JP2009255503A - Manufacturing method of plastic molded product and plastic molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic molded product having a transparent and conductive layer, capable of being manufactured at low cost and showing high design. <P>SOLUTION: The manufacturing method of the plastic molded product comprises a process of arranging a transparent and conductive film in a cavity of a molding mold, the transparent and conductive film having a thin film laminate composed of a transparent and conductive layer and at least one of a high refractive index layer and a low refractive index layer both having different refractive indexes from each other on a transparent base material, a process of injecting a thermoplastic material in the cavity of the molding mold, and a process of taking out the laminate of the thermoplastic molded product of the transparent and conductive film or the plastic molded article from the molding mold. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention includes a transparent conductive layer useful as a transparent electrode, a touch panel member, an electromagnetic shielding member, a building material, a portable game machine member, an automobile member, a vehicle member, a household appliance member, a mobile phone member, a personal computer member, and a car navigation member. It relates to plastic molded products.

  In recent years, electrical appliances having a display such as a portable game machine, a mobile phone, and an apparatus operation panel have been increasing in number having a touch panel in the display portion, and a transparent conductive layer is also used for a simple power switch or button as a building material. The touch panel provided with is used. For these exterior members, plastic molded products molded by injection molding are generally used. Usually, the touch panel part and the casing part (exterior part around the switch and the display part) are molded separately, and the switch And a touch panel separately manufactured on the surface of the casing of the display. However, since this method requires many manufacturing process steps and increases manufacturing costs, it is required to simplify the manufacturing process.

  In addition, there is a demand to make the outer frame of the display thinner, the bezelless structure that integrates the frame, and the boundary part that distinguishes the display part and the housing part from the viewpoint of product design. The same applies to products equipped with touch panels. However, in the conventional manufacturing method, since the touch panel is fitted into the frame of the display or the switch later, it is difficult to make a bezel-less and highly integrated structure.

JP 2007-12354 A

  In the method of producing a plastic molded body by injection molding and bonding the plastic molded body and a functional member having a transparent conductive layer and combining them to form a plastic molded product, there are problems in that there are many steps and the manufacturing cost is increased. Also, it has been difficult to achieve a structure with a sense of unity that has a high design.

  In the present invention, focusing on the above problems, it is an object of the present invention to provide a plastic molded product having a transparent conductive layer and having a low production cost and a high design property.

  In order to solve the above-mentioned problems, the invention according to claim 1 is a method for producing a plastic molded article provided with a transparent conductive layer, wherein a transparent conductive layer is formed on a transparent substrate in a cavity of a molding die, Disposing a transparent conductive film comprising a thin film laminate comprising at least one high refractive index layer or low refractive index layer having different refractive indices, and injecting a thermoplastic material into a cavity of a molding die Production of a plastic molded article comprising the steps of forming a thermoplastic molded article and taking out a plastic molded article that is a laminate of a transparent conductive film and a thermoplastic molded article from a molding die It was a method.

  According to a second aspect of the present invention, the step of arranging the transparent conductive film inside the cavity of the molding die, wherein the cavity wall surface of the molding die is provided with an uneven structure. 2. The plastic according to claim 1, which is a step of disposing a transparent conductive film inside the cavity of the molding die so that the hollow wall surface provided with the concave-convex structure of the mold is in contact with the transparent conductive film. It was set as the manufacturing method of the molded article.

  According to a third aspect of the present invention, there is provided a plastic molded article which is molded by the manufacturing method according to the first or second aspect and has a transparent conductive film on the surface of the thermoplastic molded article. did.

  According to a fourth aspect of the present invention, there is provided a plastic molded article produced by the production method according to the second aspect, comprising a transparent conductive film on a surface of the thermoplastic molded article, and the thermoplastic The plastic molded product is characterized in that the transparent conductive film is patterned in accordance with the uneven structure of the plastic molded body.

  The invention according to claim 5 is characterized in that the average visual reflectance of the surface of the plastic molded article at the place where the transparent conductive film is provided is 5% or more and 90% or less. Or it was set as the plastic molded product of Claim 4.

  According to a sixth aspect of the present invention, the transparent conductive film has a thin-film laminate on the surface side of the transparent substrate, and the surface of the plastic molded product at the location where the transparent conductive film is provided. The plastic molded article according to claim 3 or 4, wherein the sensitive average reflectance is 0.1% or more and 3% or less.

  According to a seventh aspect of the present invention, the total haze of a plastic molded article provided with an antiglare hard coat layer on one surface of the transparent base material and provided with the transparent conductive film is 7%. The plastic molded product according to any one of claims 3 to 6, wherein the plastic molded product is 40% or less.

  By adopting the method for producing a plastic molded article having the above-described configuration, it was possible to obtain a plastic molded article having low production cost and high design properties.

  The plastic molded product of the present invention will be described.

