JP6681562B2 - Transfer hard coat film and decorative member using the same - Google Patents

Description

  The present invention is a transfer hard coat film for forming a hard coat layer, which is disposed on the front surface of a radio wave radar device and is used for a decorative member including an indium gloss layer, a resin substrate, and a hard coat layer in this order, and The present invention relates to a decorative member using this.

  The auto cruise system measures the inter-vehicle distance and relative speed between the vehicle in front and the own vehicle by the sensor mounted on the front side of the vehicle, and based on this information, controls the throttle and brake to accelerate and decelerate the own vehicle, It is a technology that controls distance. A laser radar or a millimeter wave radar is generally used as a sensor used in the auto cruise system. For example, a millimeter-wave radar transmits a millimeter wave having a frequency of 30 GHz to 300 GHz and a wavelength of 1 to 10 mm, and receives a millimeter wave reflected by an object, so that the difference between the transmitted wave and the received wave causes the vehicle to move forward. Measure the distance and relative speed to your vehicle. A radio wave transmitting decorative member (a radio wave transmitting cover) is arranged in front of the millimeter wave radar. The millimeter wave emitted from the millimeter wave radar passes through the radio wave transmitting decorative member and is output in front of the vehicle.

  Further, the millimeter-wave radar in the 70 GHz band has a theoretical resolution of about 10 mm, but an object such as a person whose radar reflection is weak may have a low resolution and may not be detected. Therefore, a near-infrared radar having a frequency of 300 THz and a wavelength of about 1 μm, which is excellent in resolution, may be used together.

  For example, Patent Document 1 below proposes a specific configuration of a radio wave transmitting decorative member and a manufacturing method thereof.

  FIG. 10 is a schematic diagram showing an example of a conventional radio wave transmitting decorative member 100. The radio wave transmitting decorative member 100 includes a transparent first resin substrate 101, a coloring layer 102 (coloring material layer 1021 and metallic luster layer 1022) from the front side when viewed from the front with the front of the vehicle as the front. The heat resistant layer 103 and the second resin substrate 104 are formed in this order.

  The back surface of the first resin substrate 101 has an uneven shape, and the coloring material layer 1021 of the colored layer 102 is formed on the convex portion 101A on the back surface of the first resin substrate 101. On the other hand, the metallic luster layer 1022 is formed including the concave portion 101B on the back surface of the first resin substrate 101. When viewed from the front, the metallic luster layer 1022 formed in the concave portion 101B is located in front of the color material layer 1021 formed around the metallic luster layer 1022. The color material layer 1021 can be made to appear as if it were raised.

  Further, in the radio wave transmitting decorative member 100, a hard coat layer 105 is formed by applying a hard coat agent to both surfaces of the resin substrate 101 in order to impart scratch resistance (see FIG. 11). Known methods for applying the hard coat agent include spraying, dipping, spin coating, roll coating, curtain coating, and flow coating.

JP, 2008-230497, A

  By the way, in order for the metallic luster layer 1022 to have radio wave transmission, the metallic luster layer 1022 has a discontinuous structure, that is, the metallic luster layer 1022 is not continuous on one side, and a large number of fine metallic luster layers 1022 are island-shaped. It is necessary to form a structure (sea-island structure) that exists in a state of being slightly separated from each other. For this reason, it is general to use indium for the metallic luster layer 1022, which has glitter and easily forms a discontinuous structure.

  However, according to the study by the present inventors, this indium has poor weather resistance, and in the above-described decorative member 100, even if the hard coat layer 105 is formed, it is exposed to sunlight for a long period of time. It was found from the above that the metallic luster layer 1022 made of indium is easily discolored.

  Further, the conventional step of applying the hard coat agent is performed in the final step of manufacturing the radio wave transmitting decorative member 100. Therefore, if the first resin substrate 101 is scratched by the final step of applying the hard coat agent, the first resin substrate on which the metallic luster layer 1022 made of expensive indium is formed becomes a defective product. Therefore, it is desired to form the hard coat layer 105 at an early stage of manufacturing the radio wave transmitting decorative member 100 to suppress the loss due to the generation of defective products as much as possible.

  Further, according to the above method, the hard coat layer 105 is directly formed on the surface of the first resin substrate 101, but from the viewpoint of improving the weather resistance of the radio wave transmitting decorative member 100, the hard coat layer 105. It is preferable to make a multi-layer. However, when the coating method is applied in multiple layers, it is necessary to repeat coating and drying for each layer, which imposes a heavy burden on the work and may lead to further deterioration of the yield.

  The present invention has been made in view of the above circumstances. That is, an object thereof is to provide a transfer hard coat film capable of imparting excellent weather resistance and productivity to a decoration member arranged on the front surface of a radio wave radar device, and a decoration member using the same. .

  As a result of intensive studies to solve the above problems, the present inventors have used a transfer hard coat film having a transfer layer in which a hard coat layer, a primer layer, and an adhesive layer are arranged in this order, and a primer layer In order to solve the above problems, it was found that the above problem can be solved by incorporating an ultraviolet absorber that effectively absorbs ultraviolet rays having a wavelength of 350 nm or more and 400 nm or less, thereby controlling the light transmittance of the transfer layer, and the present invention is developed. Came to. More specifically, the present invention provides the following.

(1) A transfer hard coat film for forming the hard coat layer in a decorative member, which is arranged in front of a radio wave radar device and includes an indium gloss layer, a resin substrate, and a hard coat layer in this order,
On the base film, at least, a transfer layer in which a hard coat layer, a primer layer and an adhesive layer are arranged in this order,
Contains an ultraviolet absorber in the primer layer,
The transfer layer is a transfer hard coat film having an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less.

(2) The transfer hard coat film according to (1), wherein the ultraviolet absorber is a first ultraviolet absorber having an absorption peak in a wavelength range of 350 nm to 400 nm.

(3) The primer layer further contains a second ultraviolet absorber that is not the first ultraviolet absorber,
The transfer hard coat film according to any one of (1) to (2), wherein the transfer layer has an average light transmittance of 0.5% or less at wavelengths of 300 nm to 350 nm.

(4) An intermediate product which is disposed on the front surface of the radio wave radar device and is used as a decorative member having an indium gloss layer,
On the resin substrate, at least, a transfer layer in which an adhesive layer, a primer layer, a hard coat layer and a substrate film are arranged in this order,
Contains an ultraviolet absorber in the primer layer,
The transfer layer is an intermediate product of a decorative member having an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less.

(5) A decoration member arranged on the front surface of the radio wave radar device,
The decorative member has at least an indium gloss layer, a resin substrate, a transfer layer including an adhesive layer, a primer layer, and a hard coat layer in this order,
Contains an ultraviolet absorber in the primer layer,
The said transfer layer is a decoration member whose average of the light transmittance of wavelength 350nm or more and 400nm or less is 25% or less.

(6) A decoration member arranged on the front surface of the radio wave radar device,
The decorative member includes at least a second resin substrate, an indium gloss layer, a first resin substrate, a transfer layer including an adhesive layer, a primer layer, and a hard coat layer in this order,
Contains an ultraviolet absorber in the primer layer,
The said transfer layer is a decoration member whose average of the light transmittance of wavelength 350nm or more and 400nm or less is 25% or less.

  According to the present invention, it is possible to provide a transfer hard coat film capable of imparting excellent weather resistance and productivity to a decoration member arranged on the front surface of a radio wave radar device, and a decoration member using the same. .

1 is an embodiment of a transfer hard coat film of the present invention, and is a schematic cross-sectional view showing a layer structure. It is one Embodiment of the intermediate product of the decorating member of this invention, Comprising: (a) The embodiment in which a base material film exists, (b) The embodiment which peeled the base material film. It is a schematic diagram showing an example of a manufacturing method of an intermediate product of the above-mentioned decoration member. It is one Embodiment of the decoration member of this invention, Comprising: It is a cross-sectional schematic diagram showing a layer structure. It is a graph which shows the light absorbency of each ultraviolet absorber. 5 is a graph showing the transmittance of Example 1. 5 is a graph showing the transmittance of Example 2. 9 is a graph showing the transmittance of Comparative Example 2. 9 is a graph showing the transmittance of Comparative Example 3. It is an example of the conventional decoration member, and is a schematic cross-sectional view showing a layer structure. It is another example of the conventional decorative member, and is a schematic cross-sectional view showing a layer structure.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. it can.

