Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/548—No curing step for the last layer
  • B05D7/5483—No curing step for any layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
  • B32B37/025—Transfer laminating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/111—Anti-reflection coatings using layers comprising organic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
  • B32B2037/243—Coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
  • B32B2037/268—Release layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/77—Uncured, e.g. green
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/416—Reflective
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/536—Hardness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/554—Wear resistance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/584—Scratch resistance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/738—Thermoformability
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

• the present invention relates to a laminated film and a laminated member.
• displays In addition to computers, televisions, mobile phones, and personal digital assistants (tablet PCs, mobile devices, electronic organizers, etc.), displays include digital meters, instrument panels, navigation systems, console panels, center clusters, and heater control panels. It is used in various fields such as display panels for computers. Such products are often covered with protective material.
• the protective material is usually obtained by molding a film having a hard coat layer.
• the protective material of the display may be further provided with a low refractive index layer for the purpose of reducing the reflectance of the surface on the visual side.
• Patent Document 1 Japanese Unexamined Patent Publication No. 2015-004937 teaches a laminated film in which a hard coat layer and a low refractive index layer (optical interference layer) are laminated in order on a transparent support.
• the present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a laminated film that can be molded into a complicated shape.
• an uncured hard coat layer formed on at least one surface of the transparent support substrate It has an uncured optical interference layer formed on the uncured hard coat layer.
• the uncured hard coat layer contains an active energy ray-curable hard coat layer forming composition.
• the uncured optical interference layer contains an active energy ray-curable optical interference layer forming composition.
• the thickness of the transparent support base material is 50 ⁇ m or more and 600 ⁇ m or less.
• the visual reflectance including the specularly reflected light measured from the uncured optical interference layer side is 0.1% or more and 4.0% or less.
• the hardness measured by the nanoindentation method from the optical interference layer side of the laminated film irradiated with active energy rays having an integrated light amount of 500 mJ / cm 2 is more than 0.5 GPa and 1.2 GPa or less.
• the laminated film of the present invention can be molded into a complicated shape.
• a laminated film called a precure type may be used as a protective film for the display.
• the hard coat layer and the optical interference layer contained in the precure type laminated film are usually cured in a step prior to the preform step, that is, in a step of forming each layer, as shown in Patent Document 1. Therefore, at the time of preform, the laminated film cannot follow the mold having a complicated shape, and the laminated film may be cracked.
• the laminated film including the uncured hard coat layer and the uncured optical interference layer is, that is, an aftercure type.
• the aftercure type laminated film Since the aftercure type laminated film is subjected to the preform process in an uncured state, it can be molded into a complicated shape without causing cracks. Since the occurrence of cracks is suppressed, the appearance of the molded product is improved, and the functions of the hard coat layer and the optical interference layer are effectively exhibited. In addition, since the draw ratio at 160 ° C. is 50% or more and the thickness of the transparent supporting base material is 50 ⁇ m or more and 600 ⁇ m or less, the laminated member obtained even when molded into a complicated shape can be obtained. Has sufficient rigidity.
• each layer can be formed with a layer forming composition having a high crosslink density. That is, the hardness of each layer after curing can be increased.
• both the hard coat layer and the optical interference layer are uncured, the adhesion between the layers is high. Further, by heat treatment, the unevenness of the surface of each layer can be leveled. As a result, a laminated film having high smoothness can be obtained.
• the visual reflectance of the laminated film including the specularly reflected light is 0.1% or more and 4.0% or less. Therefore, it has excellent antireflection performance.
• the laminated member obtained by curing this also has excellent antireflection performance. The antireflection effect reduces the reflection of external light on the laminated member.
• the laminated film according to the present embodiment is formed on a transparent support base material, an uncured hard coat layer formed on at least one surface of the transparent support base material, and an uncured hard coat layer. It has an uncured optical interference layer.
• the uncured hard coat layer contains an active energy ray-curable hard coat layer forming composition.
• the uncured photo-interference layer contains an active energy ray-curable photo-interference layer forming composition.
• Uncured means a state in which it is not completely cured.
• the hard coat layer and the light interference layer contained in the laminated film may be in a semi-cured state.
• the laminated film is an aftercure type.
• Curing is synonymous with "curing and drying” defined in JIS K 5500 (paint terminology). That is, for curing, a) When the center of the test piece is strongly sandwiched between the thumb and index finger, the coated surface does not have dents due to fingerprints, the movement of the coating film is not felt, and the coated surface is rapidly pressed with the fingertips. It means that when you rub it repeatedly, it becomes a state without scratches (dry hard).
• the laminated film irradiated with the active energy ray having an integrated light amount of 100 mJ / cm 2 is cured.
• Semi-curing is also synonymous with "semi-curing drying" defined in JIS K 5500 (paint terminology). That is, semi-curing refers to a state in which the center of the coated surface is lightly rubbed with a fingertip and no scratch marks are left on the coated surface (dry to touch). It can be said that the laminated film irradiated with the active energy rays having an integrated light amount of 1 mJ / cm 2 or more and less than 100 mJ / cm 2 is semi-cured.
• Uncured refers to a state in which the hard coat layer and the optical interference layer are not exposed to active energy rays or are exposed to active energy rays of less than 1 mJ / cm 2 .
• the visual reflectance including the specularly reflected light measured from the uncured optical interference layer side of the laminated film is 0.1% or more and 4.0% or less.
• the lower limit of the visual reflectance of the laminated film is 0.1%
• the upper limit is 4.0%. That is, the laminated film has excellent antireflection properties.