FIG. 1 is an explanatory cross-sectional view showing one embodiment of a transparent conductive film used in the plastic molded article of the present invention.
In the transparent conductive film of this invention, the transparent conductive layer 12 and the thin film laminated body 13 are provided on the transparent base material 11 at least. The thin film laminate includes at least one of a high refractive index layer and a low refractive index layer. In the thin film laminate 13 of FIG. 1, the high refractive index layer 14 is sandwiched by the low refractive index layer 15. Provide structure.

  In the present invention, the transparent conductive layer 12 is a conductive layer, and functions as an electrode or electrical wiring of various electrical devices in the obtained plastic molded product. Further, the transparent conductive layer 12 can also function as an electromagnetic wave shielding layer in the obtained plastic molded product.

  On the other hand, a thin film laminate is a laminate comprising at least one high refractive index layer or at least one low refractive index layer, a half mirror layer having a metallic luster due to optical interference between the high refractive index layer and the low refractive index layer, and antireflection It can function as a layer or a colored layer, and can improve the design of the resulting plastic molded product. For the thin film laminate, a single layer structure of a high refractive index layer or a low refractive index layer, or a laminated structure of a high refractive index layer and a low refractive index layer can be selected. When the thin film stack is provided with functions as a half mirror layer, an antireflection layer, and a colored layer, the optical film thickness is adjusted by adjusting the optical film thickness of the high refractive index layer and the low refractive index layer of the thin film stack. Can be realized.

  In the transparent conductive film used for the plastic molded article of the present invention, the transparent conductive layer 12 and the thin film laminate 13 are provided on at least one surface of the transparent substrate. In the transparent conductive film 1 in FIG. 1A, a high refractive index layer 14, a low refractive index layer 15, and a high refractive index layer are sequentially formed on one surface of the transparent substrate 11 from the transparent substrate 11 side. The thin film laminated body 13 comprised by 14 and the transparent conductive layer 12 are provided. In the transparent conductive film 1 in FIG. 1B, a transparent conductive layer 12, a high refractive index layer 14, and a low refractive index layer are sequentially formed on one surface of the transparent substrate 11 from the transparent substrate 11 side. 15 and a thin film laminate 13 composed of the high refractive index layer 14. Moreover, in the transparent conductive film 1 of FIG.1 (c), it has the transparent conductive layer 12 in one surface of the transparent base material 11, and a high refractive index layer in the surface on the opposite side to the transparent conductive layer 12 formation surface. 14, a thin film laminate 13 including a low refractive index layer 15 and a high refractive index layer 14 is provided. In the transparent conductive film of the present invention, the transparent conductive layer 12 may be provided on both surfaces of the transparent substrate 11. Similarly, the thin film laminate 13 may be provided on both surfaces of the transparent substrate 11. Further, two or more transparent conductive layers 12 may be provided on one surface of the transparent substrate 11, and similarly, two or more thin film laminates 13 are provided on one surface of the transparent substrate 11. Also good. In the transparent conductive film of the present invention, the transparent conductive layer 12 may also serve as the high refractive index layer 14 of the thin film laminate 13.

  In addition, as shown in FIG. 2, an antiglare hard coat layer 16 may be provided on one surface of the transparent substrate 11. FIG. 2 is an explanatory cross-sectional view showing an embodiment of a transparent conductive film having an antiglare hard coat layer 16. The antiglare hard coat layer of the present invention is a hard coat layer having surface irregularities, and can protect the surface of the substrate from mechanical trauma such as scratches by pencils, scratches by steel wool, etc. It is used for obtaining a matte metallic luster with less glare and making the boundary between the housing part and the display part inconspicuous.

In the transparent conductive film 1 of FIG. 2A, an antiglare hard coat layer 16, a high refractive index layer 14, and a low refractive index layer are formed on one surface of the transparent substrate 11 in this order from the transparent substrate 11 side. A thin film laminate 13 composed of a refractive index layer 15 and a high refractive index layer 14 and a transparent conductive layer 12 are provided. In the transparent conductive film 1 of FIG. 2B, an antiglare hard coat layer 16, a transparent conductive layer 12, and a high layer are formed on one surface of the transparent substrate 11 in order from the transparent substrate 11 side. A thin film laminate 13 including a refractive index layer 14, a low refractive index layer 15, and a high refractive index layer 14. Moreover, in the transparent conductive film 1 of FIG.1 (c), it has the anti-glare hard-coat layer 16 and the transparent conductive layer 12 in one surface of the transparent base material 11, and is opposite to the transparent conductive layer 12 formation surface. A thin film laminate 13 including a high refractive index layer 14, a low refractive index layer 15, and a high refractive index layer 14 is provided on the side surface.
The antiglare hard coat layer 16 in FIG. 2 is laminated on the transparent substrate 11 on the surface on which the transparent conductive layer 12 is laminated, but is not limited thereto, and the transparent conductive layer 12 is laminated. You may laminate | stack on the transparent base material 11 on the opposite side to the surface.