<Transfer hard coat film>
The transfer hard coat film 10 of the present embodiment is a laminate in which the transfer layer 12 is arranged on the base film 11 (see FIG. 1). The transfer layer 12 is composed of at least a hard coat layer 121, a primer layer 122, and an adhesive layer 123 in this order from the base film 11. By using the transfer hard coat film 10 of the present embodiment, an intermediate product of a decorative member in which the transfer layer 12 including the hard coat layer 121 is laminated on the first resin substrate 20 (see FIG. 2) is manufactured. You can

  The transfer hard coat film 10 of the present embodiment is an embodiment of the transfer hard coat film of the present invention. The “arranged in this order” in the present invention means not limited to a configuration in which only the base film 11, the hard coat layer 121, the primer layer 122, and the adhesive layer 123 are laminated. For example, even if other layers such as a release layer and a coloring layer are laminated between the base film 11 and the hard coat layer 121, the lamination order of the present invention is satisfied within a range that does not impair the effects of the present invention. As long as it is within the scope of the present invention.

  The transfer layer 12 contains an ultraviolet absorber in the primer layer 122 and has an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less. Since the average of the light transmittance of the wavelength 350 nm or more and 400 nm or less is 25% or less, the intermediate product or the decorative member of the decorative member in which the transfer hard coat film 10 is laminated has a low energy of ultraviolet rays or a short wavelength. Even when exposed to visible light, fading of the indium gloss layer of the decorative member described later is suppressed, and excellent weather resistance is provided.

  Here, the average light transmittance means that the base film 11 is peeled from the transfer hard coat film 10 to form only the transfer layer 12, and the spectrophotometer (manufactured by Hitachi High-Technologies Corporation, "Model number: U-4100") The light transmittance of a light beam having a wavelength of 350 nm to a wavelength of 400 nm is measured every 1 nm, and the average thereof is calculated.

  In addition, in the present embodiment, the transfer layer 12 includes only three layers of the hard coat layer 121, the primer layer 122, and the adhesive layer 123, but the transfer layer 12 may include other layers in addition to these three layers. Good. Further, the transfer layer 12 preferably has an average light transmittance of 90% or more in a visible region having a wavelength of 400 nm or more and 750 nm or less.

  Hereinafter, the base film 11 and the transfer layer 12 that form the transfer hard coat film 10 of the present embodiment will be described respectively.

[Base film]
The base film 11 is not particularly limited, but is preferably composed of a polyester resin film or a polyolefin resin film. Moreover, it is preferable that it is a stretched film among the above-mentioned films. When the base film 11 is made of these resin films, the hard coat layer 121 and the like can be easily formed on the base film 11, and when the hard coat film for transfer 10 is manufactured, heat shrinkage or a hard coat layer occurs. When an ionizing radiation curable resin is used for forming 121, it has excellent shrinkage resistance that shrinkage due to irradiation of ionizing radiation does not easily occur, and the transfer hard coat film 10 is manufactured with excellent stability and efficiency. It becomes possible. Further, since heat shrinkage due to the heating temperature does not occur when the transfer hard coat film 10 is transferred to the first resin substrate 20, it is possible to easily manufacture an intermediate product for a decorative member.

  As the polyester resin film, for example, a film made of a polyester resin such as polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer and the like. Are preferred. Among these, polyethylene terephthalate and polybutylene terephthalate are preferable, and especially polyethylene terephthalate, in consideration of heat shrinkage during production of the transfer hard coat film 10 of the present embodiment, shrinkage due to irradiation with ionizing radiation, and the like. Is preferred.

  As the polyolefin resin film, in consideration of heat shrinkage during manufacturing of the transfer hard coat film 10 and shrinkage due to irradiation of ionizing radiation, etc., for example, polyethylene resin, polypropylene resin, polybutene resin, ethylene-propylene A stretched resin film made of a polyolefin resin such as a copolymer resin, an ethylene-propylene-butene copolymer resin, and an olefin thermoplastic elastomer is preferable. Among these, a stretched polypropylene resin film is preferable.

  The stretched polyolefin resin may be either uniaxially stretched or biaxially stretched, but in consideration of heat shrinkage during production of the transfer hard coat film, shrinkage due to irradiation of ionizing radiation, etc. It is preferably biaxially stretched. The sheet of the biaxially stretched polyolefin resin is usually heated to a glass transition temperature (Tg) or higher by using a longitudinal stretching machine, preferably stretched by 5 times or more and 30 times or less, and then using a width direction stretching machine. It is obtained by heating to a glass transition temperature (Tg) or more and stretching in the width direction preferably 5 times or more and 30 times or less. Further, when the stretching ratio is within the above range, heat shrinkage during the production of the transfer hard coat film 10 and shrinkage due to irradiation with ionizing radiation are less likely to occur.

  The thickness of the base film 11 is not particularly limited, but may be 4 μm or more and 200 μm or less. If it is 4 μm or more, curling and wrinkles are less likely to occur, and if it is 200 μm or less, the cost can be kept low, the heat conduction efficiency does not decrease, and each layer is taken when peeling the base film 11 after transfer. Therefore, excellent transferability can be obtained. The base film 11 may have a multilayer structure. In that case, it is preferable that the thickness of the entire multilayer structure is within the above range.

  The base film 11 may be subjected to a known release treatment on the surface of the base film 11 or a silicone resin, if necessary, in order to secure releasability between the base film 11 and the hard coat layer 121 during transfer. You may provide a mold release layer. On the contrary, in order to improve the adhesion with the hard coat layer 121, surface treatment such as corona discharge treatment, plasma treatment, chrome oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, and application of an easily adhesive coating agent. May be given.

[Transfer layer]
The transfer layer 12 is composed of a hard coat layer 121, a primer layer 122, and an adhesive layer 123 in this order from the base film 11.

[Hard coat layer]
The hard coat layer 121 is a layer formed of a cured product of a curable resin composition, and is a layer that imparts scratch resistance (hard coat property) to the first resin substrate 20.

[Curable resin composition]
(Curable resin)
The hard coat layer 121 is not particularly limited, but for example, polyester resin, epoxy resin, polyurethane resin, aminoalkyd resin, melamine resin, guanamine resin, urea resin, thermosetting acrylic resin, ionizing radiation curable resin. And the like, a layer formed of a cured product of From the viewpoint of weather resistance and scratch resistance, a cured product of an ionizing radiation curable resin is preferable.

  Ionizing radiation curable resin is a curable resin that is cured by irradiation with ionizing radiation, and as ionizing radiation, one having an energy quantum capable of polymerizing or crosslinking molecules among radio waves or charged particle beams, for example, Ultraviolet rays (UV) or electron beams (EB) are used, as well as radio waves such as X rays and γ rays, and charged particle rays such as α rays and ion rays.

  As the ionizing radiation curable resin that can be used for the hard coat layer 121, a polymerizable oligomer (prepolymer) or a polymerizable polymer that has been conventionally used as a resin having ionizing radiation curability can be appropriately selected and used. From the viewpoint of being able to obtain good curing characteristics, it is preferable to use a material that is unlikely to bleed out and hard to cause shrinkage upon curing to form the hard coat layer 121. Further, in the case of coating with a solventless system, it is preferable to have coatability even when the solid content is about 95% or more and 100% or less.

  As the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyether urethane (meth) acrylate or caprolactone-based urethane (meth) Preferred examples include acrylate, polyester (meth) acrylate-based, and polyether (meth) acrylate-based oligomers, and urethane (meth) acrylate-based oligomers are more preferred. The above (meth) acrylate means acrylate or methacrylate.

  Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 or more and 15 or less from the viewpoint of imparting scratch resistance due to a high crosslinking density, and 2 or more and 8 or less from the viewpoint that curing shrinkage hardly occurs. It is more preferably 2 or more and 6 or less. Examples of the monofunctional polymerizable oligomer include caprolactone-based urethane (meth) acrylate obtained by the reaction of caprolactone-based polyol, organic isocyanate and hydroxy (meth) acrylate, and (meth) acrylate in the side chain of polybutadiene oligomer. Polymeric urethane (meth) acrylates such as polybutadiene (meth) acrylate having a group and having high hydrophobicity can be mentioned.

  As the polymerizable polymer, a polymer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyether-based urethane (meth) acrylate or polycaprolactone-based urethane (meth ) Acrylate, polyester (meth) acrylate-based, polyether (meth) acrylate-based polymers and the like are preferable, and polycaprolactone-based urethane (meth) acrylate or urethane (meth) acrylate-based is more preferable. The above (meth) acrylate means acrylate or methacrylate. These polymers may be used alone or in combination of two or more.

