JP6932922B2 - Transfer sheet, manufacturing method of decorative molded product using transfer sheet, and decorative molded product - Google Patents

Description

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

Conventionally, in the fields of household electric appliances, automobile interior parts, miscellaneous goods, etc., high functionality and design have been exhibited by decorating the surface of the object to be transferred with characters, patterns, and the like. As a method of decorating the surface of the object to be transferred, there is a transfer method. The transfer method uses a transfer sheet in which a transfer layer composed of a release layer, a pattern layer, an adhesive layer, etc. is formed on a substrate, and is heated and pressed to bring the transfer layer into close contact with the object to be transferred, and then the substrate is pressed. This is a method of peeling off and transferring only the transfer layer to the surface of the object to be transferred for decoration.

Further, depending on the application, the surface of the object to be transferred may be required to have an excellent design property such as a high-class feeling and a different texture such as glossiness and matteness.
For example, Patent Document 1 describes a release layer containing a matting agent entirely on a substrate sheet, a mask layer partially containing an active energy ray-curable resin, and a release layer and a design layer as transfer layers. A partially matte transfer sheet, characterized in that the above is formed, is disclosed.

Japanese Patent No. 5095598

However, in the partially matte transfer sheet of Patent Document 1, when defects such as scratches and cracks occur in the transfer layer during manufacturing or when the transfer layer is transferred to the surface of the object to be transferred, the defects are easily noticeable. rice field. Therefore, the partially matte transfer sheet of Patent Document 1 cannot sufficiently enhance the design of the transferred object and cannot improve the yield.

The present invention has been made in view of such circumstances, and a transfer sheet for obtaining a decorative molded product having excellent design and yield, a method for manufacturing a decorative molded product using the transfer sheet, and addition. An object is to provide decorative molded products.

In order to solve the above problems, the present invention provides the following [1] to [3].
[1] A transfer sheet having a transfer layer on the release sheet, the surface of the release sheet on the side in contact with the transfer layer is adjacent to a first region X having an uneven portion and the first region X. The transfer layer comprises a second region Y to be formed, and the transfer layer comprises a protective layer containing a cured product of the curable resin composition and a resin layer located on the opposite side of the protective layer from the release sheet. A transfer sheet, wherein the resin layer contains a binder resin and particles, and the refractive index n _{1 of the} binder resin and the refractive index n _{2 of the} particles are different.
[2] A method for producing a decorative molded product, comprising a step of transferring the transfer layer of the transfer sheet according to the above [1] to an object to be transferred and a step of peeling off the release sheet of the transfer sheet.
[3] A decorative molded product having a transfer layer on the transfer material, the surface of the transfer layer opposite to the transfer material has a first region X'having an uneven portion and the first region. It has a second region Y'adjacent to the region X', and the transfer layer is a cured product of a resin layer and a curable resin composition located on the opposite side of the resin layer from the transferred product. The resin layer contains a binder resin and particles, and the refractive index n _{1 of the} binder resin and the refractive index n _{2 of the} particles are different. Decorative molded products.

According to the present invention, it is possible to provide a transfer sheet from which a decorative molded product having excellent design and a good yield can be obtained, a method for producing a decorative molded product using the transfer sheet, and a decorative molded product. ..

It is sectional drawing which shows one Embodiment of the transfer sheet of this invention. It is a top view which shows one Embodiment of the release sheet which comprises the transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the decorative molded article obtained by using the transfer sheet of this invention.

[Transfer sheet]
The transfer sheet of the present invention has a transfer layer on the release sheet, and the surface of the release sheet on the side in contact with the transfer layer has a first region X having an uneven portion and the first region X. The transfer layer has a second region Y adjacent to the protective layer, and the transfer layer is a protective layer containing a cured product of the curable resin composition and a resin layer located on the opposite side of the protective layer from the release sheet. The resin layer contains a binder resin and particles, and the refractive index of the binder resin and the refractive index of the particles are different from each other.

FIG. 1 is a cross-sectional view showing an embodiment of the transfer sheet of the present invention.
The transfer sheet 100 of FIG. 1 has a transfer layer 40 on the release sheet 10. Further, the release sheet 10 is composed of a support 11 and a partially uneven layer 12, and the surface of the release sheet 10 on the side in contact with the transfer layer 40 is adjacent to the first region X having the uneven portion and the first region X. It has a second region Y to be used. Further, the transfer layer 40 has a protective layer 20 containing a cured product of the curable resin composition, and a resin layer 30 located on the opposite side of the protective layer 20 from the release sheet 10. Further, the resin layer 30 contains the binder resin 31 and the particles 32.