  FIG. 3 shows an explanatory sectional view of the plastic molded product of the present invention. In the plastic molded product of the present invention, a transparent conductive film 1 and a thermoplastic molded body 2 made of a thermoplastic material are laminated. 3 (a-1) and 3 (a-2) show a plastic molded product 3 provided with the transparent conductive film 1 shown in FIG. 1 (a). 3 (b-1) and 3 (b-2) show a plastic molded product 3 provided with the transparent conductive film 1 shown in FIG. 1 (b). 3 (c-1) and 3 (c-2) show a plastic molded product 3 provided with the transparent conductive film 1 shown in FIG. 1 (c). As shown in FIG. 3, in the plastic molded article 3 of the present invention, the transparent conductive layer 12 may be provided between the transparent base film 11 and the thermoplastic molded article 2, or the transparent conductive layer 12. May be provided on the surface of the transparent substrate 11 opposite to the surface on which the thermoplastic plastic laminate 2 is formed. Similarly, in the plastic molded article 3 of the present invention, the thin film laminate 13 may be provided between the transparent substrate film 11 and the thermoplastic plastic molded body 2, or the thin film laminate 13 may be provided as the transparent substrate 11. It may be provided on the surface opposite to the surface on which the thermoplastic laminate 2 is formed.

  The configuration of the plastic molded product 3 of the present invention is applied depending on the use of the molded product. For example, in the case where the plastic molded product of the present invention is used as a resistive film type touch panel member, the transparent molded layer 12 is provided on the surface of the plastic molded product 3 as shown in FIGS. 3 (a-1) and 3 (c-1). Plastic molded products can be used. When the plastic molded product of the present invention is used as a capacitive touch panel member, the structure is not limited to the structure having the transparent conductive layer 12 on the surface of the plastic molded product 3.

  In the plastic molded product of the present invention, other functional layers may be provided. For example, by providing a hard coat layer on the surface of the plastic molded product, the scratch resistance of the surface of the plastic molded product can be improved. Moreover, by providing the antifouling layer on the surface of the plastic molded product, the antifouling property on the surface of the plastic molded product can be improved. Other functional layers may be provided between the respective layers.

  The manufacturing method of the plastic molding of this invention is demonstrated.

FIG. 4 shows an explanatory view of the method for producing a plastic molded product of the present invention. The plastic molded product of the present invention is manufactured by the following steps.
・ Process 1
Step of disposing the transparent conductive film 1 in the cavity 41 of the molding die 4 (FIGS. 4 (1) and (2))
・ Process 2
A step of injecting a thermoplastic material into the cavity 41 of the molding die 4 (FIG. 4 (3))
・ Process 3
A step of taking out a plastic molded product 3 which is a laminate of the thermoplastic molded product 2 of the transparent conductive film 1 from the molding die 4 (FIG. 4 (4)).

  By producing a plastic molded article having a transparent conductive layer by the above method, a plastic molded article with low production cost and high designability could be obtained. In the plastic molded product of the present invention, since the transparent conductive film 1 and the plastic molded product 2 are integrally molded, it is possible to obtain a plastic molded product with a bezel-less and high unity feeling. By having the transparent conductive layer, the transparent conductive layer can be made to function as an electrode, an electrical wiring, and an electromagnetic wave shielding layer, whereby a high-value-added plastic molded product can be obtained.

  In this invention, the design property of a plastic molded product can be improved further by using a transparent conductive film provided with a thin film laminated body. The thin film laminate can function as a half mirror layer, an antireflection layer, and a colored layer by interference of light between the high refractive index layer and the low refractive index layer, and can improve the design of the plastic molded product. When the plastic molded product functions as an antireflection layer, the plastic molded product of the present invention is a thin film laminate on the surface of the plastic molded product as shown in FIGS. 3 (b-1) and (c-2). It is preferable to provide.

  FIG. 5 shows an explanatory view of another aspect of the method for producing a plastic molded product of the present invention. In the method of manufacturing a plastic molded article in FIG. 5, the wall surface of the molding die has an uneven structure, and a step of injecting a thermoplastic material into the mold (FIG. 5 (3) )), The transparent conductive layer adjacent to the concavo-convex structure on the mold wall surface is broken by the pressure in the mold when the thermoplastic material is injected, and can be patterned. Therefore, the obtained plastic molded product can be a plastic molded product in which the transparent conductive layer is patterned corresponding to the uneven structure of the mold wall surface. In other words, a plastic molded product having a transparent conductive layer patterned corresponding to the uneven structure on the surface of the plastic molded product can be obtained. By using this production method, the transparent conductive layer can be patterned at a low cost.

  The height of the uneven structure on the inner wall surface of the mold is preferably 0.5 mm or more. If it is lower than this, the transparent conductive layer may not be completely broken.

  By using the method for producing a plastic molded product of the present invention as shown in FIG. 5, it is possible to easily produce a plastic molded product having electrodes that require patterning and a transparent conductive layer as electrical wiring. For example, by using a transparent conductive layer of a plastic molded product as an electrode of a capacitively coupled touch panel, a digital touch panel having a plurality of channels to which surface protection performance and design properties are added can be manufactured.