(particle)
Further, the curable resin composition forming the hard coat layer 121 may further contain particles in order to improve scratch resistance. The particles include inorganic particles and organic particles, and examples of the inorganic particles include particles of alumina, silica, kaolinite, iron oxide, diamond, silicon carbide and the like. The particle shape may be a sphere, an ellipsoid, a polyhedron, a scaly shape or the like, and is not particularly limited, but a spherical shape is preferable from the viewpoint of higher hardness and excellent scratch resistance. The average particle diameter of the particles is not particularly limited, but from the viewpoint of hardness and smoothness of the hard coat layer 121, 0.1 μm or more and 4 μm or less, and preferably 0.5 μm or more and 3 μm or less. In the present embodiment, the average particle size of the particles is the volume average particle size. The volume average particle diameter can be measured by a laser diffraction type or a laser scattering type particle size distribution measurement.

  Among these inorganic particles, silica particles are one of the preferable ones. This is because the silica particles improve scratch resistance and do not impair the transparency of the hard coat layer 121. As the silica particles, it is possible to appropriately select and use from conventionally known silica particles, and colloidal silica particles and the like are also suitable. Even if the amount of colloidal silica particles is increased, the transparency is less affected.

  On the other hand, as the organic particles, synthetic resin beads such as crosslinked acrylic resin and polycarbonate resin are preferably mentioned.

  The content of the particles is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, and further preferably 1 part by mass with respect to 100 parts by mass of the curable resin. It is above 5 parts by mass. When the content of the particles is within the above range, excellent scratch resistance, transparency, and adhesion with the primer layer 122 can be obtained.

(Other components)
The curable resin composition forming the hard coat layer 121 may be diluted with a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate for the purpose of adjusting the viscosity of the resin composition. , Can be used in combination as long as the object of the present invention is not impaired. The monofunctional (meth) acrylates may be used alone or in combination of two or more, and may be used in combination with a low molecular weight polyfunctional (meth) acrylate.
As the diluent, an ordinary organic solvent may be used in addition to the above-mentioned monomers to ensure the coatability of the resin composition.

  Further, in the curable resin composition, in addition to the curable resin, if desired, a lubricant such as a non-reactive silicone compound may be contained within a range that does not impair the performance of imparting scratch resistance to the decorative member. Good.

The curable resin composition may contain a non-reactive silicone compound from the viewpoint of improving scratch resistance and weather resistance and obtaining excellent transparency. The non-reactive silicone compound is not particularly limited as long as it is a silicone compound having no reactive functional group such as amino group, epoxy group, mercapto group, carboxy group, hydroxy group, (meth) acryloyl group, allyl group, and the like. , Silicone oil consisting of polysiloxane, polyether modified silicone oil, aralkyl modified silicone oil, fluoroalkyl modified silicone oil, long chain alkyl modified silicone oil, higher fatty acid ester modified silicone oil, higher fatty acid amide modified silicone oil, phenyl modified Preferred examples include silicone oil.
The reactive silicone compound having a reactive functional group in the molecule as described above tends to undergo shrinkage upon curing, and therefore it is preferable not to include it in the curable resin composition.

  The content of the non-reactive silicone compound is preferably 0.05 parts by mass or more and 30 parts by mass or less, and more preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the curable resin. And more preferably 0.1 part by mass or more and 5 parts by mass or less. When the content of the non-reactive silicone compound is within the above range, excellent scratch resistance and weather resistance are obtained, and curing shrinkage does not occur.

  Further, the curable resin composition used for forming the hard coat layer 121 may contain a weather resistance improver in order to obtain excellent weather resistance. Examples of the weather resistance improver include an ultraviolet absorber and a light stabilizer. The ultraviolet absorber absorbs harmful ultraviolet rays and improves the long-term weather resistance and stability of decoration. Further, the light stabilizer itself hardly absorbs ultraviolet rays, but it is possible to obtain stabilization by efficiently trapping harmful free radicals generated by ultraviolet rays.

  However, when an ultraviolet absorber is used for the hard coat layer 121, its content is preferably 0.1 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the curable resin. The amount is more preferably 2 parts by mass or more and is more preferably 0.3 parts by mass or more and 1.5 parts by mass or less. When the content of the ultraviolet absorbent in the hard coat layer 121 is in the above range, the absorbent does not bleed out and sufficient ultraviolet absorbing ability is obtained, so that excellent weather resistance is obtained. Even if the hard coat layer 121 contains a large amount of an ultraviolet absorber, it is difficult to achieve both scratch resistance and weather resistance. Therefore, as described later, it is preferable that the primer layer 122 contains a large amount of an ultraviolet absorber. It is preferable for ensuring the scratch resistance of 121. The details of the ultraviolet absorber will be described in the primer layer 122.

  Further, examples of the light stabilizer include hindered amine light stabilizers having a reactive functional group. The reactive functional group is not particularly limited as long as it has reactivity with an ionizing radiation-curable resin, and examples thereof include a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group or an allyl group. And the like, and at least one selected from these is preferable. Of these, a (meth) acryloyl group is preferred.

  Examples of the hindered amine light stabilizer having such a reactive functional group include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate and bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, bis (2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2) 2,6,6-Pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] Preferred examples thereof include -6- (2-hydroxyethylamine) -1,3,5-triazine).

  Further, the curable resin composition for forming the hard coat layer may contain various additives as long as the performance thereof is not impaired. Examples of various additives include a polymerization inhibitor, a cross-linking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, a defoaming agent, a filler, and a solvent. Etc.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add a photopolymerization initiator in an amount of 0.1 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the curable resin. The photopolymerization initiator can be appropriately selected from those conventionally used.

[thickness]
In order to suppress attenuation, diffraction, scattering and frequency fluctuations of radio waves such as millimeter waves and near infrared rays transmitted and received by the radio wave radar, the thickness of the hard coat layer 121 is preferably as thin as possible in the range that does not impair the performance of imparting scratch resistance, It is preferable to have a thickness within a range that does not impair the weather resistance. Further, from the viewpoint of making the hard coat layer 121 transparent and reducing the occurrence of curing shrinkage, the thinner the hard coat layer 121, the more preferable. In the present embodiment, the thickness of the hard coat layer 121 is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 6 μm or less, and particularly preferably 2 μm or more and 4 μm or less.

  In the present embodiment, when the hard coat layer 121 is applied to the first resin substrate (reference numeral 20 in FIG. 2) forming the radio wave transmitting decorative member provided in the vehicle or the electronic device, the transfer hard coat film 10 is used. Since the hard coat layer 121 is simultaneously transferred onto the first resin substrate 20 by injection molding, the hard coat layer 121 can be easily thinned and the film thickness can be easily made uniform. .

  Even if a conventionally known hard coating agent coating method such as a dip method, a spray method, a spin coating method, a roll coating method, a curtain coating method, or a flow coating method is adopted on the first resin substrate 20, the hard coating is performed. It is difficult to achieve both thinning of the layer 121 and uniforming of the film thickness.

[Primer layer]
The primer layer 122 is a layer that is disposed between the hard coat layer 121 and the adhesive layer 123, functions as a stress relaxation layer for the hard coat layer 121, and plays a role of improving the adhesion with the hard coat layer 121. Further, it is a layer which plays a role of improving weather resistance by further containing an ultraviolet absorber. Further, the primer layer 122 is provided to suppress cracking due to deterioration of the hard coat layer 121, suppresses the occurrence of a blocking phenomenon during the production process and storage, and causes deterioration of the winding shape of the film and damage to the film. It is preferably a layer provided so as not to allow it.

  Further, the primer layer 122 preferably contains, as an ultraviolet absorber, a first ultraviolet absorber which is an ultraviolet absorber having an absorption peak at a wavelength of 350 nm or more and 400 nm or less. The first UV absorber is preferably a benzotriazole UV absorber or a hydroxyphenyltriazine UV absorber, more preferably a benzotriazole UV absorber. Examples of such a first ultraviolet absorber include a benzotriazole-based ultraviolet absorber having a maximum absorption wavelength of 378 nm (Tinuvin Carbon Protect (trade name) manufactured by BASF Japan Ltd.). In addition, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a maximum absorption wavelength of 356 nm (Tinuvin 477 (trade name), manufactured by BASF Japan Ltd.) can also be mentioned.