• the laminated member obtained by curing the laminated film also has excellent antireflection properties. Therefore, the laminated member has less reflection due to external light, and the laminated member has good display characteristics and good visibility.
• the visual reflectance of the laminated member can also be 0.1% or more and 4.0% or less.
• the visual reflectance of the laminated film is preferably 0.1% or more and 3.0% or less, and more preferably 0.1% or more and 2.5% or less.
• the above-mentioned visual reflectance is obtained by measuring all reflected light including specular reflected light. That is, the specular reflectance is measured by the so-called SCI (Specular Component Include) method. Since this method is not easily affected by the surface condition of the object to be measured, the visual reflectance of the uncured layer can be measured.
• SCI Standard Component Include
• the visual reflectance of the laminated film can be measured by the following method.
• a black paint for example, product name: CZ-805 BLACK (manufactured by Nikko Bics)
• CZ-805 BLACK manufactured by Nikko Bics
• the evaluation sample M is prepared by applying the coating so as to have a thickness of 6 ⁇ m or less, and then letting the mixture stand for 5 hours in a room temperature environment to dry.
• a spectrocolorimeter for example, SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
• the visual reflectance of the laminated film according to the present embodiment is 0.1% or more and 4.0% or less in the wavelength region of 380 nm or more and 780 nm or less.
• the visual reflectance of the laminated member can be measured as follows.
• the evaluation sample N is prepared by irradiating the evaluation sample M prepared above with an active energy ray having an integrated light amount of 500 mJ / cm 2 .
• the visual reflectance is measured from the optical interference layer side of the obtained evaluation sample N in the same manner as described above.
• the laminated film may be heat-treated at 80 ° C. for 1 hour before irradiation with active energy rays.
• the stretch ratio of the laminated film at 160 ° C. is 50% or more.
• the laminated film is sufficiently stretched at a molding temperature of 150 ° C. or higher and 190 ° C. or lower. Therefore, the laminated film can be shaped into a complicated three-dimensional shape without causing cracks.
• damage to the laminated film is easily suppressed. Therefore, it is possible to obtain a laminated member having the functions of a hard coat layer and an optical interference layer and having a complicated three-dimensional shape.
• the laminated film is main-molded by, for example, insert molding according to the required physical properties, shape and the like.
• the functions of the hard coat layer and the optical interference layer are, for example, excellent hard coat performance and antireflection performance.
• Hard coat performance includes, for example, high hardness, wear resistance and chemical resistance.
• the stretch ratio of the laminated film at 160 ° C. is preferably 60% or more, more preferably 70% or more.
• the stretch ratio of the laminated film at 160 ° C. may be less than 400%, less than 350%, and less than 300%. In particular, when the laminated film is stretched at a stretching rate of about 250%, it is desirable that breakage, cracks, appearance changes, etc. are not visually recognized.
• the stretch ratio of the laminated member obtained by curing the laminated film at 160 ° C. is less than 15% and may be 5% or less.
• the stretch ratio can be measured, for example, as follows.
• a tensile tester having a distance between chucks of 150 mm and an evaluation sample cut out to a length of 200 mm and a width of 10 mm are prepared.
• the long side of the evaluation sample is stretched by 50% under the conditions of a tensile force of 5.0 kgf and a tensile speed of 300 mm / min in an atmosphere of 160 ° C.
• the stretched evaluation sample is observed using a microscope having a magnification of 1000 times or more to confirm the presence or absence of cracks exceeding 100 ⁇ m in length and 1 ⁇ m in width.
• the thickness of the transparent support base material is 50 ⁇ m or more and 600 ⁇ m or less. As a result, the laminated film can maintain its rigidity even when the laminated film is stretched. In addition, warpage of the laminated film and the laminated member is easily suppressed. Further, since the transparent support base material and the laminated film can be rolled up in a roll shape, roll-to-roll processing can be performed.
• the thickness of the transparent support base material is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more.
• the thickness of the transparent support base material is preferably 500 ⁇ m or less, more preferably 480 ⁇ m or less, further preferably 450 ⁇ m or less, and particularly preferably 400 ⁇ m or less.
• the thickness of the uncured optical interference layer is not particularly limited and may be appropriately set according to the design wavelength.
• the thickness of the uncured optical interference layer is, for example, 15 nm or more and 200 nm or less.
• the thickness of the uncured optical interference layer is preferably 60 nm or more, more preferably 65 nm or more.
• the thickness of the uncured optical interference layer is preferably 180 nm or less. When the thickness of the uncured optical interference layer is within this range, good antireflection properties can be imparted to the laminated member.
• the thickness of the uncured hard coat layer is not particularly limited.
• the hard coat layer forming composition is applied so that the thickness of the uncured hard coat layer is 2 ⁇ m or more and 30 ⁇ m or less.
• the uncured hard coat layer is a hard coat layer that has been dried and has not been cured (hereinafter, simply referred to as an uncured hard coat layer). Since the uncured hard coat layer has such a thickness, warpage after curing is likely to be suppressed. Further, a hard coat layer having excellent hard coat performance can be obtained.
• the thickness of the uncured hard coat layer is more preferably 3 ⁇ m or more.
• the thickness of the uncured hard coat layer is more preferably 25 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
• the hardness of the laminated film is not particularly limited.
• the hardness Hb by the nanoindentation method measured from the optical interference layer side of the laminated film is preferably 0.1 GPa or more in that damage in the subsequent process is easily suppressed.
• the hardness Hb is 0.1 GPa or more, defects such as squeegee marks or suction marks are suppressed, and the yield is likely to be improved.