  In FIG. 5, the transparent conductive film is preferably disposed in the cavity of the molding die so that the transparent conductive layer 12 and the uneven structure of the molding die face each other. With such an arrangement, the transparent conductive layer 12 can be easily patterned. However, the transparent base material 11 is sandwiched between the transparent conductive layer 12 of the transparent conductive film 1 and the concave / convex structure of the molding die by considering the height of the concave / convex structure of the transparent base material and the molding die. Even if a transparent conductive film is disposed in the cavity of the molding die, the transparent conductive layer can be patterned.

  In the plastic molded product of the present invention, it is preferable that the luminous reflectance of the plastic molded product surface where the transparent conductive film is provided is in the range of 5% to 90%. When the thin film laminate is made to function as a colored layer, the plastic molded product obtained can have a color having a metallic luster by setting the visual average reflectance within the range of 5% to 90%. Moreover, by setting the luminous average reflectance within the range of 20% or more and 90%, it is possible to have half mirror performance and to impart decorativeness and design to a plastic molded product. The luminous reflectance of the plastic molded product in the present invention is a reflectance value obtained by calibrating the reflectance of each wavelength of visible light obtained by a spectrophotometer with the relative luminous sensitivity and averaging it. At this time, the incident angle is set to 5 degrees from the direction perpendicular to the surface of the plastic molded product, and the D65 light source is used as the light source, and the angle is obtained under the condition of a 2-degree visual field. In order to make the surface luminous average reflectance within the range of 5% or more and 90% or less, by adjusting the optical film thickness of the high refractive index layer and the low refractive index layer of the thin film laminate by an optical simulation method. Can be realized. When a thin film laminate having at least one high refractive index layer and at least one low refractive index layer and a transparent conductive layer are adjacent to each other, the transparent conductive layer and the high refractive index are formed by an optical simulation method including the transparent conductive layer. It is preferable to determine the optical film thickness of the layer and the low refractive index layer.

In addition, any color can be adjusted by designing the optical film thickness of the high refractive index layer and the low refractive index layer by the optical simulation method. By making the thin film laminate function as a colored layer, a plastic molded article with a transparent conductive film having a decorative color having a color saturation C ^{* in} the range of 0 to 100 in the L ^* a ^* b ^* color system It can be. Note that the thin film laminate can be a colorless layer without being colored.

  Here, if the luminous average reflectance exceeds 90%, the transmittance of the plastic molded product is too low, making it difficult to use as a display member. On the other hand, when the luminous average reflectance is less than 5%, a color having a sufficient metallic luster cannot be obtained, and it becomes difficult to obtain a plastic molded product having a half mirror performance.

  In the plastic molded article of the present invention, the transparent conductive film has a thin film laminate on the surface side of the transparent substrate, and the surface of the plastic molded article where the transparent conductive film is provided is viewed. The sensitive average reflectance is preferably in the range of 0.1% to 3%. By setting the luminous average reflectance within the range of 0.1% or more and 3% or less, the obtained plastic molded article can have antireflection performance, and visibility can be imparted to the plastic molded article. In order to make the surface luminous average reflectance within the range of 0.1% or more and 3% or less, the optical film thickness of the high refractive index layer and the low refractive index layer of the thin film laminate is adjusted by an optical simulation method. Can be realized. When a thin film laminate having at least one high refractive index layer and at least one low refractive index layer and a transparent conductive layer are adjacent to each other, the transparent conductive layer and the high refractive index are formed by an optical simulation method including the transparent conductive layer. It is preferable to determine the optical film thickness of the layer and the low refractive index layer.

  Here, in order to prevent reflection of light entering from the outside on the surface of the plastic molded product, and in particular to provide visibility, the visual average reflectance is preferably in the range of 0.1% to 3%. When trying to obtain a luminous average reflectance of less than 0.1%, the number of layers of the thin film laminate increases, so that productivity is poor and reproducibility of reflectance may be poor. On the other hand, when the luminous average reflectance exceeds 3%, it may not be possible to obtain a plastic molded product having sufficient antireflection performance.

  In the plastic molded article of the present invention, the total haze of the plastic molded article provided with the antiglare hard coat layer on one surface of the transparent substrate and provided with the transparent conductive film is 7%. It is preferable that it is in the range of 40% or less. If it is less than 7%, it is difficult to obtain an effect of making the boundary between the display unit and the housing unit inconspicuous due to the light scattering phenomenon, and if it exceeds 40%, the transmittance in the display unit is lowered. Total haze is measured according to JIS 7105 using a haze meter.

  The plastic molded body of the present invention will be described in more detail.

(Transparent substrate)
Here, the transparent substrate is a polyolefin such as polyethylene or polypropylene; a polyester such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate; polyamide; polyimide; polyarylate; polycarbonate; polyacrylate; A non-stretched or stretched film can be used. Also, other highly transparent plastic films can be used. Of these, polyethylene terephthalate can be used. The thickness of the transparent substrate is appropriately selected according to the intended use, and a plastic film in the range of usually 5 μm or more and 200 μm or less can be suitably used.

  The transparent substrate may contain known additives such as ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants and the like. In addition, this transparent base material may be subjected to surface treatment such as easy adhesion treatment, plasma treatment, and corona treatment.