  The content of the first ultraviolet absorber in the primer layer 122 may be appropriately adjusted so that the average light transmittance of the transfer layer 12 at a wavelength of 350 nm or more and 400 nm or less is 25% or less. The amount is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and more preferably 10 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the curable resin. It is particularly preferable that When the content of the first ultraviolet absorber in the hard coat layer 121 is in the above range, excellent weather resistance can be obtained with respect to ultraviolet rays which are light having a wavelength of 350 nm to 400 nm and visible light having a short wavelength. it can. When the content of the first ultraviolet absorber in the primer layer 122 is less than 1 part by mass, fading of the indium glossy layer described later easily proceeds, which is not preferable. When the content of the first ultraviolet absorber in the primer layer 122 exceeds 50 parts by mass, the adhesiveness is deteriorated, which is not preferable.

  As the ultraviolet absorber, a second ultraviolet absorber may be contained in addition to the above-mentioned first ultraviolet absorber. The second ultraviolet absorber is an ultraviolet absorber other than the first ultraviolet absorber. The transfer layer preferably contains the second ultraviolet absorber so that the average of the light transmittances at wavelengths of 300 nm to 350 nm is 0.5% or less.

  The content of the second ultraviolet absorber may be appropriately adjusted so that the average of the light transmittances at wavelengths of 300 nm or more and 350 nm or less is 0.5% or less, but the ultraviolet absorber contained in the transfer layer 12 Of these, 1% by mass or more and 50% by mass or less is preferable, 5% by mass or more and 40% by mass or less is more preferable, and 10% by mass or more and 35% by mass or less is particularly preferable. When the content of the second ultraviolet absorber in the hard coat layer 121 is in the above range, excellent weather resistance is obtained not only to ultraviolet rays having a wavelength of 350 nm to 400 nm but also to shorter wavelength ultraviolet rays. Obtainable.

  Hereinafter, as the second ultraviolet absorber, an inorganic ultraviolet absorber such as titanium dioxide, cerium oxide, or zinc oxide, or a benzotriazole-based or triazine-based organic ultraviolet absorber having an absorption peak at a wavelength of less than 350 nm and more than 400 nm is used. Are preferred. Among the triazine-based UV absorbers, the hydroxyphenyltriazine-based UV absorber is more preferable. Examples of the hydroxyphenyl triazine-based ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5- Triazine, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tri) Decyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy- Preferred examples include-(2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like. Alternatively, a plurality of types can be used in combination.

  Examples of the light stabilizer used in the primer layer 122 include a hindered amine light stabilizer (HALS), and more specifically, a hindered amine light stabilizer having no reactive functional group, or the hard coat layer 121. The hindered amine-based light stabilizer having a reactive functional group preferably used for the formation of In particular, from the viewpoint of providing the primer layer 122 with excellent stress relaxation performance, a hindered amine light stabilizer having no reactive functional group is preferable as the light stabilizer used in the primer layer 122. Specific examples of the hindered amine light stabilizer having no reactive functional group include 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1 , 2,2,6,6-Pentamethyl-4-piperidyl), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octyloxy-2,2,6,6- Tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like can be mentioned. These light stabilizers may be used alone or in combination of two or more.

[Binder resin]
The binder resin forming the primer layer 122 according to this embodiment preferably contains a two-component curable resin including a main agent and a curing agent.

[Main agent]
The main agent is not particularly limited, and examples thereof include polyurethane resin, (meth) acrylic resin, vinyl chloride / vinyl acetate copolymer, polyester resin, utilal resin, chlorinated polypropylene, chlorinated polyethylene and the like. These binder resins may be used alone or in combination of two or more. Among these binder resins, polyurethane resin is preferable from the viewpoint of adhesion and weather resistance.

  The polyurethane resin is more preferably a polyurethane resin having an acrylic skeleton in the polymer chain of the polyurethane resin from the viewpoint of weather resistance and durability. Examples of the polyurethane resin having an acrylic skeleton in the polymer chain include, for example, a urethane acrylic copolymer that is a copolymer of a urethane component and an acrylic component, a hydroxyl group or an isocyanate group as a polyol component or a polyisocyanate component that constitutes polyurethane. There is an acrylic resin having a, and a urethane acrylic copolymer is preferable among them. The urethane acrylic copolymer may be obtained, for example, by a method of reacting an acrylic resin having at least two hydroxyl groups in one molecule with a polyol compound and an isocyanate compound (see Japanese Patent Laid-Open No. 6-100563, etc.) or unsaturated double copolymers. It can be obtained by a method of reacting an acrylic monomer with a urethane prepolymer having a bond at both ends (see JP-A-10-1524, etc.) and the like.

  Among the above-mentioned polyurethane resins having an acrylic skeleton in the polymer chain, those having a polycarbonate skeleton or a polyester skeleton in the polymer chain are preferable from the viewpoint of adhesion to the hard coat layer. As the polyurethane having an acrylic skeleton in the polymer chain and further having a polycarbonate skeleton or a polyester skeleton, a polycarbonate urethane acrylic copolymer which is a copolymer of a polycarbonate urethane component and an acrylic component, or a polyester urethane component A polyester-based urethane acrylic copolymer, which is a copolymer of the acrylic component and acrylic component, is more preferable, and it is particularly preferable to use a polycarbonate-based urethane acrylic copolymer from the viewpoint of providing further excellent weather resistance. These polyurethanes may be used alone or in combination of two or more.

  The polycarbonate-based urethane acrylic copolymer can be obtained, for example, by copolymerizing a polycarbonate-based urethane obtained by reacting a carbonate diol and diisocyanate with a diol having an acrylic skeleton. The polycarbonate-based urethane acrylic copolymer can also be obtained by reacting a diol having an acrylic skeleton with a carbonate diol and diisocyanate. Here, as the diol having an acrylic skeleton, specifically, (meth) acrylic acid, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 6 carbon atoms, or an oligomer obtained by radical polymerization of these, or A compound in which two hydroxyl groups are introduced into a prepolymer (degree of polymerization of 2 to 10) is included.

Specific examples of the diisocyanate include aliphatic incyanates such as hexamethylene diisocyanate; alicyclic incyanates such as isophorone diisocyanate and hydrogen-converted xylylene diisocyanate. In addition, as the carbonate diol, specifically, a compound represented by the following general formula (1) (in the formula, R ^{1 s} are the same or different and have 1 to 12 carbon atoms which may have a substituent) The following alkylene groups, divalent heterocyclic groups having 1 to 12 carbon atoms which may have a substituent, or divalent fats having 1 to 12 carbon atoms which may have a substituent. It is a cyclic group, and m ₁ is an integer of 1 or more and 10 or less) and the like.
_{^{HO- [R 1 -O- (C =}} O) -O] m 1 -R 1 -OH (1)

  The polycarbonate-based urethane acrylic copolymer can also be obtained by radically polymerizing a polycarbonate-based polyurethane prepolymer having a radical-polymerizable group introduced therein, with an acrylic monomer. Specific examples of the acrylic monomer include (meth) acrylic acid and (meth) acrylic acid alkyl esters in which the alkyl group has 1 to 6 carbon atoms.

The polyester-based urethane acrylic copolymer can be obtained, for example, by copolymerizing a polyester-based urethane obtained by reacting an ester diol and diisocyanate with a diol having an acrylic skeleton. Alternatively, it can also be obtained by reacting a diol having an acrylic skeleton with an ester diol and a diisocyanate. Here, the diol and diisocyanate having an acrylic skeleton are the same as those used in the production of the above-mentioned polycarbonate urethane urethane copolymer. In addition, as the ester diol, specifically, a compound represented by the following general formula (2) (wherein R ² is the same or different, and may have a substituent group having 1 to 12 carbon atoms) Alkylene group, a divalent heterocyclic group having 1 to 12 carbon atoms which may have a substituent, or a divalent alicyclic group having 1 to 12 carbon atoms which may have a substituent. Group, and m ₂ is an integer of 1 or more and 10 or less) and the like.
_{^{HO- [R 2 -O- (C =}} O)] m 2 -R 2 -OH (2)

  The polyester-based urethane acrylic copolymer can also be obtained by radically polymerizing a polyester-based polyurethane prepolymer having a radical-polymerizable group introduced therein, with an acrylic monomer. The acrylic monomer is the same as that used in the production of the above polycarbonate-based urethane acrylic copolymer.

  The polyurethane used for the primer layer 122 preferably has an acrylic component content of 1% by mass or more and 30% by mass or less in order to provide excellent weather resistance. Here, the content of the acrylic component in the polyurethane is the proportion (mass%) of the monomers constituting the acrylic skeleton with respect to the total mass of the polyurethane. From the viewpoint of providing further excellent weather resistance, the content of the acrylic component in the polyurethane is preferably 5% by mass or more and 20% by mass or less. The content of the acrylic component in the polyurethane is calculated by measuring the NMR spectrum of the polyurethane and determining the ratio of the peak area attributed to the acrylic component to the total peak area.