<Release sheet>
The release sheet has a first region X and a second region Y on the surface on the transfer layer side, and the first region X has a concavo-convex portion. The release sheet is peeled off after the transfer layer is transferred to an object to be transferred such as a resin molded body.

The release sheet 10 is formed of, for example, the support 11 and the partially uneven layer 12 as shown in FIG. Of course, the release sheet may be a single layer of a support or a single layer of a partially concavo-convex layer, or may have a configuration of three or more layers having layers other than the support and the partially concavo-convex layer.
Although not shown, the release sheet preferably has a release layer on the surface on the transfer layer side.

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

The thickness of the support is preferably 12 to 150 μm, more preferably 25 to 100 μm, from the viewpoint of moldability, shape followability, and handling.
Further, the surface of the support may be subjected to physical treatment such as corona discharge treatment and oxidation treatment, and coating of a paint called an anchor agent or a primer in advance in order to enhance the adhesiveness with the resin layer or the like. ..
In addition, in this specification, "AA-BB" means "AA or more and BB or less". The same applies hereinafter.

<First region X and second region Y>
The surface of the release sheet 10 on the side in contact with the transfer layer has a first region X having an uneven portion and a second region Y adjacent to the first region X.
The arrangement of the first region X and the second region Y is arbitrary. For example, a configuration in which a first region X is arranged at the center of the release sheet 10 and a second region Y is arranged at a peripheral portion (configuration of FIG. 2); Configuration in which one region X is arranged; Configuration in which the first region X and the second region Y are arranged in parallel; A plurality of independent first regions X are arranged near the center of the release sheet 10, and the plurality of first regions X are arranged. A configuration in which the second region Y is arranged around the first region X; a plurality of independent second regions Y are arranged near the center of the release sheet 10, and the first region X is arranged around the plurality of second regions Y. The configuration to be arranged; etc. may be mentioned.
The release sheet may have a further region on the surface in contact with the transfer layer.

The uneven portion on the first region X corresponds to the partial unevenness formed on the surface of the transferred object after the transfer layer is transferred to the transferred object. That is, after the transfer layer is transferred to the transferred object, irregularities having a shape complementary to the irregularities on the first region X are formed on the surface of the transferred object. By forming partial irregularities on the transferred object in this way, it is possible to improve the design of the transferred object and impart partial antiglare properties to the transferred object.

The degree of unevenness of the first region X defined by the uneven portion is not particularly limited because it differs depending on the purpose (design, antiglare, etc.), but the first region measured according to JIS B0601: 1994 is measured. _{The arithmetic mean roughness Ra 1} at a cutoff value of 0.8 mm is preferably 0.05 to 2.00 μm. By _{setting Ra 1} to the above range, it is possible to easily improve the balance between the design property and the antiglare property of the transferred material.
Ra ₁ is more preferably 0.07 to 1.00 μm, further preferably 0.08 to 0.50 μm, and further preferably 0.10 to 0.20 μm.
In this specification, Ra and Rz described later are average values when measured at 20 points.

_{Further, in the first region X, the ten-point average roughness Rz 1} at a cutoff value of 0.8 mm of the first region X, which is measured according to JIS B0601: 1994, is 1.0 to 3.5 μm. It is preferably 1.1 to 3.3 μm, more preferably 1.2 to 3.0 μm.
By _{setting Rz 1} to 1.0 μm or more, when a defect such as a scratch occurs in the first region X, the defect can be made inconspicuous and the yield can be improved.
Further, by _{setting Rz 1} to 3.5 μm or less, deterioration of the design of the transferred material can be suppressed. Further, by _{setting Rz 1} to 3.5 μm or less, when the transferred object is used on the front surface of a display element such as a liquid crystal display element, glare can be suppressed. The "glare" refers to a phenomenon in which minute variations in brightness are visible in the image light due to the uneven structure.

The second region Y may have no uneven portion and may be substantially smooth, or may have an uneven portion like the first region X.
Further, from the viewpoint of clarifying the contrast between the first region X and the second region Y to enhance the design, the cutoff value of the second region Y measured in accordance with JIS B0601: 1994 is 0.8 mm. The arithmetic mean roughness Ra ₂ of the above is preferably smaller than that of _{Ra 1.} Furthermore, the Ra ₁ and Ra _2, preferably satisfy the relation of 0.06 .mu.m ≦ _Ra 1 -Ra _2, it is more preferable to satisfy the relation of _{0.06μm ≦ Ra 1 -Ra 2 <2.00μm} , 0 It is more preferable to satisfy the relationship of .07 μm ≤ Ra _{1- Ra 2} ≤ 0.50 μm, and even more preferably to satisfy the relationship of 0.08 μm ≤ Ra _{1- Ra 2} ≤ 0.20 μm.