(Transparent conductive layer)
Examples of the transparent conductive material for forming the transparent conductive layer include oxides such as indium oxide, tin oxide, and zinc oxide, or mixed oxides thereof. In particular, a mixed oxide (ITO) of indium oxide and tin oxide is preferably used.

  In addition, the transparent conductive material can contain additives such as Al, Zr, Ga, Si, and W as required. The method for producing the transparent conductive layer of the present invention is not particularly limited, but it is preferably used that a film is formed on a transparent substrate by a vacuum film formation method such as a sputtering method, a vapor deposition method, an ion plating method, or a CVD method. be able to.

  When the transparent conductive layer is used as an electrode of a capacitively coupled touch panel, the surface resistance value is preferably in the range of 100 to 1500 Ω / □.

(Thin film laminate)
The thin film laminate in the present invention has a high refractive index layer single layer, a low refractive index layer single layer, or a laminated structure in which one or more high refractive index thin films and low refractive index thin films are alternately laminated. By making a thin film laminated body into a laminated structure, the antireflection performance, half mirror performance, and coloring performance of the thin film laminated body can be improved. However, when the number of high refractive index layers and low refractive index layers is increased, the manufacturing cost is improved.

  The high refractive index layer in the thin film laminate of the present invention is preferably a layer having a refractive index of 1.75 to 2.4 at a light wavelength of 550 nm and an extinction coefficient of 0.5 or less.

  Examples of the material for forming a high refractive index layer include indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, platinum, carbon, tantalum, aluminum, germanium, gallium, antimony, neodymium, and lanthanum. , Thorium, hafnium, yttrium, rhodium, selenium, europium, ytterbium, scandium, praseodymium, samarium, etc., or oxides, fluorides, sulfides, nitrides or oxides, fluorides of these elements, Examples thereof include a mixture of sulfides and nitrides. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition. When a plurality of high refractive index layers are provided, the high refractive index layer forming material may be the same or different.

  The low refractive index layer in the thin film laminate of the present invention is preferably a layer having a refractive index of 1.3 to 1.75 and an extinction coefficient of 0.5 or less at a light wavelength of 550 nm.

  Examples of the material for forming the low refractive index layer include silicon oxide, aluminum oxide, magnesium oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, hafnium fluoride, lanthanum fluoride, sodium fluoride, aluminum fluoride. , Carbon fluoride, lead fluoride, strontium fluoride, ytterbium fluoride, neodymium fluoride, lithium fluoride, samarium fluoride, or a mixture of these compounds. The chemical composition of these compounds may not match the stoichiometric composition. When providing a plurality of low refractive index layers, the low refractive index layer forming material may be the same or different.

  The high refractive index layer and the low refractive index layer in the present invention are preferably formed by a vacuum film forming method such as a vapor deposition method, a sputtering method, a plasma CVD method, an ion plating method, an ion beam assist method.

  For the optical constants of the refractive index and extinction coefficient of the high refractive index layer and the low refractive index layer, the change in the polarization state of the light reflected from the surface of the thin film stack is measured using a spectroscopic ellipsometry method. Can be obtained. With respect to the extinction coefficient, if it is greater than 0.5, light absorption increases, which is not preferable as a material for forming the high refractive index layer and the low refractive index layer having the light reflection performance of the present invention.

(Thermoplastic material)
As the thermoplastic material in the present invention, acrylic, polycarbonate (PC), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polypropylene, polyethylene, polystyrene, polystyrene, nylon, and a mixed material thereof may be used. However, the present invention is not limited to this.

(Anti-glare hard coat layer)
The antiglare hard coat layer of the present invention has surface unevenness, and as a method for forming the surface unevenness, there are a method of embossing the formed resin material, a method of mixing particles in the resin material, and the like. Can be used.

  The resin material used for the antiglare hard coat layer is not particularly limited as long as it has an appropriate hardness and mechanical strength, and examples thereof include materials such as acrylic resins, organosilicon resins, and polysiloxanes.

  Examples of acrylic resins include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, and triethylene. Glycol di (meth) acrylate, tripropylene glycolic di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropionate, Trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-butadiene di (Meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (Meth) acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4- Bis ((meth) acryloyl Examples thereof include a mixture of oxymethyl) cyclohexane, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate and the like.

  Examples of the organosilicon resin include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Examples thereof include a mixture of butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, and the like.

  Particles used in the antiglare hard coat layer include organic particles such as acrylic particles, acrylic-styrene particles, polystyrene particles, polycarbonate particles, melamine particles, silica particle talc, various aluminosilicates, kaolin clay, MgAl hydrotalcite And inorganic particles. The average particle diameter of the particles is preferably about 1 to 20 μm. If the thickness is 1 μm or less, it is difficult to form unevenness on the surface of the antiglare hard coat layer that causes light scattering, and the boundary between the display unit and the case unit of a portable game machine or mobile phone It is difficult to obtain the effect of making the image inconspicuous, and if it is 20 μm or more, the transmittance of the display unit is lowered.

