass, More preferably, it is 0 mass%.

The embodiment of the curable resin composition of the protective layer is the same as the embodiment of the curable resin composition of the uneven layer described above.
The cured product of the curable resin composition is in a semi-cured state at the time of forming the protective layer, and after being transferred to the transfer object, the cured curable resin composition is cured by heating, irradiation with ionizing radiation, or the like. May be allowed to proceed to complete curing. By doing in this way, since the followable | trackability of the transfer sheet with respect to a to-be-transferred object becomes favorable, a moldability can be made favorable.

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

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

The average particle diameter 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 diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is represented by a cumulative distribution. The 50% particle diameter 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.

  The thickness of the protective layer is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and still more preferably 3 to 10 μm, from the viewpoint of the balance between surface hardness and moldability.

<Adhesive layer>
The adhesive layer has a role of improving the transfer work by improving the adhesion between the transfer object such as a resin molded body and the transfer layer.
In addition, when the adhesiveness between the protective layer and the transfer object is good, the adhesive layer may not be provided.

For the adhesive layer, it is preferable to use a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer object. For example, when the material of the transfer object is an acrylic resin, it is preferable to use an acrylic resin. If the material of the transferred material is polyphenylene oxide / polystyrene resin, polycarbonate resin, or styrene resin, use an acrylic resin, polystyrene resin, polyamide resin, or the like that has an affinity for these resins. Is preferred. Furthermore, when the material of the transferred material is a polypropylene resin, it is preferable to use a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin.
You may mix | blend additives, such as a ultraviolet absorber and an infrared absorber, with an adhesive bond layer.
The thickness of the adhesive layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

<Anchor layer>
The anchor layer is a layer provided as necessary 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 and the adhesive layer.

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.
Embodiments of the thermosetting resin composition and the ionizing radiation curable resin composition of the anchor layer are the same as those 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, and more preferably 0.5 to 5 μm.

<Print layer>
The transfer layer may further have a printing layer. The printed layer has a role of imparting a desired design property to the decorative molded product.
The pattern of the printing layer is arbitrary, and examples thereof include wood grain, stone grain, cloth grain, grain grain, circle, square, polygon, geometric pattern, character, solid printing, and the like.

The printed layer preferably contains a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and a pigment and / or a dye.
The thickness of the printing layer is preferably 0.5 to 40 μm, more preferably 1 to 30 μm from the viewpoint of design.

  Each layer such as a protective layer, an adhesive layer, an anchor layer, and a printing layer constituting the transfer layer is prepared, for example, by adjusting ink containing the constituent components of each layer, and on the release sheet, such as a gravure coating method and a roll coating method. It can be formed by coating and drying by a printing method such as a coating method, a gravure printing method, a screen printing method, etc., and curing by irradiation with ionizing radiation as required.

[Method of manufacturing decorative molded product]
The method for producing a decorative molded product of the present invention includes a step of transferring the transfer layer of the transfer sheet of the present invention described above to a transfer target, and a step of peeling the release sheet of the transfer sheet.
Examples of the material to be transferred include a resin molded body.

  A known transfer method can be used for the method of manufacturing the decorative molded product. For example, (i) a method in which a transfer sheet is attached to a preliminarily molded transfer object, the transfer layer of the transfer sheet is transferred, and then the release sheet of the transfer sheet is peeled off; A method of sticking a transfer sheet to a transfer material, transferring the transfer layer of the transfer sheet, peeling off the release sheet of the transfer sheet, and then forming a transfer material on which the transfer layer is laminated, (iii) ) A method of integrating a transfer material with a transfer sheet at the time of injection molding and then peeling the release sheet of the transfer sheet [in-mold molding (injection molding simultaneous transfer decoration method)]. Among them, according to in-mold molding (injection molding simultaneous transfer decoration method), it is possible to perform decorative 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 producing a decorative molded product using the transfer sheet of the present invention by in-mold molding,
(Z1) a step of disposing the transfer layer side of the transfer sheet toward the inside of the in-mold mold,
(Z2) a step of injecting a resin into the in-mold mold,
(Z3) integrating the transfer sheet and the resin, and transferring the transfer layer of the transfer sheet onto the surface of a resin molded body (transfer object);
(Z4) After removing the resin molded body (transfer object) from the mold, there is a step of peeling the release sheet of the transfer sheet.
When the protective layer is in a semi-cured state, it is preferable to completely cure the protective layer by irradiating with ultraviolet rays after the completion of the step (z4).