Further, Ra ₂ is preferably less than 0.10 μm, more preferably 0.07 μm or less, and further preferably 0.05 μm or less.
Generally, when Ra of an arbitrary region is less than 0.10 μm, when a defect such as a scratch occurs in the region, the defect becomes conspicuous and the yield is lowered. Since the transfer sheet of the present invention contains particles that cause internal haze (internal diffusion) in the resin layer described later _{, even if Ra 2 of} the second region Y is less than 0.10 μm, defects in the second region Y are present. It can be made inconspicuous and the yield can be improved.

<Partial uneven layer>
The partially uneven layer constituting the release sheet preferably contains a resin component such as a thermoplastic resin, a cured product of a thermosetting resin composition, and 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 partially 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 which is excellent in strength and can impart an accurate and precise shape because it cures instantly is preferable. Further, from the viewpoint of facilitating the effect of the ionizing radiation curable resin composition, it is preferable to contain 70% by mass or more of the cured product of the ionizing radiation curable resin composition among all the resin components constituting the partially concavo-convex layer. It is more preferably contained in an amount of 90% by mass or more, further preferably contained in an amount of 95% by mass or more, and further preferably contained in an amount of 100% by mass or more.

The partially uneven layer may be formed by coating, but from the viewpoint of forming an accurate and precise shape, it is formed by printing using a plate having a shape complementary to the first region X and the second region Y. Is preferable. If the partially concavo-convex layer has other regions, the plate preferably has a shape complementary to the other regions. Details of the method for forming the partially uneven layer using the plate will be described later.

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 needed.

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

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

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

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

The thickness of the partially concavo-convex layer is not particularly limited, but is preferably 1 to 15 μm, more preferably 2 to 12 μm.

From the viewpoint of improving the releasability between the release sheet and the transfer layer, it is preferable that the partially concavo-convex layer does not substantially contain particles. Specifically, the content of the particles in the partially concavo-convex layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. , 0% by mass is even more preferable.

<Release layer>
The interface between the release sheet and the transfer layer is formed so that it can be peeled off when it comes into close contact with the transfer material.
In order to improve the release property, the release sheet preferably has a release layer on at least a part of the surface on the side in contact with the transfer layer. Further, from the viewpoint of making the in-plane releasability of the transfer sheet uniform, it is preferable that the release sheet has a release layer on the entire surface of the surface in contact with the transfer layer.
Further, by forming the release layer on the uneven portion of the first region X, it is possible to form an uneven shape with few high frequency components on the surface of the transferred object, and it is possible to suppress whitening and glare of the transferred object. ..

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

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

The thickness of the release layer is preferably 0.1 to 5.0 μm, more preferably 0.3 to 1.0 μm.

The release sheet may have other layers.
Examples of the other layer include an antistatic layer. By having the antistatic layer, peeling charge when peeling the release sheet can be suppressed, and transfer workability can be improved.

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

<Manufacturing method of release sheet>
The release sheet having the first region X and the second region Y can be produced, for example, by the following steps (A1) to (A2).

(A1) A step of applying an ink for forming a partially uneven layer containing an ionizing radiation curable resin composition onto a support to form a layer containing the ionizing radiation curable resin composition.
(A2) Using a plate having a shape complementary to the first region X and the second region Y, the uncured partially uneven layer is formed, and at the same time, ionizing radiation is irradiated to form the shaped partial uneven layer. The process of curing.

When the ionizing radiation curable resin composition contains a solvent, it is preferable to dry the solvent in the step (A1).
When the release sheet has a release layer, the step of forming the release layer on the partially uneven layer (A3) may be performed after the step (A2).

When the release sheet has other regions, a plate having a shape complementary to the first region X, the second region Y, and the other regions may be used as the plate for the step (A2).

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, a long male plate (a plate having the same shape as the first region X and the second region Y) is produced by laser engraving, stereolithography, etc., and the inverted version is wound around the surface of the cylinder. Can be obtained by
The surface of the plate used in the step (A2) is preferably hard-plated with chrome or the like.

The release sheet can also be produced by, for example, the following steps (B1) to (B2).
(B1) A step of filling a plate having a shape complementary to the first region X and the second region Y with ink for forming a partially uneven layer.
(B2) A step of transferring the ink for forming a partially uneven layer filled in a plate onto a support, drying and curing as necessary to form a partially uneven layer.

From the viewpoint of forming an accurate and precise shape, the above-mentioned steps (A1) to (A2) are suitable.