  In the antiglare hard coat layer of the present invention, the content of the particles with respect to the resin material is preferably 0.1 wt% or more and 30 wt% or less. When the content of the particles with respect to the resin material is less than 0.1 wt%, it may not be possible to have sufficient external light reflection prevention properties. In addition, when the content of the particles with respect to the resin material exceeds 30 wt%, the content of the particles is excessively increased in the coating liquid for coating the antiglare hard coat layer, and the storage stability of the coating liquid is increased. May be lost, and appearance defects and a decrease in surface height are likely to occur.

  In the antiglare hard coat layer of the present invention, other functional additives may be added to the resin material. However, it should not affect the light diffusivity. As the functional additive, an antistatic agent, an ultraviolet absorber, an infrared absorber, an antifouling agent, a water repellent, a refractive index adjuster, an adhesion improver, a curing agent, and the like can be used. The antiglare hard coat layer of the present invention may have functions other than the antiglare hard coat function such as an antistatic function, an ultraviolet absorbing function, an infrared absorbing function, an antifouling function, and a water repellent function.

  The film thickness of the antiglare hard coat layer used in the present invention is 0.5 μm or more, preferably 3 μm or more and 20 μm or less, more preferably 3 μm or more and 8 μm or less in average film thickness. In the present invention, the average film thickness of the antiglare hard coat layer is the average value of the film thickness of the antiglare hard coat layer having surface irregularities. The average film thickness can be determined by an electronic micrometer or a fully automatic fine shape measuring instrument.

The surface hardness (pencil hardness) of the antiglare hard coat layer used in the present invention is preferably 2H or more. When it is less than 2H, it is easy to be damaged in display applications, and the scratch resistance is insufficient. Furthermore, the surface hardness (pencil hardness) of the antiglare hard coat layer is preferably 4H or more.
The pencil hardness is a value obtained by a pencil hardness test according to JIS K 5400. In the pencil hardness test, the measurement operation of the pencil hardness test is repeated five times, and when no abnormality in appearance such as a scratch is observed two or more times, the pencil hardness used in the test is taken as the pencil hardness. .

  The antiglare hard coat layer used in the present invention is formed by a conventionally known method such as a gravure coating method, a spray coating method, an air knife coating method, a roll brush method, a curtain coating method, an impregnation coating method, and the like. It is formed by curing using ultraviolet curing or ionizing radiation curing.

  Hereinafter, the present invention will be specifically described based on examples.

Example 1
A PET film having a thickness of 100 μm was used as a transparent substrate, and a thin film laminate and a transparent conductive layer were sequentially laminated on one surface of the substrate film. In forming the thin film laminate, a high refractive index layer, a low refractive index layer, and a high refractive index layer were sequentially laminated.
First, a high refractive index layer (refractive index of light with a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical film thickness of 131 nm as a high refractive index layer is formed on a transparent substrate by a sputtering method. Formed.
Next, a low refractive index layer (refractive index 1.46 of light having a wavelength of 550 nm, extinction coefficient 0) made of silicon dioxide (SiO ₂ ) having a physical thickness of 65 nm is sputtered on the high refractive index layer as a low refractive index layer. Formed by the method.
Next, a high refractive index layer (refractive index of light having a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 152 nm is sputtered as a high refractive index layer on the low refractive index layer. Formed by the method.
Furthermore, ITO, which is a mixed oxide of indium oxide and tin oxide, was used as a transparent conductive layer forming material on the high refractive index layer, and was formed by direct current magnetron sputtering to form a transparent conductive layer. At this time, the film thickness of the transparent conductive layer was 20 nm, and the surface resistance value was 300Ω / □.
The transparent conductive film was produced by the above.

Next, an injection molding machine is prepared, polycarbonate (PC) is used as the thermoplastic material, the obtained transparent conductive film is arranged so that the transparent conductive layer faces the mold wall surface, and the polycarbonate is placed inside the mold. The plastic molded product with a transparent conductive layer having a transparent conductive layer on the surface was obtained.
When the average luminous reflectance and chromaticity at an incident angle of 5 ° and a wavelength of 380 to 780 nm of the obtained plastic molded product were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), the luminous average reflection was measured. The rate was 24%, L ^* = 55.94, a ^* = − 1.85, b ^* = − 29.40 chromaticity and C ^* = 29.46 saturation. The obtained plastic molded article has a transparent conductive layer, has a blue color, has a half mirror performance, has a high design, and is a bezel-less plastic molded article having a high unity feeling. became.