<Resin molding>
As the resin molding, it is preferable to use a thermoplastic resin or a thermosetting resin that can be injection-molded, 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 resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

1. Production of plate 1-1. Production of Plate A A cylinder having a copper plating layer having a thickness of 200 μm was prepared. While the cylinder was rotating, the surface of the cylinder was sandblasted under the following conditions to prepare plate A.
[Sandblasting conditions]
・ Cylinder diameter: 300mm
・ Number of passes ^* : 5 times ・ Abrasive particles: Glass beads with an average particle diameter of 83 μm ・ Diameter of injection nozzle: 400 mm
・ Injection pressure: 0.20 MPa
・ Frequency: 90Hz
* “Number of passes” is the number of rotations of the cylinder from the start to the end of the sandblasting process. That is, the longer the number of passes, the longer the time for sandblast processing.

1-2. Preparation of plates B and C Plate B was prepared in the same manner as plate A, except that the injection pressure was changed to 0.23 MPa.
Plate C was prepared in the same manner as Plate A, except that the injection pressure was changed to 0.26 MPa.

2. Production of release sheet [Example 1]
On a polyethylene terephthalate film having a thickness of 50 μm, an ink for forming an uneven layer having the following formulation was applied and dried to form an uncured uneven layer.
<Ink for forming uneven layer>
-60 parts by mass of ionizing radiation curable resin composition (manufactured by Kyoei Chemical Co., ES105M)
・ Methyl ethyl ketone 40 mass parts ・ Silicone leveling agent 0.5 mass parts

  Next, using the plate B produced in the above “1”, an uncured resin layer is shaped, and at the same time, ionizing radiation is irradiated from the polyethylene terephthalate film side to cure the shaped resin layer, and a polyethylene terephthalate film An uneven layer was formed thereon. It was 3.0 micrometers when the thickness of the uneven | corrugated layer was measured by the method as described in this specification text.

Next, a release layer forming ink having the following formulation was applied on the entire surface of the uneven layer and dried to form a release layer to obtain a release sheet. It was 0.3 micrometer when the thickness of the mold release layer was measured by the method as described in this specification text.
<Ink for forming release layer>
Acrylic polyol 70 parts by mass (manufactured by Soken Chemical Co., Ltd., trade name: Thermolac SU100A)
・ Isocyanate 25 parts by mass (Mitsui Chemicals, trade name: Takenate D-110N)
・ Ethyl acetate 161 parts by mass ・ Methyl isobutyl ketone 56 parts by mass

[Example 2]
A release sheet was obtained in the same manner as in Example 1 except that the thickness of the release layer was changed to 0.5 μm.

[Example 3]
A release sheet was obtained in the same manner as in Example 1 except that the thickness of the release layer was changed to 0.8 μm.

[Example 4]
A release sheet was obtained in the same manner as in Example 1 except that the plate B was changed to the plate A, the thickness of the uneven layer was changed to 2.5 μm, and the thickness of the release layer was changed to 0.5 μm.

[Example 5]
A release sheet was obtained in the same manner as in Example 1 except that the plate B was changed to the plate C, the thickness of the uneven layer was changed to 3.5 μm, and the thickness of the release layer was changed to 0.5 μm.

[Comparative Example 1]
A release sheet was obtained in the same manner as in Example 1 except that the thickness of the release layer was changed to 1.0 μm.

3. Measurement and Evaluation The following evaluation and measurement were performed on the release sheets obtained in Examples and Comparative Examples or intermediates of release sheets. The results are shown in Table 1.

3-1. Surface shape of concavo-convex layer Using a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Co., Ltd.), the intermediates (on the support) of the release sheets of Examples and Comparative Examples under the following measurement conditions Ry, Ra, Rz and Sm of JIS B0601: 1994 with a cut-off value of 0.8 mm were measured. In addition, Ry, Ra, Rz, and Sm were made into the average value of the measured value of 20 points | pieces according to description of the specification text.
[Surface probe for surface roughness detection]
Product name SE2555N manufactured by Kosaka Laboratory Ltd. (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
Reference length (roughness curve cut-off value λc): 0.8 mm
Evaluation length (reference length (cutoff value λc) × 5): 4.0 mm
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

3-2. Haze According to JIS K7136: 2000, the haze of the release sheet obtained in the examples and comparative examples was measured. The light incident surface was on the support side.