  When the polyurethane and the other binder resin are used in combination in the primer layer 122, the mixing ratio thereof is not particularly limited, but for example, the polyurethane is 50 parts by mass or more per 100 parts by mass of the binder resin. It is preferable that the amount is set to 70 parts by mass or more, and more preferably 85 parts by mass or more.

[Curing agent]
From the viewpoint of accelerating the curing of the above-mentioned base compound, for example, an isocyanate curing agent such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, etc. may be mentioned.

  From the viewpoint of improving the stress relaxation performance and the adhesion between the surface protective layer and the adhesive layer, the amount of the curing agent used is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin as the main component. The amount is more preferably 30 parts by mass or more, and particularly preferably 20 parts by mass or more and 30 parts by mass or less.

  The primer layer 122 according to the present embodiment may contain various additives other than the above, as necessary, within a range that does not impair the effects of the present invention. Examples of such additives include abrasion resistance improvers, infrared absorbers, light stabilizers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, and defoamers. Examples include agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used additives.

[thickness]
In order to suppress attenuation, diffraction, scattering, and frequency fluctuations of radio waves such as millimeter waves and near infrared rays transmitted and received by the radio wave radar, the thickness of the primer layer 122 is preferably as thin as possible without impairing the performance of imparting weather resistance. It is preferable to have a thickness in the range where the average of the light transmittance of 350 nm or more and 400 nm or less is 25% or less. In the present embodiment, the thickness of the primer layer 122 is preferably 0.1 μm or more and 10 μm or less, more preferably 0.1 μm or more and 5 μm or less, and particularly preferably 1 μm or more and 4 μm or less.

[Adhesive layer]
The adhesive layer 123 according to the present embodiment is a layer provided to adhere the hard coat layer 121 to the first resin substrate 20 in order to form the hard coat layer 121 on the surface of the first resin substrate 20. In addition to the function of adhering the hard coat layer 121 to the first resin substrate 20, the adhesive layer 123 is transparent by softening the so-called cue in which particles contained in the primer layer 122 are projected to the surface of the primer layer 122. It is also preferable to have a function of suppressing deterioration of properties and ensuring excellent optical performance.

  The adhesive resin that can be used for the adhesive layer 123 according to the present embodiment is determined according to the material of the first resin substrate 20 and the transfer temperature and pressure at the time of transfer, but in general, acrylic resin, chloride A heat fusion resin such as a vinyl-vinyl acetate copolymer, a polyamide resin, a polyester resin, a chlorinated polypropylene, a chlorinated rubber, a urethane resin, an epoxy resin or a styrene resin is preferable, and the material of the first resin substrate 20 or a transfer product. One or two or more resins are selected from the above resins according to the application. It is particularly preferable to use an acrylic resin alone as the heat fusion resin from the viewpoints of a small difference in refractive index from the particles contained in the primer layer 122, excellent transparency, and improved transparency and weather resistance.

  In order to suppress attenuation, diffraction, scattering, and frequency fluctuation of radio waves such as millimeter waves and near infrared rays transmitted and received by the radio wave radar, the thickness of the adhesive layer 123 is preferably as thin as possible so long as the performance of providing adhesiveness is not impaired. The thickness of the adhesive layer 123 is preferably thicker than that of the primer layer 122. From the viewpoint of suppressing attenuation, diffraction, scattering, and frequency fluctuation of millimeter waves transmitted and received by the radio wave radar, from the viewpoint of adhering the transfer layer including the hard coat layer 121 to the first resin substrate 20, and from the viewpoint of excellent transparency. From the viewpoint of ensuring the thickness, the thickness of the adhesive layer 123 is preferably 1 μm or more and 7 μm or less, more preferably 1 μm or more and 6 μm or less, and particularly preferably 1 μm or more and 5 μm or less.

  In addition, in order to suppress attenuation, diffraction, scattering, and frequency fluctuations of radio waves transmitted and received by the radio wave radar, the total thickness of the hard coat layer 121, the primer layer 122, and the adhesive layer 123 is also the total of each layer. The thinner the thickness, the better as long as the original performance is not impaired. The total thickness of the hard coat layer 121, the primer layer 122, and the adhesive layer 123 is preferably 15 μm or less, and more preferably 10 μm or less.

  Further, the transfer hard coat film 10 according to the present embodiment is such that a surface is protected by attaching a cover film (protective film) made of a resin such as a polyethylene resin on the adhesive layer 123 to keep the product. It is preferable above. When providing a cover film, the hard coat film for transfer 10 of the present embodiment is peeled off the cover film to expose the adhesive layer 123, and is transferred to the first resin substrate 20 through the surface of the adhesive layer 123. .

[Colored layer]
Although not essential in the transfer hard coat film of the present invention, in order to improve the designability of the decorative member, a coloring layer (decorative layer) may be further provided on a part or the entire surface of the transfer hard coat film, if necessary. It may be provided. Although the pattern of the colored layer is arbitrary, for example, a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letter, or the like can be provided.

  The coloring layer is laminated, for example, between the primer layer and the adhesive layer, but is not limited to this and may be formed on the adhesive layer in the case of a material having adhesiveness.

  The method for forming the colored layer is, for example, using a resin such as polyvinyl resin, polyester resin, acrylic resin, polyvinyl acetal resin, or cellulose resin on the primer layer 122 as a binder, and a pigment or dye of an appropriate color. It can be formed by printing with a printing ink that contains as a colorant. Examples of the printing method include known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and inkjet printing. The thickness of the colored layer is preferably 5 μm or more and 40 μm or less, more preferably 5 μm or more and 30 μm or less from the viewpoint of designability.

<Method for producing transfer hard coat film>
The method for producing the transfer hard coat film 10 according to the present embodiment is not particularly limited, and examples thereof include a method for producing a transfer hard coat film having at least the following steps in order.

a) Step of forming hard coat layer 121 on base film 11 b) Step of forming primer layer 122 using composition for forming primer layer on hard coat layer 121 c) Formation of adhesive layer on primer layer 122 Of forming the adhesive layer 123 using the composition for use

  Each step will be described below.

[A) Step of forming hard coat layer on base film]
As a method for forming a transfer layer including the hard coat layer 121 on the base film 11, a resin composition for forming a hard coat layer is gravure coated so that the thickness after curing is usually about 1 μm or more and 10 μm or less. , Bar coating, roll coating, reverse roll coating, comma coating, and the like, preferably by gravure coating, followed by curing. When the resin composition contains a solvent, it is preferable that after coating, the coating layer is preliminarily heated and dried by a hot air dryer or the like, and then further subjected to heat treatment or irradiation with ionizing radiation.

  Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected depending on the resin and the thickness of the layer to be used. It is preferable to cure the uncured resin layer.

[B) Step of forming a primer layer using the composition for forming a primer layer]
Next, the primer layer 122 is formed using the composition for forming a primer layer on the hard coat layer 121. The primer layer 122 can be formed by a coating method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, slit coating, or die coating, or a transfer coating method. Here, the transfer coating method is a method of forming a coating film of the primer layer 122 on a thin sheet (film base material) and then coating the surface of the hard coat layer 121. Gravure coating is preferred.

  Further, when forming the primer layer 122 according to the present embodiment, in order to improve the adhesion between the hard coat layer 121 and the primer layer 122, the hard coat layer 121 is cured only in a semi-cured state, and thereafter, It is also possible to enhance the adhesion between the hard coat layer 121 and the primer layer 122 by completely curing the hard coat layer 121 after applying the resin composition for forming the primer layer.

The surface of the primer layer 122 may be dried as long as the uncured state can be maintained. Here, the uncured state is a state in which the unreacted curing agent remains in the primer layer 122, and the higher the residual rate, the more preferable from the viewpoint of preventing the transparency of the primer layer 122 from decreasing. It is preferable that the peak intensity of the infrared spectrum 2260 cm ⁻¹ corresponding to the isocyanate portion of the curing agent is 50% or more based on the peak intensity immediately after coating the primer layer 122.

[C) Step of forming an adhesive layer using the composition for forming an adhesive layer]
Next, the adhesive layer 123 is formed on the primer layer 122 using the adhesive layer forming composition. The method of forming the adhesive layer 123 may be the same as that of the above b) and is not particularly limited.