• the hardness Hb is preferably 0.5 GPa or less because the adhesion between the uncured hard coat layer and the uncured optical interference layer can be easily improved.
• the hardness Hb of the laminated film can be regarded as the maximum value of the hardness of the uncured hard coat layer or the uncured optical interference layer.
• the hardness Hb is 0.5 GPa or less, when the uncured optical interference layer is laminated on the uncured hard coat layer, the two are easily adhered to each other. Further, when the uncured hard coat layer and the uncured optical interference layer are laminated by laminating, air entry (air biting) between the layers is suppressed.
• the hardness Hb is preferably 0.1 GPa or more and 0.5 GPa or less.
• the hardness Hb is more preferably 0.15 GPa or more, further preferably 0.2 GPa or more, and particularly preferably 0.25 GPa or more.
• the hardness Hb is more preferably 0.45 GPa or less, further preferably 0.42 GPa or less, and particularly preferably 0.4 GPa or less.
• the hardness Hb of the laminated film is calculated from the optical interference layer side of the laminated film based on the value measured by the nanoindentation method.
• the measurement is performed within a range of 300 nm from the surface of the optical interference layer, particularly within a range of 50 nm or more and 100 nm or less from the surface layer of the optical interference layer.
• the hardness Hb of the laminated film is, for example, the maximum value of hardness calculated from a value measured by a nanoindentation method within a range of 50 nm or more and 100 nm or less from the surface layer of the optical interference layer.
• the hardness of the laminated member is usually higher than the hardness of the laminated film. Therefore, the hardness Ha measured by the nanoindentation method from the optical interference layer side of the laminated member can be set based on the hardness Hb of the laminated film.
• the hardness Ha measured by the nanoindentation method from the optical interference layer side of the laminated film (laminated member) irradiated with active energy rays having an integrated light amount of 500 mJ / cm 2 is For example, it is more than 0.5 GPa and less than 1.2 GPa.
• the hardness Ha of the laminated member may be more than 0.7 GPa and 1.2 GPa or less.
• the hardness Ha of the laminated member is, for example, more than 0.4 GPa and 1.2 GPa or less.
• the hardness Ha of the laminated member may be more than 0.7 GPa and 1.2 GPa or less.
• the hardness Ha is more than 0.5 GPa, the hard coating performance of the laminated member is likely to be improved.
• the hardness by the nanoindentation method is determined by, for example, the continuous stiffness measurement method using a nanoindentation device.
• a minute load (alternating current (AC) load) is applied to the sample in addition to a quasi-static test load (direct current (DC) load).
• AC alternating current
• DC direct current
• the stiffness with respect to the depth is calculated from the vibration component of the displacement generated as a result and the phase difference between the displacement and the load. As a result, a continuous profile of hardness can be obtained with respect to the depth.
• the continuous rigidity measurement method for example, Advanced Dynamic E and H. NMT method can be used.
• the nanoindentation device include NANOMECHANICS, INC. IMicro Nanoindenter made by the company can be used.
• iMicro dedicated software may be used to calculate the load and stiffness.
• the sample is loaded by an indenter until a maximum load of 50 mN is reached.
• the indenter for example, a berkovich type diamond indenter is used.
• the Poisson's ratio and the load of the coating layer may be appropriately set to appropriate values.
• the laminated member has excellent wear resistance.
• the laminated film is irradiated with active energy rays at an integrated light intensity of 500 mJ / cm 2 to obtain a laminated member.
• the surface of the optical interference layer is rubbed 5000 times with a vertical load of 4.9 N. It is preferable that no scratches are visible on the laminated member after this wear test. The fact that the scratches are not visible means that the deterioration of visibility due to the change in appearance is suppressed.
• the wear test is performed using a known method under the above conditions.
• a friction element to which a cotton cloth is fixed is usually used for the abrasion test.
• a vertical load of 4.9 N is applied to the sample by this friction element.
• the laminated film may be heat-treated for 30 to 60 seconds in an atmosphere of 150 to 190 ° C. before irradiation with active energy rays. As a result, the surface of the laminated film is flattened by leveling, and the wear resistance is more likely to be improved.
• scratches are not visible means that the scratches cannot be observed visually.
• a “scratch” is, for example, a rough surface. As long as no scratches are visually observed, very slight scratches may be observed when the sample after the abrasion test is observed using a microscope having a magnification of 100 times.
• the transparent supporting base material is not particularly limited as long as it is transparent. As a result, when the laminated member is provided with a decorative layer described later, the designability is further enhanced. "Transparent” specifically means that the total light transmittance is 80% or more. The total light transmittance of the transparent supporting base material is 80% or more, preferably 90% or more. The total light transmittance can be measured by a method conforming to JIS K 7361-1. As the transparent supporting base material, those known in the art are used without particular limitation. The transparent support base material may be colorless or colored.
• the transparent support base material is appropriately selected according to the application.
• the transparent support base material include polyester films such as polypropylene (PC) films, polyethylene terephthalates and polyethylene naphthalates; cellulose films such as diacetyl cellulose and triacetyl cellulose; acrylic films such as polymethyl methacrylate (PMMA).
• Amid-based film can be mentioned.
• the transparent supporting base material is a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinylbutyral, polyallylate, polyoxymethylene, and epoxy resin. It may be a film containing a mixture of these polymers.
• the transparent support base material may be a laminate of a plurality of films.
• the transparent support base material may be, for example, a laminate of a film made of an acrylic resin and a film made of a polycarbonate resin.
• the transparent supporting base material may be optically anisotropic or isotropic.
• the size of the birefringence of the optically anisotropic transparent supporting substrate is not particularly limited.