(Example 2)
A 100 μm thick PET film was used as a transparent substrate, a thin film laminate was laminated on one surface of the transparent substrate, and a transparent conductive layer was laminated on the other surface. In forming the thin film laminate, a high refractive index layer, a low refractive index layer, and a high refractive index layer were sequentially laminated.
First, a high refractive index layer (refractive index of light with a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 99 nm is formed on the transparent substrate by a sputtering method. Formed.
Next, a low-refractive index layer (refractive index of 1.46 light having a wavelength of 550 nm, extinction coefficient of 0) made of silicon dioxide (SiO ₂ ) having a physical thickness of 74 nm is sputtered on the high-refractive index layer as a low refractive index layer. Formed by the method.
Next, a high refractive index layer (refractive index of light having a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 47 nm is sputtered on the low refractive index layer as a high refractive index layer. Formed by the method.
Next, a transparent conductive layer was formed on the transparent substrate surface opposite to the surface on which the thin film laminate was formed. On the high refractive index layer, ITO, which is a mixed oxide of indium oxide and tin oxide, was used as a transparent conductive layer forming material, and a transparent conductive layer was formed by forming a film by a direct current magnetron sputtering method. At this time, the film thickness of the transparent conductive layer was 20 nm, and the surface resistance value was 300Ω / □.
The transparent conductive film was produced by the above.

Next, an injection molding machine is prepared, polycarbonate (PC) is used as the thermoplastic material, the obtained transparent conductive film is arranged so that the thin film laminate faces the mold wall surface, and the polycarbonate is placed inside the mold. To obtain a plastic molded article with a transparent conductive layer having a thin film laminate on the surface and having a transparent conductive layer between the transparent substrate and the plastic molded article.
When the average luminous reflectance and chromaticity at an incident angle of 5 ° and a wavelength of 380 to 780 nm of the obtained plastic molded product were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), the luminous average reflection was measured. The rate was 40%, L ^* = 69.55, a ^* = − 7.99, b ^* = 7.65 chromaticity and C ^* = 11.06 saturation. The obtained plastic molded article has a transparent conductive layer, has a half mirror performance, has high designability, and can be a plastic molded article with a bezel-less and high unity feeling. .

(Example 3)
The transparent conductive film obtained in Example 1 was used as the transparent conductive film.

  Next, an injection molding machine is prepared, polycarbonate (PC) is used as the thermoplastic material, the obtained transparent conductive film is arranged so that the transparent conductive layer faces the mold wall surface, and the polycarbonate is placed inside the mold. The plastic molded product with a transparent conductive layer having a transparent conductive layer on the surface was obtained. At this time, a mold having a linear step with a height of 0.5 mm is used as the mold of the injection molding machine, the mold wall surface having the step and the transparent conductive layer of the transparent conductive film face each other, and the polycarbonate Was injected into the mold.

  In the obtained plastic molded product, it was confirmed that the transparent conductive layer was broken at the step portion of the mold, and the transparent conductive layer was patterned following the uneven structure of the plastic molded product.

Example 4
A 100 μm thick PET film was used as a transparent substrate, a thin film laminate was laminated on one surface of the transparent substrate, and a transparent conductive layer was laminated on the other surface. In forming the thin film laminate, a high refractive index layer, a low refractive index layer, and a high refractive index layer were sequentially laminated.
First, a high refractive index layer (refractive index of light with a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 30 nm as a high refractive index layer is formed on a transparent substrate by sputtering. Formed.
Next, a low refractive index layer (refractive index 1.46 of light having a wavelength of 550 nm, extinction coefficient 0) made of silicon dioxide (SiO ₂ ) having a physical thickness of 21 nm is sputtered on the high refractive index layer as a low refractive index layer. Formed by the method.
Next, a high refractive index layer (refractive index of light with a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 62 nm is sputtered on the low refractive index layer as a high refractive index layer. Formed by the method.
Next, a low refractive index layer (refractive index of 1.46 light having a wavelength of 550 nm, extinction coefficient of 0) made of silicon dioxide (SiO ₂ ) having a physical thickness of 94 nm is sputtered on the high refractive index layer as a low refractive index layer. Formed by the method.
Next, a transparent conductive layer was formed on the transparent substrate surface opposite to the surface on which the thin film laminate was formed. On the high refractive index layer, ITO, which is a mixed oxide of indium oxide and tin oxide, was used as a transparent conductive layer forming material, and a transparent conductive layer was formed by forming a film by a direct current magnetron sputtering method. At this time, the film thickness of the transparent conductive layer was 20 nm, and the surface resistance value was 300Ω / □.
The transparent conductive film was produced by the above.

Next, an injection molding machine is prepared, polycarbonate (PC) is used as the thermoplastic material, the obtained transparent conductive film is arranged so that the thin film laminate faces the mold wall surface, and the polycarbonate is placed inside the mold. To obtain a plastic molded article with a transparent conductive layer having a thin film laminate on the surface and having a transparent conductive layer between the transparent substrate and the plastic molded article.
When the average luminous reflectance and chromaticity at an incident angle of 5 ° and a wavelength of 380 to 780 nm of the obtained plastic molded product were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), the luminous average reflection was measured. The rate was 1.3%, L ^* = 11.15, a ^* = 13.50, b ^* = − 22.31 chromaticity and C ^* = 26.08 saturation. The obtained plastic molded article has a transparent conductive layer and antireflection performance, and can prevent reflection of external light such as sunlight and fluorescent lamps, and has high visibility. In addition, it was a bezel-less plastic molded product with a high sense of unity.