<Transfer layer>
A transfer layer is formed on the release sheet.
The transfer layer 40 is a layer that is transferred to the object to be transferred. For example, as shown in FIG. 1, the transfer layer 40 has a protective layer 20 and a resin layer 30 in order from the side closer to the release sheet 10.

<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, etc. after the transfer layer is transferred from the transfer sheet to the object to be transferred.

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. Is even more preferable.
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, the cured product of the ionizing radiation curable resin composition is preferable.
Further, the protective layer may contain a thermoplastic resin, but the amount thereof is preferably a small amount from the viewpoint of improving scratch 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, and even more preferably less than 0.1% by mass. It is even more preferably 0% by 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 partially uneven layer described above.
The cured product of the curable resin composition is left in a semi-cured state at the time of forming the protective layer, and after being transferred to the transferred material, the curable resin composition is cured by heating, irradiation with ionizing radiation, or the like. May be allowed to proceed and be completely cured. By doing so, the followability of the transfer sheet to the transferred material is improved, so that the moldability can be improved.

The protective layer may contain particles such as organic particles and inorganic particles, but the content is preferably small.
When the transfer layer is transferred to the object to be transferred to obtain a decorative molded product, the protective layer is located on the surface side. Therefore, when the transferred material has a convex shape, the protective layer needs to have a larger area than the other layers at the time of molding, so that a load is likely to be applied. Further, even when the decorative molded product is bent, the protective layer is likely to be loaded. Then, when the particles are contained in the protective layer located on the surface side, the particles act as a trigger, and defects such as cracks are likely to occur in the protective layer during molding or the like. The reason for this is considered as follows (1) to (3).
(1) The physical characteristics of the particles and the cured product of the curable resin composition are different.
(2) Since the physical characteristics of the two are different, they try to behave differently at the time of molding, but a protective layer containing a cured product of the curable resin composition (particularly, a cured product of the ionizing radiation curable resin composition). Within, the behavior of the particles is limited.
(3) As a result of limiting the behavior of the particles in the protective layer, a load is applied to the interface of the particles, and defects such as cracks occur in the protective layer.
The content of the particles in the protective layer is preferably less than 5% by mass, more preferably less than 1% by mass, further preferably less than 0.1% by mass, and preferably 0% by mass. Even more preferable.

<Resin layer>
The resin layer is a layer located on the opposite side of the protective layer from the release sheet. Further, the resin layer contains the binder resin and the particles, and is configured such that _{the refractive index n 1} of the binder resin and the refractive index n _{2 of the particles are different.} The resin layer may be only one layer or may have two or more layers.

By configuring the binder resin in the resin layer so that the refractive index n ₁ and the refractive index n _{2 of the} particles are different, internal haze (internal diffusion) is expressed, defects are less noticeable, and the yield can be improved. can.
As described above, when particles are contained in the protective layer, defects such as cracks are likely to occur during molding or the like. However, as in the present invention, when particles are contained in the resin layer located closer to the object to be transferred than the protective layer, defects such as cracks can be suppressed during molding or the like.
Further, when the resin layer is transferred to the transferred material, the resin layer is located below the protective layer. Therefore, the configuration in which the particles are contained in the resin layer as in the present invention is easier to spread over a wider angle range until the internally diffused light reaches the surface of the protective layer, as compared with the configuration in which the particles are contained in the protective layer. It is possible to make defects generated on the surface of the protective layer less noticeable, and it is possible to easily suppress glare. Further, the configuration containing particles in the resin layer as in the present invention has the above-mentioned effect (invisibility of defects, suppression of glare) even if the content of particles is small, as compared with the configuration containing particles in the protective layer. It is suitable because it is easy to obtain.
In order to facilitate the above-mentioned effects, the resin layer is preferably located on the outermost surface of the transfer layer on the opposite side of the release sheet. In other words, the resin layer is preferably located on the side to be transferred most in the transfer layer when it is transferred to the material to be transferred.

The refractive index _{n 1} of the binder resin, the ratio of the refractive index _{n 2} of the _particle, n 2 / _{n 1} is 0.98 or less, or is preferably 1.02 or more.
Further, from the viewpoint of strengthening the internal haze (internal diffusion) and making defects and glare less noticeable, it is more preferable that _{n 2} / n _{1 is 0.98 or less.} Further, when n ₂ / n _{1 is set} to 0.98 or less, it is preferable in that the amount of particles for obtaining the same degree of internal haze (internal diffusion) can be easily reduced.
It should be noted that when n ₂ / n ₁ is 0.98 or less or 1.02 or more, it is also preferable in that interference fringes can be easily suppressed.
In the present invention, the refractive index is based on light having a wavelength of 589 nm.