• the phase difference of the transparent supporting substrate having anisotropy may be 1/4 ( ⁇ / 4) of the wavelength and 1/2 ( ⁇ / 2) of the wavelength.
• the uncured hard coat layer contains an active energy ray-curable hard coat layer forming composition (hereinafter, may be referred to as composition HC).
• composition HC is cured by active energy rays.
• the active energy rays are ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• the composition HC is particularly preferably UV curable.
• the composition HC contains an active energy ray-curable resin component.
• the active energy ray-curable resin component has a polymerizable group having an unreacted unsaturated bond (polymerizable unsaturated group, typically (meth) acryloyl group).
• the elimination rate of unreacted polymerizable unsaturated groups may be 15% or more and 90% or less, and 20% or more and 80. It may be% or less, 30% or more and 70% or less, and 30% or more and 60% or less.
• the elimination rate of unreacted polymerizable unsaturated groups may be 10% or more and 50% or less.
• the elimination rate of unreacted polymerizable unsaturated groups may be 10% or more and 30% or less, and 10% or more and 50. It may be less than or equal to%.
• the hardness and / or stretch ratio of the hard coat layer can be controlled by adjusting the integrated light amount of the active energy rays.
• preform is applied to a laminated film that has not been irradiated with active energy rays. Then, before the main molding step, the laminated film is irradiated with active energy rays to the extent that it is not completely cured to reduce the stretch ratio of the laminated film to 1% or more and 15% or less. As a result, the laminated film can be slightly stretched to the extent that the shape applied in the preform step can be maintained. Therefore, even if there is a slight dimensional difference between the mold used in the preform process and the mold used in the main molding process, the laminated film is suppressed in the main molding process while suppressing the occurrence of cracks. Can be shaped. In addition, since the hardness of the hard coat layer is increased by irradiation with active energy rays, it is possible to prevent the hard coat layer from sticking to the mold in this molding step. Examples of the main molding include injection molding such as insert molding.
• the laminated film is irradiated with active energy rays having an integrated light amount of 1 mJ / cm 2 or more and 100 mJ / cm 2 or less (semi-curing).
• active energy rays having an integrated light amount of 1 mJ / cm 2 or more and 100 mJ / cm 2 or less (semi-curing).
• the laminated film can be easily formed along the mold used in the main molding while suppressing the occurrence of cracks.
• the main molding is performed.
• an active energy ray having an integrated light intensity of 100 mJ / cm 2 or more is irradiated (main curing).
• the rate of disappearance of unreacted polymerizable unsaturated groups does not change much before and after heating.
• the heat treatment hardly progresses the curing of the composition HC. Therefore, the uncured hard coat layer can be heat-treated before the semi-curing or main curing without affecting the adhesion of the hard coat layer and the stretch ratio of the laminated film.
• the smoothness of the hard coat layer can be improved. Therefore, the smoothness of the obtained laminated member is also improved.
• the molecular weight distribution of the active energy ray-curable resin component does not change much before and after the heat treatment.
• the fact that the molecular weight distribution does not change much means that the peak of the weight average molecular weight, the amount of shift in the height direction of each molecular weight peak when there are multiple weight peaks, and the amount of shift in the horizontal direction are all in the range of ⁇ 5%. It means that it fits.
• the heat treatment is performed under conditions that do not affect the performance of the hard coat layer.
• the conditions of the heat treatment may be appropriately set according to the composition of the composition HC.
• the temperature of the heat treatment may be 90 ° C. or higher and 200 ° C. or lower, 100 ° C. or higher and 200 ° C. or lower, and 110 ° C. or higher and 200 ° C. or lower.
• the heat treatment time may be 10 seconds or more and 10 minutes or less.
• the heat treatment may be performed by utilizing the heat applied in the preform process.
• the preform By performing the preform at about 150 ° C. or higher and 190 ° C. or lower, the uncured hard coat layer can be sufficiently leveled while being preformed.
• composition HC composition HC
• the hard coat layer is laminated with the uncured optical interference layer in an uncured state. Further, the laminated film is subjected to various processing in an uncured state. Therefore, the uncured hard coat layer has high hardness, low tack and is hard to be contaminated, damage during processing and appearance change are suppressed, and heat shrinkage with other layers. It is required that curl due to the difference is suppressed.
• Examples of damage during processing include dents such as suction marks and squeegee marks in the printing process.
• Examples of the change in appearance during processing include foaming and cracking in the preform process.
• the physical characteristics of the uncured hard coat layer can be adjusted by the thickness thereof, the composition of the composition HC, and the like.
• the composition HC contains an active energy ray-curable resin component.
• the active energy ray-curable resin component includes a monomer, an oligomer, or a polymer that is crosslinked and cured by the active energy ray.
• the active energy ray-curable resin component include a monomer, oligomer or polymer having at least one polymerizable unsaturated group (hereinafter, may be referred to as a reactive resin). More specifically, as the active energy ray-curable resin component, (meth) such as (meth) acrylate monomer, (meth) acrylate oligomer and (meth) acrylate polymer having at least one unsaturated double bond.
• Urethane (meth) acrylate compound such as urethane (meth) acrylate monomer, urethane (meth) acrylate oligomer, urethane (meth) acrylate polymer; silicon (meth) acrylate monomer, silicon (meth) acrylate oligomer and silicon (meth) Examples thereof include silicon (meth) acrylate compounds such as acrylate polymers. These may be used alone or in combination of two or more.
• “(Meta) acrylate” represents acrylate and / or methacrylate.
• reactive resin is preferable. Due to the reactive resin, the crosslink density of the cured hard coat layer tends to be high. Therefore, excellent hard coat performance is exhibited.