[D) Step of curing primer layer]
Optionally, primer layer 122 may be cured. The curing here is a step of completely reacting the curing agent remaining in the primer layer 122 with the main component. Specifically, the curing reaction may be accelerated by a conventionally known method, and depending on the type of curing agent, it is typically placed at a temperature of 40 ° C. or higher and 60 ° C. or lower for 24 hours or longer and 72 hours or shorter. Good.

<Intermediate product of decorative material>
The intermediate product of the decorative member is that the adhesive layer 123, the primer layer 122, the hard coat layer 121, and the base material film 11 as needed are laminated on the surface of the first resin substrate 20 in this order. It is a laminated body. By laminating the transfer layer 12 including the hard coat layer 121 on the surface of the first resin substrate 20, it is possible to impart sufficient scratch resistance to the first resin substrate 20 (see FIG. 2).

[First resin substrate]
The resin forming the first resin substrate 20 can be appropriately selected according to the application. Above all, the transfer hard coat film 10 of the present embodiment is preferably a resin that is excellent in scratch resistance, weather resistance, and transparency, and that can prevent peeling of the hard coat layer 121 due to simultaneous injection molding transfer.

  Examples of the first resin substrate 20 having high transparency include polycarbonate resin, acrylic resin, polyester resin and the like. Above all, the resin forming the first resin substrate 20 is preferably a polycarbonate resin because of its excellent impact resistance.

  Concavities and convexities are formed on the back surface of the first resin substrate 20. The colored layer is formed on the convex and concave portions and the indium luster layer is formed on both the concave and convex portions, so that when the first resin substrate 20 is viewed from the hard coat layer 121 side, the concave layer is formed. The formed indium gloss layer 312 can be made to appear as if it were raised with respect to the surrounding color material layer 311 (see FIG. 4).

  In order to suppress attenuation, diffraction, scattering, and frequency fluctuations of radio waves transmitted and received by the radio wave radar, it is preferable that the thickness of the first resin substrate 20 be as thin as possible without impairing practical strength such as surface rigidity. In the present embodiment, the thickness of the first resin substrate 20 is usually preferably 1 mm or more and 15 mm or less, and more preferably 2 mm or more and 5 mm or less. If the first resin substrate 20 is too thin, practical strength such as surface rigidity becomes insufficient, and if the first resin substrate 20 is too thick, attenuation, diffraction, scattering, and scattering of millimeter waves transmitted and received by the millimeter wave radar are performed. Affects frequency fluctuations.

  The depth of the irregularities of the first resin substrate 20 is not particularly limited, but is preferably 1 mm or more and 5 mm or less, more preferably 1 mm or more and 3 mm or less. If the unevenness is too shallow, even if the colored layer 31 is formed on the back surface of the first resin substrate 20 (see FIG. 4), the design is inferior and the indium gloss layer 312 of the colored layer 31 is less than the color material layer 311. I can't make it appear three-dimensional. If the unevenness is too deep, it may affect the practical strength such as surface rigidity of the first resin substrate 20.

[Method for manufacturing intermediate product of decorative member]
FIG. 3 is a schematic view showing an example of a method for manufacturing an intermediate product of a decorative member according to this embodiment. The manufacturing method of the intermediate product of the decorative member has at least the following steps in order.
a) A step of setting the transfer hard coat film 10 in the fixed mold 51A for injection molding, in which the transfer hard coat film 10 is fixed to the fixed mold 51A so that the surface of the base film 11 contacts the surface of the fixed mold 51A. Step of setting b) Step of setting movable mold 51B having an uneven shape on the back surface of the adhesive layer 123 c) Step of injecting the first resin substrate forming composition 20 ′ onto the back surface of the adhesive layer 123, A step of injection-integrating the transfer hard coat film 10 and the first resin substrate 20 formed on the back surface of the transfer hard coat film 10 and having irregularities on the back surface.

[A) Step of setting the hard coat film for transfer on a fixed mold for injection molding]
In step a), first, the adhesive layer 123 side (the side opposite to the base film 11) of the transfer hard coat film 10 is directed toward the fixed mold 51A for injection molding from the adhesive layer 123 side by the heater 52. The coat film 10 is heated ((a1) in FIG. 3).

  The temperature at which the transfer hard coat film 10 is heated is preferably in the range above the glass transition temperature of the substrate film 11 and below the melting temperature (or melting point). Usually, it is more preferable to carry out at a temperature near the glass transition temperature. The term “near the glass transition temperature” refers to a range of the glass transition temperature ± 5 ° C., and when a polyester film suitable as the substrate film 11 is used, it is generally about 70 to 130 ° C.

  Next, the transfer hard coat film 10 is preformed (vacuum forming) so as to follow the shape of the fixed mold 51A, and the transfer hard coat film 10 is brought into close contact with the fixed mold 51A ((a2) in FIG. 3).

  The molding surface of the fixed die 51A is a smooth curved surface, and the shape transferred by the molding surface of the fixed die 51A becomes the shape of the surface of the intermediate product of the decorative member.

[B) Step of setting movable mold 51B on the back surface of adhesive layer 123]
Next, the movable mold 51B for injection molding is set on the side of the adhesive layer 123 of the transfer hard coat film 10 (the side opposite to the base film 11), and the mold is clamped ((b) of FIG. 3).

  Although illustration is omitted, the molding surface of the movable die 51B has an uneven shape. The shape transferred by the molding surface of the movable die 51B becomes the shape of the back surface of the intermediate product of the decorative member.

[C) Process of injection-integrating the transfer hard coat film and the first resin substrate]
Next, the first resin substrate-forming composition 20 ′ is injected onto the back surface of the adhesive layer 123, and is formed on the transfer hard coat film 10 and the back surface of the transfer hard coat film 10. The resin base 20 of No. 1 is injection-integrated ((c) of FIG. 3).

  In the present embodiment, the suitable first resin substrate-forming composition 20 '(for example, a polycarbonate resin composition) is thermoplastic and therefore is injected in a fluidized state by heating and melting. Then, the first resin substrate-forming composition 20 'is cooled and solidified. As a result, the transfer hard coat film 10 is integrally attached to the formed first resin substrate 20 and adhered, and the intermediate product of the base film-added decorative member is obtained. The heating temperature of the first resin substrate-forming composition 20 'depends on the type of the first resin substrate-forming composition 20', but is generally about 180 to 320 ° C.

[D) Post-process]
After forming the intermediate product of the base film-added decorative member, the intermediate product of the base film-added decorative member is taken out from the injection molding die 51 (fixed die 51A and movable die 51B) ((d) of FIG. 3). Then, if necessary, the base film 11 is peeled off from the primer layer 122 to obtain an intermediate product of a decorative member. The base film 11 may be peeled from the primer layer 122 at the same time when the intermediate product of the base film-added decorative member is taken out of the injection mold 51.

  In the present embodiment, when the hard coat layer 121 is applied to the first resin substrate (reference numeral 20 in FIG. 2) that constitutes the radio wave transmitting decorative member, the first resin is formed by using the transfer hard coat film 10. Since the hard coat layer 121, the primer layer 122, and the adhesive layer 123 are simultaneously transferred onto the substrate 20 by injection molding, the respective layers can be easily thinned and the film thickness can be easily made uniform. .

  When a conventionally known hard coating agent coating method such as a dip method, a spray method, a spin coating method, a roll coating method, a curtain coating method, or a flow coating method is adopted on the first resin substrate 20, a hard coating layer is used. It is necessary to individually repeat the coating and drying of the coating composition, the coating and drying of the primer layer composition, and the coating and drying of the adhesive layer composition, which imposes a heavy burden on the work. Further, if the film thickness of each layer is prioritized, it is difficult to make the film thickness uniform. On the other hand, if the film thickness is made uniform, it is difficult to make each layer thin. In addition, since the conventionally known hard coating agent application method is generally performed in the final manufacturing step of the decorative member, there is a risk that the first resin substrate 20 may be damaged by this final step. On the other hand, in the present embodiment, by simultaneously transferring the transfer hard coat film 10 onto the first resin substrate 20 by injection molding, the hard coat layer 121 can be easily thinned and the film thickness can be simplified. It can be said that it can be made uniform and is excellent in productivity. In addition, in the present embodiment, since the first hard coat layer 121 is provided on the first resin substrate, the number of defective products caused by scratching the first resin substrate is reduced, the yield is improved, and the production is improved. It can be said that it is excellent in sex.