3-3. Appearance of the decorative molded product After performing the steps (z1) to (z4) in the main body of the specification using the transfer sheets of Examples 1 to 5 and Comparative Example 1 prepared in “4” described later, a protective layer Ultraviolet irradiation (in the atmosphere, H bulb, 800 mJ / cm ² ) was performed from the side, and the protective layer was completely cured to obtain a decorative molded product. The mold was a flat mold having a thickness of 2 mm, polycarbonate was used as the injection resin, and the temperature of the injection resin during injection was 285 ° C.
The obtained decorative molded product was observed from various angles under the illumination of a fluorescent lamp, and 3 points were found that the locally distorted part was not concerned, and the locally distorted part was slightly anxious. Twenty subjects evaluated and calculated the average score, with 2 points being within the allowable range and 1 point being locally distorted and out of the allowable range. As a result, an average score of 2.5 or higher is “A”, an average score of 1.5 to less than 2.5 is “B”, an average score of less than 1.5 is “B” C ”.

4). Production of Transfer Sheet On the release layer of the release sheet of Examples 1 to 5 and Comparative Example 1, the adhesion amount after drying the protective layer forming ink of the following formulation was 6.5 g / m ² (6.0 μm). After coating to form a coating film, the protective layer was semi-cured by irradiating the light source with a fusion UV lamp system under the conditions of an H bulb, a conveyance speed of 20 m / min, and an output of 40%. The integrated light quantity at this time was 15 mJ / m ² when measured by an illuminance meter (trade name: UVPF-A1) manufactured by Eye Graphics.
<Protective layer forming ink>
・ 70 parts by mass of urethane acrylate UV curable resin composition (manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam HT-X)
(Solid content 35% by mass, toluene / ethyl acetate mixed solvent)
-30 parts by mass of urethane acrylate ultraviolet curable resin composition (manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam EXF-HT-1)
(Solid content 40% by mass, toluene / methyl ethyl ketone mixed solvent)

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

Next, an adhesive layer forming ink having the following formulation was applied onto the anchor layer so that the adhesion amount after drying was 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 solution for adhesive layer>
-100 parts by mass of acrylic resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-R600, solid content 20%)
(Ethyl acetate / n-propyl / methyl ethyl ketone mixed solvent)
・ Methyl ethyl ketone 40 parts by mass

  From the results in Table 1, the release sheets of Examples 1 to 5 satisfying the conditions (1) and (2) have a good appearance when the transfer layer is transferred to the transfer object using the release sheets, and the design It can be confirmed that the property and the yield can be improved.

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

10: Release sheet 11: Support 12: Concavity and convexity layer 13: Release layer

Claims (8)

A release sheet having a concavo-convex layer and a release layer on a support, wherein the concavo-convex layer has a maximum height Ry at a cut-off value of 0.8 mm measured according to JIS B0601: 1994, JIS B0601: 1994. Arithmetic mean roughness Ra at a cut-off value of 0.8 mm of the uneven layer measured according to JIS, 10-point average roughness at a cut-off value of 0.8 mm of the uneven layer measured according to JIS B0601: 1994 A release sheet in which the thickness Rz and the thickness T of the release layer satisfy the following conditions (1) and (2).
3.0 ≦ Ry / Ra (1)
T / Rz ≦ 0.50 (2)   The release sheet according to claim 1, wherein the maximum height Ry of the uneven layer is 0.7 to 7.0 μm.   The release sheet according to claim 1 or 2, wherein an arithmetic average roughness Ra of the uneven layer is 0.05 to 2.00 µm.   The ten-point average roughness Rz at a cut-off value of 0.8 mm of the uneven layer measured according to JIS B0601: 1994, and the arithmetic average roughness Ra of the uneven layer are Rz / Ra ≦ 10.0. The release sheet according to any one of claims 1 to 3, which satisfies a relationship.   The release sheet according to any one of claims 1 to 4, wherein a thickness T of the release layer is less than 1.0 µm.   The release sheet according to any one of claims 1 to 5, wherein a haze of the release sheet measured according to JIS K7136: 2000 is more than 2.0%.   The transfer sheet which has a transfer layer on the release sheet of any one of Claims 1-6.   A method for producing a decorative molded product, comprising: a step of transferring the transfer layer of the transfer sheet according to claim 7 to a transfer target; and a step of peeling the release sheet of the transfer sheet.