• the weight average molecular weight (Mw) of the reactive resin is preferably 5000 or more and 100,000 or less, more preferably 6000 or more and 95,000 or less, and further preferably 9000 or more and 90000 or less.
• the glass transition temperature (Tg) of the reactive resin is, for example, preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 40 ° C. or higher and 110 ° C. or lower. This makes it easier to further improve the smoothness and rigidity of the uncured hard coat layer.
• a reactive acrylic resin is preferable.
• the weight average molecular weight (Mw) can be calculated from the chromatogram measured by the gel permeation chromatograph based on the molecular weight of standard polystyrene.
• the composition HC may contain a non-reactive resin.
• the composition HC may contain a non-reactive resin as well as a reactive resin.
• the composition HC may contain two or more kinds of reactive resins and two or more kinds of non-reactive resins.
• the non-reactive resin is a resin that does not react even when irradiated with active energy rays (typically, ultraviolet rays) or shows almost no reactivity.
• active energy rays typically, ultraviolet rays
• examples of the non-reactive resin include urethane resin, acrylic resin, polyester resin, and epoxy resin.
• the weight average molecular weight (Mw) of the non-reactive resin is preferably 5000 or more and 100,000 or less, and more preferably 6000 or more and 95,000 or less.
• the Mw of one type of resin may be 5000 or more and 100,000 or less.
• the Mw of other resins is not particularly limited.
• the Mw of the other resin may be, for example, 10,000 or more and 80,000 or less.
• the composition HC preferably contains at least one of a non-reactive acrylic resin and a reactive acrylic resin. Although not limited to a particular theory, this can increase the smoothness and rigidity of the uncured hardcoat layer.
• the total content of the reactive acrylic resin and / or the non-reactive acrylic resin is preferably more than 20 parts by mass and 60 parts by mass or less, and 30 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the solid content of the composition HC. More preferably, it is 35 parts by mass or more and 60 parts by mass or less.
• the solid content of the composition HC is the above-mentioned active energy ray-curable resin component, non-reactive resin, photopolymerization initiator, inorganic oxide fine particles, and the like. The same applies to the solid content of the optical interference layer forming composition.
• the composition HC preferably contains at least one selected from a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, and a polyfunctional silicon (meth) acrylate compound.
• a polyfunctional (meth) acrylate compound preferably contains at least one selected from a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, and a polyfunctional silicon (meth) acrylate compound.
• the composition HC preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin, and a polyfunctional urethane (meth) acrylate monomer and / or an oligomer.
• the composition HC is composed of a reactive acrylic resin and / or a non-reactive acrylic resin having a Mw of 5000 or more and 100,000 or less, and an acrylate equivalent of 100 g / eq. More than 200 g / eq. It preferably contains the following polyfunctional urethane (meth) acrylate monomers and / or oligomers. As a result, the low tack property of the uncured hard coat layer is further improved.
• the content of the polyfunctional urethane (meth) acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the solid content of the composition HC. It is preferably 13 parts by mass or more and 68 parts by mass or less.
• the acrylate equivalent of the polyfunctional urethane (meth) acrylate monomer and / or oligomer is 110 g / eq. 180 g / eq. It may be 115 g / eq. More than 160 g / eq. It may be:
• the composition HC comprises a reactive acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of a polyfunctional silicon (meth) acrylate monomer and / or an oligomer and inorganic oxide fine particles. It may be included.
• the composition HC preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicone (meth) acrylate monomer and / or an oligomer, and inorganic oxide fine particles.
• the polyfunctional silicon (meth) acrylate monomer and / or oligomer makes it possible to lower the surface tension of the uncured hard coat layer and improve the leveling property.
• the inorganic oxide fine particles suppress the volume shrinkage of the uncured hard coat layer and facilitate the increase in rigidity. Therefore, changes in appearance during the manufacturing process of the uncured hard coat layer are likely to be suppressed. Further, the appearance change and curl of the cured hard coat layer are suppressed. In addition, the tackiness of the cured hard coat layer is reduced and the wear resistance is likely to be increased.
• the Mw of the polyfunctional silicon (meth) acrylate monomer and / or oligomer is preferably 700 or more and 100,000 or less, more preferably 800 or more and 90000 or less, and preferably 800 or more and 85,000 or less.
• the content of the polyfunctional silicon (meth) acrylate monomer and / or oligomer is preferably 0.1 part by mass or more and 50 parts by mass or less, and 1 part by mass or more and 45 parts by mass or less, based on 100 parts by mass of the solid content of the composition HC. Is more preferable, and 1.5 parts by mass or more and 40 parts by mass or less are particularly preferable.
• the content of the inorganic oxide fine particles is preferably 1 part by mass or more and 55 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and 12 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the solid content of the composition HC. More than parts by mass is particularly preferable.
• the inorganic oxide fine particles are not particularly limited.
• examples of the inorganic oxide fine particles include silica (SiO 2 ) particles, alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, zinc oxide particles, and zirconia oxide particles.
• the surface of the inorganic oxide fine particles may be modified with a functional group containing an unsaturated double bond.
• a (meth) acryloyl group is desirable.
• silica particles and alumina particles are preferable from the viewpoint of cost and coating stability, and silica particles and alumina particles whose surface is modified with a functional group are particularly preferable.
• the form of the inorganic oxide fine particles may be a sol.
• the primary particle size of the inorganic oxide fine particles is not particularly limited. From the viewpoint of transparency and paint stability, the primary particle size of the inorganic oxide fine particles is preferably 5 nm or more and 100 nm or less.