<Radio-transparent decorative member>
The radio wave transmitting decorative member of the present embodiment is a decorative member arranged on the front surface of the radio wave radar device, and the decorative member includes the indium luster layer 312 and the first resin substrate 20 which is a resin substrate. , A transfer layer 12 including an adhesive layer 123, a primer layer 122, and a hard coat layer 121 in this order, and the primer layer 122 contains a first ultraviolet absorber, and the transfer layer 12 has a wavelength of 350 nm or more. The average light transmittance of 400 nm or less is 25% or less.

  Further, the radio wave transmitting decorative member 30 of the present embodiment is a decorative member arranged on the front surface of the radio wave radar device, and as shown in FIG. 4, the decorative member 30 is the second resin substrate 33. The indium gloss layer 312, the first resin substrate 20, the transfer layer 12 including the adhesive layer 123, the primer layer 122, and the hard coat layer 121 in this order, and the first in the primer layer 122. Of the ultraviolet absorber, the transfer layer 12 has an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less.

  The indium luster layer 312 is provided to improve the design of the radio wave transmitting decorative member 30. The indium luster layer 312 of the radio wave transmitting decorative member 30 is formed as a coloring layer 31 described later together with the coloring material layer 311 formed on the resin substrate 20. In order to prevent the colored layer 31 from being corroded by heat, a heat-resistant layer 32 is formed between the colored layer 31 and the second resin substrate 33 as needed (see FIG. 4).

[Colored layer]
The colored layer (decorative layer) 31 is provided to improve the design of the radio wave transmitting decorative member 30. The colored layer 31 includes a color material layer 311 formed on the convex portion 20A of the resin substrate 20 and at least an indium gloss layer 312 formed on the concave portion 20B of the resin substrate 20.

  The colored layer 31 is a layer (characters, symbols, figures, patterns, etc.) formed by disposing concealing (light non-transmissive or low light transmissive) materials in a desired pattern. By forming the color material layer 311 on the convex portion 20A of the resin substrate 20 and forming the indium luster layer 312 on the concave portion 20B of the resin substrate 20, it is possible to visually recognize the radio wave transmitting decorative member 30 from the hard coat layer 121 side. The indium luster layer 312 can be made to appear to the person three-dimensionally with respect to the surrounding color material layer 311.

[Color material layer]
The color material forming the color material layer 311 is not particularly limited. When the desired pattern is a single color, only one color layer appropriately selected as the color material layer 311 may be formed. When the desired pattern has a plurality of colors, the color material layer 311 is appropriately selected. You may form with a layer of multiple colors.

  The color material layer 31 can be formed by printing using a known printing ink or paint.

  The thickness of the color material layer 31 is particularly preferably within a range in which the color material layer 311 is formed evenly and the attenuation, diffraction, scattering and frequency fluctuation of radio waves such as millimeter waves and near infrared rays transmitted and received by the radio wave radar can be suppressed. Not limited.

[Indium gloss layer]
The indium luster layer 312 is formed in a discontinuous structure forming a structure (sea-island structure) in which indium exists in a state of being slightly separated from each other in an island shape as described above.

  Since indium is a rare metal and is expensive, research into alternative materials such as nickel, copper, silver, tin, gold, and alloys thereof in place of indium has been advanced in recent years. In the present embodiment, the indium gloss layer 312 may include a substitute material other than indium as long as it has radio wave transmission.

  The method of forming the indium glossy layer 312 is not particularly limited, but it is preferable to form the indium glossy layer 312 by vapor deposition because it can be made thinner. The vapor deposition may be physical vapor deposition or chemical vapor deposition. Examples of physical vapor deposition include vacuum vapor deposition, ion plating, and sputtering. Examples of the chemical vapor deposition include plasma CVD using plasma, catalytic chemical vapor deposition (Cat-CVD) in which a material gas is catalytically pyrolyzed using a heating catalyst, and the like. Among these vapor deposition methods, sputtering is preferable from the viewpoint of adhesion and film quality.

  The thickness of the indium glossy layer 312 is not particularly limited as long as the indium glossy layer 312 is uniformly formed and the attenuation, diffraction, scattering, and frequency fluctuation of the radio waves transmitted and received by the radio wave radar can be suppressed. The thickness of the indium luster layer 312 is preferably 10 nm or more and 300 nm or less, and more preferably 20 nm or more and 200 nm or less.

[Heat-resistant layer]
A heat resistant layer 32 is formed on the back surface of the colored layer 31 as needed.

  The heat resistant layer 32 is provided to prevent the indium glossy layer 312 from being corroded by heat. The heat resistant layer 32 is preferably a cured product of an acrylic resin composition or a urethane resin composition.

  The thickness of the heat-resistant layer 32 is not particularly limited as long as the heat-resistant layer 32 is uniformly formed and the attenuation, diffraction, scattering and frequency fluctuation of the radio waves transmitted and received by the radio radar can be suppressed. The heat-resistant layer 32 preferably has a thickness of 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 30 μm or less.

[Second resin substrate]
A second resin substrate 33 is formed on the back surface of the heat resistant layer 32 by, for example, an insert molding method.

  The resin forming the second resin base 33 is not particularly limited. Above all, the resin base 20 is preferably an AES resin because the transfer hard coat film of the present embodiment has excellent weather resistance. The AES resin is a synthetic resin whose weather resistance is enhanced by using ethylene-propylene-diene rubber (EPDM) instead of B (butadiene) of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin).

  In order to suppress attenuation, diffraction, scattering, and frequency fluctuation of radio waves transmitted and received by the radio wave radar, it is preferable that the thickness of the second resin substrate 33 is as thin as possible without impairing practical strength such as surface rigidity. In the present embodiment, the thickness of the second resin substrate 33 is usually preferably 1 mm or more and 15 mm or less, and more preferably 2 mm or more and 5 mm or less. If the second resin substrate 33 is too thin, practical strength such as surface rigidity becomes insufficient, and if the second resin substrate 33 is too thick, attenuation, diffraction, scattering, and scattering of millimeter waves transmitted and received by the millimeter-wave radar. Affects frequency fluctuations.

  The second resin substrate 33 is a laminate in which the adhesive layer 123, the primer layer 122, and the hard coat layer 121 are arranged in this order on the surface of the resin substrate 20, and the colored layer 31 and the like are arranged on the back surface of the resin substrate 20. The resin composition, which is a constituent of the second resin substrate, is injected into the body and is insert-molded to be laminated.

<Method of manufacturing radio wave transmitting decorative member>
The method of manufacturing the radio wave transmitting decorative member 30 is not particularly limited. For example, the coloring material layer 311 is formed on the convex portion 20A on the back surface of the resin substrate 20 in the intermediate product of the decorative member of the present embodiment by screen-printing with the coloring material layer forming composition to form the coloring material layer 311. After the indium gloss layer 312 is formed by vapor-depositing a metal having a radio wave transmission property on the back surface of the, heat-resistant by a coating method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, or a transfer coating method. The radio wave transmitting decorative member 30 can be obtained by forming the layer 32 and insert-molding the second resin base 33 on the back surface of the heat resistant layer 32.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Example 1>
A film (“TOYOBO ester film A4100 (trade name)” manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate resin (PET) having a thickness of 50 μm was used as the base film 11, and the following was formed on one surface of the base film 11. A curable resin composition for forming a hard coat layer is applied to form an uncured resin layer, which is then irradiated with an electron beam under the conditions of 90 kV and 10 Mrad (100 kGy) to crosslink and cure the uncured resin layer. Then, the hard coat layer 121 (layer thickness: 3.5 μm) was formed. Then, the surface of the hard coat layer 121 is subjected to a corona discharge treatment, and then the following resin composition for forming a primer layer is applied to form a primer layer 122 (layer thickness: 2.5 μm). A transfer hard coat film having a base film 11, a hard coat layer 121, a primer layer 122, and an adhesive layer 123, which are sequentially laminated with an adhesive layer 123 (layer thickness: 4 μm) using a resin (acrylic resin). Got 10. Then, the intermediate product of the decorative member can be obtained by performing simultaneous transfer molding by injection molding on the surface of the first resin substrate 20 having the unevenness on the back surface. Then, by forming the color material layer 311, the indium luster layer 312, and the second resin substrate 33 on the back surface of the intermediate product of the decorative member, the radio wave transmitting decorative member 30 can be obtained.