As the particles, one or more kinds selected from organic particles and inorganic particles can be used.
Examples of the organic particles include particles composed of polymethylmethacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, polyester resin and the like. Can be mentioned.
Examples of the inorganic particles include particles made of silica, alumina, antimony, zirconia, titania and the like.
The shape of the particles may be spherical or indeterminate, but the indeterminate shape is preferable from the viewpoint of strengthening the internal haze (internal diffusion).

The average particle size of the particles is preferably 0.05 to 8.0 μm, more preferably 0.5 to 5.0 μm.
In the present specification, the average particle size is 50% particle size (d50: median diameter) when the particles dispersed in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed as a cumulative distribution. The 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

The content of the particles in the resin layer is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass.
By setting the content of the particles to 0.1% by mass or more, defects can be made less noticeable and glare can be easily suppressed. By setting the content of the particles to 20% by mass or less, it is possible to suppress the difficulty in distinguishing between the first region X and the second region Y, and to suppress the deterioration of the design.

Examples of the binder resin of the resin layer include a cured product of a thermosetting resin composition, a cured product of a curable resin composition such as a cured product of an ionizing radiation curable resin composition, and a thermoplastic resin. Among these, a thermoplastic resin is preferable from the viewpoint of suppressing cracks during molding and the like. When a thermoplastic resin is contained as the binder resin, the behavior of the particles in the resin layer is less likely to be restricted during molding, and a load is less likely to be applied to the interface of the particles, so that it is considered that cracks are easily suppressed.

Further, the binder resin of the resin layer preferably contains a thermoplastic resin as a main component. The main component means 50% by mass or more of the total solid content constituting the resin layer, and the ratio is preferably 70% by mass or more, more preferably 90% by mass or more, and 100% by mass. % Is even more preferable.
By using a thermoplastic resin as the main component of the binder resin in the resin layer, the behavior of the particles in the resin layer during molding is not further restricted, and the occurrence of defects can be further suppressed. Further, by using the main component of the binder resin of the resin layer as a thermoplastic resin and locating the resin layer on the outermost surface of the transfer layer on the opposite side of the release sheet, the adhesion to the transferred material is improved. It can be made easier or act as a heat seal layer during molding.

The embodiment of the curable resin composition is the same as the embodiment of the curable resin composition of the partially uneven layer described above.
Examples of the thermoplastic resin include acrylic resins, styrene resins, amide resins, cellulose resins, urethane resins, vinyl chloride resins, ester resins, olefin resins, carbonate resins, and the like. Modified resin can be mentioned.
From the viewpoint of improving the adhesion to the transferred material, it is preferable to select a resin suitable for the material of the transferred material. For example, when the material of the object to be transferred is an acrylic resin, it is preferable to use an acrylic resin. When the material of the object to be transferred is a polyphenylene oxide polystyrene resin, a polycarbonate resin, or a styrene resin, an acrylic resin, polystyrene resin, polyamide resin, or the like having an affinity for these resins should be used. Is preferable. Further, when the material of the object to be transferred 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 kumaron indene resin.

Additives such as an ultraviolet absorber and an infrared absorber may be blended in the resin layer.
The thickness of the resin layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

<Anchor layer>
The anchor layer is a layer provided as needed to improve heat resistance when placed in a high temperature environment such as in-mold molding. The anchor layer is preferably formed between the protective layer and the resin 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.
The embodiment of the thermosetting resin composition and the ionizing radiation curable resin composition of the anchor layer is the same as the embodiment of the thermosetting resin composition and the ionizing radiation curable resin composition of the partially concavo-convex layer.
The thickness of the anchor layer is preferably 0.1 to 6 μm, more preferably 0.5 to 5 μm.

It is also possible to contain particles in the anchor layer to act as a resin layer. In this case, it is preferable to have a heat seal layer containing a thermoplastic resin as a main component on the surface of the anchor layer (resin layer) opposite to the protective layer.

<Print layer>
The transfer layer may further have a print layer. The printed layer has a role of enhancing the design of the transferred material.
The position of the print layer in the thickness direction may be arranged on the resin layer, may be arranged between the resin layer and the protective layer, or may be arranged between the protective layer and the release sheet. good. Further, the position of the print layer in the plane is arbitrary.

The pattern of the printing layer is arbitrary, and examples thereof include wood grain, stone grain, cloth grain, sand grain, circle, quadrangle, polygon, geometric pattern, character, and solid printing.
The printing layer preferably contains a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, and a cellulose resin, and a pigment and / or a dye.
The thickness of the print layer is preferably 0.5 to 40 μm, more preferably 1 to 30 μm from the viewpoint of designability.