• the primary particle size of the inorganic oxide fine particles is a value measured by using image processing software from a cross-sectional image obtained by an electron microscope. The average particle size of other particles can be determined by the same method.
• silica particles Commercially available products of silica particles (colloidal silica) are illustrated below. Made by Nissan Chemical Industries, Ltd .: IPA-ST, MEK-STM, IBK-ST, PGMST, XBA-ST, MEK-AC-2101, MEK-AC-2202, MEKAC-4101M IBK-SD Made by Fuso Chemical Industry Co., Ltd .: PL-1-IPA, PL-1-TOR, PL-2-IPA, PL-2-MEK, PL-3-TL JGC Catalyst Kasei Co., Ltd .: OSCAL series, ELECOM series Big Chemy Japan Co., Ltd .: NANOBYK-3605
• Allumina particles Commercially available products of alumina particles are illustrated below. Made by Sumitomo Osaka Cement Co., Ltd .: AS-150 I, AS-150T Made by Big Chemie Japan: NANOBYK-3601, NANOBYK-3602, NANOBYK-3610
• zirconia oxide particles Commercially available products of zirconia oxide particles are illustrated below. Made by Sakai Chemical Industry: SZR-K, SZR-KM Made by CIK Nanotech: ZRANB15WT% -P02, ZRMIBK15WT% -P01, ZRMIBK15WT% -F85 Made by Solar: NANON5ZR-010, NANON5ZR-020
• Examples of the (meth) acrylate monomer or oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
• Examples of the (meth) acrylate polymer include at least one polymer of the above (meth) acrylate monomer and oligomer.
• KRM-8200 9-functional urethane (meth) acrylate
• KRM-7804 9-functional urethane (meth) acrylate
• 10-functional urethane (meth) acrylate KRM-8452” manufactured by Daicel Ornex
• KRM-8509 15-functional urethane (meth) acrylate
• the urethane (meth) acrylate monomer or oligomer can also be prepared by reacting, for example, a polycarbonate diol, a (meth) acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule, and a polyisocyanate. it can.
• Examples of the urethane (meth) acrylate polymer include at least one polymer of the above-mentioned urethane (meth) acrylate monomer and oligomer.
• the silicon (meth) acrylate monomer or oligomer is a (meth) acrylate monomer or oligomer having a siloxane bond.
• a functional group containing a fluorine atom may be bonded to the silicon atom.
• the composition HC contains a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional urethane acrylate monomer and / or an oligomer, a polyfunctional silicon (meth) acrylate monomer and / or an oligomer containing a fluorine atom, and inorganic oxide fine particles. It may include at least one selected from the group consisting of.
• the composition HC preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy ray-curable resin component.
• photopolymerization initiator examples include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, and an oxime ester-based polymerization initiator.
• alkylphenone-based photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-.
• acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
• titanosen-based photopolymerization initiator for example, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium is used. Can be mentioned.
• Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2). -Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy) Ethoxy) ethyl ester can be mentioned.
• These photopolymerization initiators may be used alone or in combination of two or more.
• the content of the photopolymerization initiator is preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC.
• the composition HC may contain a solvent.
• the solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of the transparent supporting base material, the coating method, and the like.
• the solvent examples include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether.
• aromatic solvents such as toluene and xylene
• ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone
• diethyl ether isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether.
• Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone Amido-based solvents such as; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; halogen-based solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more. Of these, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferable.
• the composition HC can contain various additives, if necessary.
• Additives include, for example, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, surface conditioners, leveling agents and light stabilizers (eg, hindered amine light stabilizers (HALS)). Be done.
• HALS hindered amine light stabilizers
• the uncured optical interference layer contains an active energy ray-curable optical interference layer forming composition (hereinafter, may be referred to as composition R).
• composition R is cured by active energy rays.
• the composition R is preferably cured by the same type of active energy rays as the composition HC.
• the optical interference layer can function as a layer having a low refractive index.
• the refractive index of the cured optical interference layer may be, for example, 1.35 or more and 1.55 or less, 1.38 or more and 1.55 or less, and 1.38 or more and 1.51 or less. As a result, good antireflection property is exhibited.
• the optical interference layer may function as a layer having a high refractive index or a layer having a medium refractive index.
• the refractive index of the high refractive index layer may be more than 1.55 and 2.00 or less.
• the refractive index of the medium refractive index layer is not particularly limited, and may be between the low refractive index layer and the high refractive index layer.
• the refractive index of the medium refractive index layer may be, for example, 1.55 or more and 1.70 or less.
• the thickness of the optical interference layer is not particularly limited.
• the thickness of the optical interference layer may be 10 nm or more and 300 nm or less.
• the thickness of the optical interference layer is preferably 15 nm or more, more preferably 40 nm or more, and particularly preferably 60 nm or more.
• the thickness of the optical interference layer is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.
• the composition R contains an active energy ray-curable resin component.
• the active energy ray-curable resin component has a polymerizable group having an unreacted unsaturated bond (polymerizable unsaturated group, typically (meth) acryloyl group).
• the uncured optical interference layer When the uncured optical interference layer is irradiated with active energy rays having an integrated light amount of 500 mJ / cm 2 , 10% to 100% of the unreacted polymerizable unsaturated groups contained in the uncured optical interference layer disappear.
• the elimination rate of unreacted polymerizable unsaturated groups may be 15% or more and 90% or less, and 20% or more and 80. It may be% or less, 30% or more and 70% or less, and 30% or more and 60% or less.