(Example 5)
A 100 μm-thick PET film was used as a transparent substrate, and an antiglare hard coat layer, a thin film laminate, and a transparent conductive layer were laminated in this order on one surface of the transparent substrate. In forming the thin film laminate, a high refractive index layer, a low refractive index layer, and a high refractive index layer were sequentially laminated.
First, a high refractive index layer (refractive index of light with a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 58 nm as a high refractive index layer is formed on a transparent substrate by a sputtering method. Formed.
Next, a low-refractive index layer (refractive index of light of wavelength 550 nm 1.46, extinction coefficient 0) made of silicon dioxide (SiO ₂ ) having a physical thickness of 90 nm is sputtered on the high-refractive index layer as a low-refractive index layer. Formed by the method.
Next, a high refractive index layer (refractive index of light having a wavelength of 550 nm: 2.32, extinction coefficient: 0) made of titanium dioxide (TiO ₂ ) having a physical thickness of 93 nm is sputtered on the low refractive index layer as a high refractive index layer. Formed by the method.
Furthermore, ITO, which is a mixed oxide of indium oxide and tin oxide, was used as a transparent conductive layer forming material on the high refractive index layer, and was formed by direct current magnetron sputtering to form a transparent conductive layer. At this time, the film thickness of the transparent conductive layer was 20 nm, and the surface resistance value was 300Ω / □.

Next, an injection molding machine is prepared, polycarbonate (PC) is used as the thermoplastic material, the obtained transparent conductive film is arranged so that the transparent conductive layer faces the mold wall surface, and the polycarbonate is placed inside the mold. The plastic molded product with a transparent conductive layer having a transparent conductive layer on the surface was obtained.
When the average luminous reflectance and chromaticity at an incident angle of 5 ° and a wavelength of 380 to 780 nm of the obtained plastic molded product were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), the luminous average reflection was measured. The rate was 24%, L ^* = 56.33, a ^* = 44.36, b ^* = − 1.46 chromaticity and C ^* = 44.38 saturation. Moreover, when the total haze of the obtained plastic molded product was measured using a haze meter NDH-2000 (manufactured by Nippon Denshoku), the total haze was 10%. The plastic molded product has a transparent conductive layer, has a high-quality matte metallic luster and a red color, has a high design, and is a bezel-less plastic molded product with a high sense of unity. It was.

FIG. 1 is an explanatory cross-sectional view of one embodiment of a transparent conductive film used in the plastic molded article of the present invention. FIG. 2 is an explanatory cross-sectional view of one embodiment of a transparent conductive film used in the plastic molded article of the present invention. FIG. 3 is an explanatory sectional view of the plastic molded article of the present invention. FIG. 4 is an explanatory view of the method for producing a plastic molded product of the present invention. FIG. 5 is an explanatory view of another embodiment of the method for producing a plastic molded product of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent conductive film 11 Transparent base material 12 Transparent conductive layer 13 Thin film laminated body 14 High refractive index layer 15 Low refractive index layer 16 Anti-glare hard coat layer 2 Thermoplastic plastic molded body 3 Plastic molded product 4 Mold 41 Mold cavity

Claims (7)

A method for producing a plastic molded article comprising a transparent conductive layer,
A transparent conductive film including a transparent conductive layer and a thin film laminate including at least one high refractive index layer or low refractive index layer having different refractive indexes on a transparent base material is disposed in a cavity of a molding die. And a process of
A step of injecting a thermoplastic material into a mold cavity to form a thermoplastic molded body;
A method for producing a plastic molded product comprising the step of taking out a plastic molded product, which is a laminate of a transparent conductive film and a thermoplastic molded product, from a molding die. The cavity wall surface of the molding die has an uneven structure, and
The step of disposing the transparent conductive film inside the cavity of the molding die is configured so that the transparent conductive film is in contact with the cavity wall surface provided with the concave-convex structure of the molding die. 2. The method for producing a plastic molded product according to claim 1, wherein the method is a step of arranging the mold inside a cavity of the mold.   A plastic molded article, which is molded by the production method according to claim 1 or 2, and comprises a transparent conductive film on a surface of the thermoplastic molded article.   A plastic molded article produced by the production method according to claim 2, comprising a transparent conductive film on a surface of the thermoplastic molded article, and corresponding to the concavo-convex structure of the thermoplastic molded article. A plastic molded product, wherein a transparent conductive film is patterned.   The plastic molded article according to claim 3 or 4, wherein the average visual reflectance of the surface of the plastic molded article at a location where the transparent conductive film is provided is 5% or more and 90% or less. The transparent conductive film comprises a thin film laminate on the surface side of the transparent substrate, and
The plastic molded article according to claim 3 or 4, wherein a visual average reflectance of the surface of the plastic molded article at a location where the transparent conductive film is provided is 0.1% or more and 3% or less. Provided with an antiglare hard coat layer on one surface of the transparent substrate, and
The plastic molded product according to any one of claims 3 to 6, wherein a total haze of the plastic molded product provided with the transparent conductive film is 7% or more and 40% or less.

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