The transfer layer preferably has light transmission. Specifically, the total light transmittance of JIS K7361-1: 1997 in the transfer layer is preferably 80% or more, and more preferably 90% or more. It should be noted that the portion of the transfer layer having the print layer may be concealed without having light transmission.

For each layer such as the protective layer, the resin layer, the anchor layer, and the printing layer constituting the transfer layer, for example, the ink containing the constituent components of each layer is adjusted, and the release sheet is coated with a gravure coating method, a roll coating method, or the like. It can be formed by applying, drying, and curing by irradiating ionizing radiation as necessary by a printing method such as a method, a gravure printing method, or a screen printing method.

[Manufacturing method of decorative molded products]
The method for producing a decorative molded article of the present invention includes a step of transferring the transfer layer of the transfer sheet of the present invention described above to an object to be transferred, and a step of peeling off the release sheet of the transfer sheet.
Examples of the transferred product include a resin molded product and the like.

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

As one embodiment of the method for producing a decorative molded product using the transfer sheet of the present invention by in-mold molding,
(Z1) A step of arranging the transfer layer side of the transfer sheet toward the inside of the in-mold molding die, and
(Z2) A step of injecting resin into the in-mold molding die and
(Z3) A step of integrating the transfer sheet and the resin to transfer the transfer layer of the transfer sheet onto the surface of the resin molded product (transfered product).
(Z4) Examples thereof include a step of removing the release sheet of the transfer sheet after taking out the resin molded body (transfered object) from the mold.

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

FIG. 3 is a cross-sectional view showing an embodiment of a decorative molded article according to the present invention. The decorative molded product 300 has a transfer layer 40 (resin layer 30 and partially uneven layer 20) on one surface of the resin molded product (transferred product) 200.

[Decorative molded products]
The decorative molded product of the present invention is a decorative molded product having a transfer layer on the object to be transferred, and the surface of the transfer layer opposite to the object to be transferred is a first region X having an uneven portion. 'And a second region Y'adjacent to the first region X', the transfer layer is a curable resin layer located on the opposite side of the resin layer from the object to be transferred. it has a protective layer comprising a cured product of the resin composition, the resin layer contains a binder resin and particles, and the refractive index of the refractive index n ₁ and the particles of the binder resin n ₂ is different.

The embodiment of the object to be transferred is the same as the embodiment of the object to be transferred in the method for producing a decorative molded article of the present invention described above.
The transfer layer corresponds to the transfer layer of the transfer sheet of the present invention described above. The first region X'and the second region Y'of the transfer layer of the decorative molded product have a shape complementary to the first region X and the second region Y of the release sheet of the transfer sheet.

Since the decorative molded product of the present invention contains particles in a resin layer that is not located on the surface of the decorative molded product, defects such as cracks can be suppressed when the decorative molded product is bent. Further, since the decorative molded product of the present invention contains particles in the resin layer located below the protective layer, it is easy to spread the internally diffused light over a wider angle range until it reaches the surface of the protective layer. It is possible to make defects generated on the surface of the protective layer less noticeable, and it is possible to easily suppress glare.

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

1. 1. Evaluation and measurement The following evaluation and measurement were performed on the decorative molded products obtained in Examples and Comparative Examples. The results are shown in Table 1.
1-1. Cracks The presence or absence of cracks on the surface of the decorative molded products obtained in Examples and Comparative Examples was visually evaluated. As a result, the one without cracks was designated as A, and the one with cracks was designated as C.

1-2. Visibility of Scratches The visibility of scratches after rubbing the surface of the first region X of the decorative molded product obtained in Examples and Comparative Examples with a nail was visually evaluated. As a result, those with almost inconspicuous scratches were designated as A, those with slightly noticeable scratches were designated as B, and those with very noticeable scratches were designated as C.

1-3. Glitter The surface of the decorative molded product obtained in Examples and Comparative Examples on the transparent acrylic sheet side was attached to the screen of the liquid crystal display device, and the screen of the liquid crystal display device was observed from the front. The one with the least noticeable glare was designated as A, the one with the second least noticeable glare was designated as B, and the one with the third least noticeable glare was designated as C.