• the elimination rate of unreacted polymerizable unsaturated groups may be 10% or more and 30% or less, and 10% or more and 50. It may be less than or equal to%.
• the elimination rate of unreacted polymerizable unsaturated groups may be 10% or more and 50% or less.
• the hardness of the optical interference layer is high, and the draw ratio tends to be low.
• the hardness and / or the stretching ratio of the optical interference layer can be controlled.
• the uncured optical interference layer Even in the uncured optical interference layer, the disappearance rate of unreacted polymerizable unsaturated groups does not change much before and after the heat treatment. In other words, the heat treatment hardly progresses the curing of the composition R. Therefore, before the activation energy ray irradiation step, the uncured light interference layer can be heat-treated without affecting the adhesion of the light interference layer and the stretch ratio of the laminated film. The smoothness of the optical interference layer can be improved by the heat treatment. Therefore, the smoothness of the obtained laminated member is also improved.
• the heat treatment is performed under conditions that do not affect the performance of the optical interference layer.
• the conditions of the heat treatment may be appropriately set according to the composition of the composition R.
• the temperature of the heat treatment may be 90 ° C. or higher and 200 ° C. or lower, 100 ° C. or higher and 200 ° C. or lower, and 110 ° C. or higher and 200 ° C. or lower.
• the heat treatment time may be 10 seconds or more and 10 minutes or less.
• This heat treatment may also be performed by utilizing the heat applied in the preform process.
• the uncured optical interference layer can be sufficiently leveled while being preformed.
• composition R The optical interference layer is laminated with the uncured hard coat layer in an uncured state. Further, as described above, the laminated film is subjected to various processing in an uncured state. Therefore, the optical interference layer is required to have the same performance as the hard coat layer in addition to the antireflection performance. In particular, the optical interference layer is required to have excellent antireflection performance, low tack and resistance to contamination, damage during processing, and suppression of appearance change. Examples of the change in appearance during processing include streaks called zipping marks that occur when the protective film is peeled off.
• the physical characteristics of the uncured optical interference layer can be adjusted by the thickness thereof, the composition of the composition R, and the like.
• the composition R contains an active energy ray-curable resin component.
• the active energy ray-curable resin component includes a monomer, an oligomer, or a polymer (reactive resin) that is crosslinked and cured by the active energy ray.
• Examples of the active energy ray-curable resin component contained in the composition R include those similar to the active energy ray-curable resin component contained in the above composition HC.
• the weight average molecular weight (Mw) of the reactive resin is preferably 5000 or more and 100,000 or less, more preferably 6000 or more and 95,000 or less, and further preferably 9000 or more and 90000 or less.
• the glass transition temperature (Tg) of the reactive resin is, for example, preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 40 ° C. or higher and 110 ° C. or lower. This makes it easier to further improve the smoothness and rigidity of the uncured optical interference layer.
• a reactive acrylic resin is preferable.
• the composition R may contain a non-reactive resin.
• the non-reactive resin include those similar to the non-reactive resin contained in the above composition HC.
• the weight average molecular weight (Mw) of the non-reactive resin is preferably 5000 or more and 100,000 or less, and more preferably 6000 or more and 95,000 or less.
• the composition R may contain a non-reactive resin together with the reactive resin.
• the composition R may contain two or more kinds of reactive resins and two or more kinds of non-reactive resins.
• the total content of the reactive acrylic resin and / or the non-reactive acrylic resin is preferably more than 5 parts by mass and 40 parts by mass or less, and 10 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the solid content of the composition R. It is more preferably 15 parts by mass or more, and particularly preferably 25 parts by mass or less.
• the Mw of one type of resin may be 5000 or more and 100,000 or less.
• the Mw of other resins is not particularly limited.
• the Mw of the other resin may be, for example, 10,000 or more and 80,000 or less.
• the composition R preferably contains a reactive acrylic resin and / or a non-reactive acrylic resin, and a polyfunctional urethane (meth) acrylate monomer and / or an oligomer.
• a reactive acrylic resin and / or a non-reactive acrylic resin and a polyfunctional urethane (meth) acrylate monomer and / or an oligomer.
• the polyfunctional urethane (meth) acrylate monomer and oligomer include those similar to the polyfunctional urethane (meth) acrylate monomer and oligomer contained in the above composition HC.
• the composition R contains a reactive acrylic resin and / or a non-reactive acrylic resin having a Mw of 5000 or more and 100,000 or less, and an acrylate equivalent of 100 g / eq. More than 200 g / eq. It preferably contains the following polyfunctional urethane (meth) acrylate monomers and / or oligomers.
• the content of the polyfunctional urethane (meth) acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the solid content of the composition R. It is preferably 13 parts by mass or more and 68 parts by mass or less.
• the acrylate equivalent of the polyfunctional urethane (meth) acrylate monomer and / or oligomer is 110 g / eq. 180 g / eq. It may be 115 g / eq. More than 160 g / eq. It may be:
• the composition R is at least one selected from the group consisting of a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicone (meth) acrylate monomer and / or an oligomer, a fluororesin, and inorganic oxide fine particles. And may be included.
• the composition R may contain a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicone (meth) acrylate monomer and / or an oligomer, a fluororesin, and inorganic oxide fine particles. preferable.
• polyfunctional silicon (meth) acrylate monomers and / or oligomers reduce the surface tension of the uncured optical interference layer, improve leveling and reduce tack. It will be possible. Since the fluororesin imparts slipperiness to the uncured and cured optical interference layer, the abrasion resistance is likely to be improved.