(Curable resin composition for forming hard coat layer)
(Curable resin)
Hexafunctional urethane acrylate: 50 parts by mass Caprolactone-based urethane acrylate: 50 parts by mass The following materials were added to 100 parts by mass (solid content 70%) of the curable resin.
Hydroxyphenyltriazine ultraviolet absorber C (maximum absorption wavelength 322 nm) ^{* 1} : 0.7 parts by mass Light stabilizer having a reactive functional group ^{* 2} : 4.2 parts by mass Non-reactive silicone compound ^{* 3} : 0.2 Parts by mass Particles (silica particles, average particle diameter: 2 μm): 2 parts by mass * 1, Tinuvin 479 (trade name), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6 -Bis (4-phenylphenyl) -1,3,5-triazine, manufactured by BASF Japan Ltd. * 2, Sanol LS-3410 (trade name), 1,2,2,6,6-pentamethyl-4-piperidi Nyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd. * 3, Polyether-modified silicone oil

(Resin composition for forming a primer layer)
Polycarbonate urethane acrylic copolymer ^{* 5} : 100 parts by mass Benzotriazole ultraviolet absorber A (maximum absorption wavelength 378 nm) ^{* 6} : 13 parts by mass Hydroxyphenyltriazine ultraviolet absorber C (absorption peak 322 nm): 17 parts by mass Hindered amine System light stabilizer ^{* 7} : 3 parts by mass Anti-blocking agent ^{* 8} : 9 parts by mass Curing agent: Hexane methylene diisocyanate: 25 parts by mass * 5, The mass ratio of urethane component and acrylic component in the polycarbonate urethane acrylic copolymer is 70 / 30.
* 6, tinuvin carbon protect (trade name), BASF Japan Ltd. * 7, tinuvin 123 (trade name), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate), BASF Japan Ltd. * 8, silica particles, average particle diameter: 3 μm

<Example 2>
The same as Example 1, except that the ultraviolet absorber A contained in the primer layer 122 was replaced with hydroxyphenyltriazine-based UV absorber B (maximum absorption wavelength 356 nm) ^{* 9 in} 24 parts by mass. Then, a hard coat film 10 for transfer was obtained. Then, the intermediate product of the decorative member can be obtained by performing simultaneous transfer molding by injection molding on the surface of the first resin substrate 20 having the unevenness on the back surface. Then, by forming the color material layer 311, the indium luster layer 312, and the second resin substrate 33 on the back surface of the intermediate product of the decorative member, the radio wave transmitting decorative member 30 can be obtained.
* 9, Tinuvin 477 (trade name), hydroxyphenyltriazine-based UV absorber (about 80%), 1-methoxy-2-propylacetate (about 20%), manufactured by BASF Japan Ltd.

<Comparative Example 1>
In Example 1, the color material layer 311, the indium luster layer 312, and the second indium luster layer 312 are formed on the first resin substrate 20 without transferring the transfer hard coat film to the first resin substrate 20, and on the first resin substrate 20 having the uneven surface. By forming the resin base 33, a decorative member having radio wave transmission can be obtained.

<Comparative example 2>
A hard coat film for transfer was obtained in the same manner as in Example 1 except that the ultraviolet absorber A contained in the primer layer 122 was not contained. Then, the intermediate product of the decorative member can be obtained by performing simultaneous transfer molding by injection molding on the surface of the first resin substrate 20 having the unevenness on the back surface. Then, by forming the colored layer, the indium luster layer and the second resin base on the back surface of the intermediate product of the decorative member, the decorative member having radio wave transmission can be obtained.

<Comparative example 3>
In Example 1, the UV absorber A contained in the primer layer 122 was not contained, and 17 parts of the hydroxyphenyltriazine-based UV absorber C (absorption peak 322 nm) and the hydroxyphenyltriazine-based UV absorber D (maximum absorption wavelength) were used. 336 nm) ^{* 10} A hard coat film for transfer was obtained in the same manner as in Example 1 except that 13 parts by mass was contained.
* 10, Tinuvin 400 (trade name), 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine (about 85%), 1-methoxy-2-propylacetate (about 15%), manufactured by BASF Japan Ltd.

<Evaluation>
The weather resistance and the average of the light transmittance of the wavelength of 350 nm or more and 400 nm or less in the transfer layer 12, the intermediate product of the decorative member (transfer layer / first substrate), and the decorative member (transfer layer / decorative member), respectively. The scratch resistance was evaluated. Table 1 shows the results. Further, FIG. 5 shows the absorbances of the ultraviolet absorbers A, B, C, and D. 6 to 9 show the transmittances of Examples 1 and 2 and Comparative Examples 2 and 3. In Table 1, the first base does not include the indium gloss layer, and the decorative member includes the indium gloss layer.

[Evaluation of weather resistance]
70 hours under light conditions (illuminance: 150 MJ or 300 MJ, black panel temperature 63 ° C., in-layer humidity 50% RH) using a metal weather resistance tester (Metal Weather (trade name), manufactured by Daipla Wintes Co., Ltd.) Exposed.
The yellow index difference (ΔYI) was read in accordance with JIS D1925, and the color difference (ΔE ^* ab) was read in SCI (diffuse reflected light + regular reflected light) according to JIS Z8792, 8730.
(Evaluation criteria)
◯: Color difference (ΔE ^* ab) is 2.8 or less Δ: Color difference (ΔE ^* ab) is more than 2.8 and 4 or less ×: Color difference (ΔE ^* ab) is more than 4

[Scratch resistance]
The surface of the hard coat layer obtained in each of Examples and Comparative Examples was rubbed 10 times with steel wool (# 0000) under a load of 1000 g / cm ³ , and the appearance was visually observed.
(Evaluation criteria)
◯: Almost no change in appearance was confirmed.
X: A change in appearance was confirmed.

  From the results shown in Table 1, in each of the transfer hard coat films of Examples 1 and 2, the average light transmittance of the transfer layer at a wavelength of 350 nm to 400 nm is 25% or less, and these transfer hard coat films are laminated. The decorative members of Examples 1 and 2 thus produced were more excellent in weather resistance than the decorative members of Comparative Examples 1 to 3. Further, the decorative members of Examples 1 and 2 were superior in weather resistance and scratch resistance as compared with Comparative Example 1 in which the transfer hard code film was not laminated.

10 Hard Coat Film for Transfer 11 Base Film 12 Transfer Layer 121 Hard Coat Layer 122 Primer Layer 123 Adhesive Layer 20 First Resin Substrate 30 Decorative Member 31 Coloring Layer 311 Coloring Material Layer 312 Indium Gloss Layer 32 Heat-Resistant Layer 33 Second Resin base

Claims (6)

A transfer hard coat film for forming the hard coat layer, which is disposed on the front surface of the radio wave radar device and is a decorative member comprising an indium gloss layer, a resin substrate and a hard coat layer in this order,
On the base film, at least, a transfer layer in which a hard coat layer, a primer layer and an adhesive layer are arranged in this order,
Contains an ultraviolet absorber in the primer layer,
The transfer layer is a transfer hard coat film having an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less.   The hard coat film for transfer according to claim 1, wherein the pre-UV absorber is a first UV absorber having an absorption peak at a wavelength of 350 nm or more and 400 nm or less. The primer layer further contains a second ultraviolet absorber which is not the first ultraviolet absorber,
The transfer hard coat film according to claim 1, wherein the transfer layer has an average light transmittance of 0.5% or less at a wavelength of 300 nm or more and 350 nm or less. An intermediate product that is arranged on the front surface of the radio wave radar device and is used as a decorative member having an indium gloss layer,
On the resin substrate, at least, a transfer layer in which an adhesive layer, a primer layer, a hard coat layer and a substrate film are arranged in this order,
Contains an ultraviolet absorber in the primer layer,
The transfer layer is an intermediate product of a decorative member having an average light transmittance of 25% or less at a wavelength of 350 nm or more and 400 nm or less. A decorative member arranged on the front surface of the radio wave radar device,
The decorative member has at least an indium gloss layer, a resin substrate, a transfer layer including an adhesive layer, a primer layer, and a hard coat layer in this order,
Contains an ultraviolet absorber in the primer layer,
The said transfer layer is a decoration member whose average of the light transmittance of wavelength 350nm or more and 400nm or less is 25% or less. A decorative member arranged on the front surface of the radio wave radar device,
The decorative member includes at least a second resin substrate, an indium gloss layer, a first resin substrate, a transfer layer including an adhesive layer, a primer layer, and a hard coat layer in this order,
Contains an ultraviolet absorber in the primer layer,
The said transfer layer is a decoration member whose average of the light transmittance of wavelength 350nm or more and 400nm or less is 25% or less.

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