1-4. Arithmetic mean roughness Ra, 10-point average roughness Rz
Using a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Co., Ltd.), the first region X of the protective layer of the decorative molded product obtained in Examples and Comparative Examples under the following measurement conditions. For'(the portion corresponding to the first region X of the transfer sheet) and the second region Y'(the portion corresponding to the second region Y of the transfer sheet), Ra and Ra of JIS B0601: 1994 at a cutoff value of 0.8 mm. Rz was measured.
[Needle of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
-Reference length (cutoff value of roughness curve λc): 0.8 mm
-Evaluation length (reference length (cutoff value λc) x 5): 4.0 mm
・ Feeding speed of stylus: 0.5 mm / s
-Preliminary length: (cutoff value λc) x 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

2. Preparation of Plate A cylinder having a copper-plated layer having a thickness of 200 μm was prepared, and the entire surface of the cylinder was covered with a mask in which the portion forming the uneven portion of the first region X was punched. Next, unevenness was formed in the portion not covered by the mask by blasting using glass beads. Next, the mask was removed, and the surface of the cylinder was hard-plated (chrome-plated) to obtain a plate.

3. 3. Preparation of Release Sheet A polyethylene terephthalate film having a thickness of 50 μm was coated with an ink for forming a partially uneven layer having the following formulation and dried to form an uncured partial uneven layer having a thickness of 8.0 μm.
<Ink for forming a partially uneven layer>
60 parts by mass of ionizing radiation curable resin composition (manufactured by Kyoei Chemical Co., Ltd., ES105M)
・ Methyl ethyl ketone 40 parts by mass ・ Silicone leveling agent 0.5 parts by mass

Next, using the plate prepared in "2" above, the uncured partially uneven layer is formed, and at the same time, ionizing radiation is irradiated from the polyethylene terephthalate film side to cure the formed partially uneven layer, and the polyethylene terephthalate is formed. A partially uneven layer was formed on the film.
Next, the release layer forming ink of the following formulation was applied to the entire surface and dried to form a release layer having a thickness of 0.5 μm to obtain a release sheet.

<Ink for mold release layer formation>
-70 parts by mass of acrylic polyol (manufactured by Soken Chemical Co., Ltd., product name: Thermolac SU100A)
25 parts by mass of isocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D-110N)
-Ethyl acetate 161 parts by mass-Methyl isobutyl ketone 56 parts by mass

4. Preparation of transfer sheet, preparation of decorative molded products 4-1. Example 1
On the release sheet obtained in "3" above, the protective layer forming ink of the following formulation ^{is applied so that the adhesion amount after drying is 6.5 g / m 2} (6.0 μm), and the coating film is applied. After the formation, the protective layer was semi-cured by irradiating the light source with an H-bulb, a transport speed of 20 m / min, and an output of 40% using a fusion UV lamp system. The integrated light intensity at this time was measured with an illuminance meter (trade name: UVPF-A1) manufactured by Eye Graphics Co., Ltd. and found to be 15 mJ / m ² .

<Ink for forming protective layer>
-Urethane acrylate-based UV curable resin composition 70 parts by mass (manufactured by Dainichiseika Co., Ltd., trade name: Seika Beam HT-X)
(Solid content 35% by mass, toluene / ethyl acetate mixed solvent)
-Urethane acrylate-based UV curable resin composition 30 parts by mass (manufactured by Dainichiseika Co., Ltd., trade name: Seika Beam EXF-HT-1)
(Solid content 40% by mass, toluene / methyl ethyl ketone mixed solvent)

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

Next, the resin layer forming ink of the following formulation was applied onto the anchor layer so that the adhesion amount after drying was 2.5 g / m ^2, and a coating film was formed. The coating film was dried to form a resin layer having a thickness of 2 μm, and a transfer sheet of Example 1 was obtained (n ₂ / n ₁ = 0.98).
<Ink for forming resin layer>
-Thermoplastic resin 465 parts by mass (acrylic ester resin ink, solid content 20% by mass)
(Refractive index n ₁ : 1.49)
-Silica particles 3 parts by mass (average particle size: 3.0 μm, refractive index n ₂ : 1.46)
・ Methyl ethyl ketone 40 parts by mass

The surface of the obtained transfer sheet on the resin layer side was superposed on a transparent acrylic sheet (manufactured by Kuraray Co., Ltd., trade name: Comoglass DK3, thickness 2 mm), and heat transfer was performed from the support side of the transfer sheet. Next, after the release sheet of the transfer sheet was peeled off, the resin molded body was irradiated with ultraviolet rays (atmosphere, H valve, 800 mJ / cm ² ) to completely cure the protective layer, and the decorative molded product of Example 1 was obtained. Obtained.

4-2. Comparative Example 1
As the protective layer forming ink, 2.75 parts by mass of acrylic-styrene copolymer particles (average particle diameter 2.5 μm, refractive index n ₂ : 1.55) was added to the protective layer forming ink of Example 1. (N ₂ / n ₁ = about 1.03), and the same as in Example 1 except that the resin layer forming ink of Example 1 from which silica particles were removed was used. Then, the transfer sheet of Comparative Example 1 and the decorative molded product were obtained.

4-3. Comparative Example 2
As the resin layer forming ink, the transfer sheet and the decorative molded product of Comparative Example 2 were obtained in the same manner as in Example 1 except that the resin layer forming ink of Example 1 from which silica particles were removed was used. rice field.

From the results in Table 1, it can be confirmed that the transfer sheet of Example 1 containing particles in the resin layer containing the thermoplastic resin can have good design and yield without cracking during molding. Furthermore, from the results in Table 1, the transfer sheet of Example 1 is a comparative example because the position of the layer containing particles is located below the protective layer when the transfer layer is transferred to the object to be transferred. It can be confirmed that the visibility of scratches and the evaluation of glare are better than those of the transfer sheet.
On the other hand, the transfer sheet of Comparative Example 1 contained particles in the layer containing the cured product of the curable resin composition, so that cracks were generated during transfer. Further, since the transfer sheet of Comparative Example 2 does not contain particles in the transfer layer, cracks do not occur during molding, but when the protective layer is scratched, the scratches are conspicuous and the design and yield cannot be improved. Met.
Although not shown in Table 1, when a thermoplastic resin is added to the protective layer of Comparative Example 1, cracks tend to be improved, but the scratch resistance of the protective layer is lowered, so that the design and design are improved. Yield cannot be improved.

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

11: Support 12: Partially concavo-convex layer 10: Release sheet 20: Protective layer 31: Binder resin 32: Particles 30: Resin layer 40: Transfer layer 100: Transfer sheet 200: Transfer product 300: Decorative molded product

Claims (10)

A transfer sheet having a transfer layer on a release sheet.
The surface of the release sheet on the side in contact with the transfer layer has a first region X having an uneven portion and a second region Y adjacent to the first region X.
The transfer layer includes a protective layer containing a cured product of the curable resin composition and a resin layer located on the opposite side of the protective layer from the release sheet.
The resin layer contains a binder resin and particles, and the refractive index n _{1 of the} binder resin and the refractive index n _{2 of the} particles are different, so that the refractive index n _{1 of the} binder resin and the above. A transfer sheet in which the ratio [n ₂ / n ₁ ] of the particles to the refractive index n ₂ is 0.98 or less or 1.02 or more. The transfer sheet according to claim 1, which contains a thermoplastic resin as the binder resin. The transfer sheet according to claim 1 or 2, wherein the resin layer contains 0.1 to 20% by mass of the particles. The transfer sheet according to any one of claims 1 to 3, wherein the resin layer is located on the outermost surface of the transfer layer opposite to the release sheet. _{The arithmetic average roughness Ra 1} at the cutoff value of 0.8 mm of the first region X, which is measured according to JIS B0601: 1994, is 0.05 to 2.00 μm, and the arithmetic mean of the second region Y. The transfer sheet according to any one of claims 1 to 4, wherein the roughness Ra _{2 is smaller than the Ra 1.} Ten-point average roughness Rz at a cutoff value of 0.8 mm in the first region X, measured according to JIS B0601: 1994. ₁ The transfer sheet according to any one of claims 1 to 5, wherein the transfer sheet is 1.0 to 3.5 μm. The resin layer is located on the outermost surface of the transfer layer opposite to the release sheet, contains the thermoplastic resin as the binder resin, and the thermoplastic resin constitutes 70 of the total solid content of the resin layer. The transfer sheet according to any one of claims 2 to 6, which is by mass% or more. The transfer sheet according to any one of claims 1 to 7, wherein the resin layer does not contain an ultraviolet absorber. Manufacture of a decorative molded product comprising a step of transferring the transfer layer of the transfer sheet according to any one of claims 1 to 8 to an object to be transferred and a step of peeling off the release sheet of the transfer sheet. Method. A decorative molded product having a transfer layer on the transfer material.
The surface of the transfer layer opposite to the transferred object has a first region X'having an uneven portion and a second region Y'adjacent to the first region X'.
The transfer layer comprises a resin layer and a protective layer containing a cured product of a curable resin composition located on the opposite side of the resin layer to the transferred product.
The resin layer contains a binder resin and particles, and the refractive index n _{1 of the} binder resin and the refractive index n _{2 of the} particles are different, so that the refractive index n _{1 of the} binder resin and the particles are different. The ratio [n ₂ / n ₁ ] to the refractive index n _{2 of} is 0.98 or less or 1.02 or more.

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