• the inorganic oxide fine particles suppress the volume shrinkage of the uncured optical interference layer and facilitate the increase in rigidity. Therefore, changes in appearance during the manufacturing process of the uncured optical interference layer are likely to be suppressed. Further, the appearance change and the occurrence of curl of the cured optical interference layer are suppressed. In addition, the tackiness of the cured optical interference layer is reduced and the abrasion resistance is likely to be increased.
• Examples of the polyfunctional silicon (meth) acrylate monomer and / or oligomer include those similar to the polyfunctional silicon (meth) acrylate monomer and / or oligomer contained in the above composition HC.
• Examples of the inorganic oxide fine particles include those similar to those of the inorganic oxide fine particles contained in the above composition HC.
• the Mw of the polyfunctional silicon (meth) acrylate monomer and / or oligomer is preferably 700 or more and 100,000 or less, more preferably 800 or more and 90000 or less, and preferably 800 or more and 85,000 or less.
• the content of the polyfunctional silicon (meth) acrylate monomer and / or oligomer is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 48 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R. It is preferable, and it is particularly preferable that it is 13 parts by mass or more and 48 parts by mass or less.
• Fluororesin does not contain a siloxane bond, and at least a part of hydrogen in the alkyl chain is replaced with fluorine.
• fluororesin include perfluorooctyl acrylate and acrylic-modified perfluoropolyether.
• the fluororesin may have a (meth) acryloyl group partially substituted with fluorine.
• Fluororesins are illustrated below. Made by DIC: Mega Fvck RS-72-K, Mega Fvck RS-75, Mega Fvck RS-76-E, Mega Fvck RS-76-NS, Mega Fvck RS-77 Made by Daikin Industries, Ltd .: Optool DAC-HP Made by Sorbet Solexis: FLUOROLINK MD700, FLUOROLINK AD1700 Made by Neos: Futergent 601ADH2
• the content of the fluororesin is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and 1.5 parts by mass or more with respect to 100 parts by mass of the solid content of the composition R. 7 parts by mass or less is particularly preferable.
• the content of the inorganic oxide fine particles is preferably 1 part by mass or more and 55 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and 12 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the solid content of the composition R. More than parts by mass is particularly preferable.
• the composition R may contain at least one selected from a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, and a polyfunctional silicon (meth) acrylate compound.
• a polyfunctional (meth) acrylate compound a polyfunctional urethane (meth) acrylate compound
• a polyfunctional silicon (meth) acrylate compound As a result, the cured optical interference layer has a high crosslink density, and thus has excellent hard coating performance. In addition, the transparency of the cured optical interference layer is likely to be improved.
• the polyfunctional (meth) acrylate compound, the polyfunctional urethane (meth) acrylate compound, and the polyfunctional silicon (meth) acrylate compound for example, those exemplified for the above composition HC can be selected.
• Composition R contains a reactive acrylic resin, a non-reactive acrylic resin, a polyfunctional urethane acrylate monomer and / or an oligomer, a polyfunctional silicon (meth) acrylate monomer and / or an oligomer containing a fluorine atom, a fluorine resin and inorganic oxide fine particles. It may contain at least one selected from the group consisting of.
• Composition R contains a reactive acrylic resin and / or a non-reactive acrylic resin, a polyfunctional urethane acrylate monomer and / or an oligomer, a polyfunctional silicon (meth) acrylate monomer and / or an oligomer containing a fluorine atom, a fluororesin and an inorganic substance. It may contain at least one selected from the group consisting of oxide fine particles.
• the composition R preferably contains a photopolymerization initiator. This facilitates the polymerization of the active energy ray-curable resin component.
• a photopolymerization initiator for example, those exemplified with respect to the above composition HC can be selected.
• the content of the photopolymerization initiator is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R.
• the composition R may contain a solvent.
• the solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of the transparent supporting base material, the coating method, and the like.
• the solvent those exemplified for the above composition HC can be selected. Of these, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferable.
• the composition R forming the low refractive index layer preferably contains a refractive index lowering component that lowers the refractive index of the cured optical interference layer.
• the refractive index lowering component is, for example, particulate (hereinafter, may be referred to as a refractive index lowering particle).
• the refractive index lowering component examples include hollow silica fine particles.
• the hollow silica fine particles can reduce the refractive index while maintaining the strength of the optical interference layer.
• the hollow silica fine particles are a structure in which a gas is filled and / or a porous structure containing a gas.
• the refractive index decreases in inverse proportion to the gas occupancy. Therefore, the hollow silica fine particles have a low refractive index as compared with the original refractive index of the silica fine particles.
• Examples of the hollow silica fine particles include thru rear 4320 (manufactured by JGC Corporation).
• silica fine particles such that a nanoporous structure is formed inside and / or at least a part of the surface may be used.
• the nanoporous structure is formed according to the morphology, structure, aggregated state, and dispersed state inside the coating film of the silica fine particles.
• the average particle size of the refractive index-reduced particles is preferably 60 nm or more and 200 nm or less.
• the average particle size is the primary particle size.
• the content of the refractive index lowering component is preferably 35 parts by mass or more and 70 parts by mass or less, and more preferably 37.5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the solid content of the composition R.
• the cured optical interference layer tends to exhibit excellent antireflection properties.
• the resin components of the composition HC and the composition R may be the same or different. Among them, it is preferable that the resin components of both are the same or the same kind. This is because the adhesion between the uncured hard coat layer and the uncured optical interference layer is improved, and peeling between layers is less likely to occur.
• the laminated film may further have at least one uncured functional layer between the uncured hard coat layer and the uncured optical interference layer.
• the functional layer reinforces the optical function of the laminated film or imparts a new optical function.
• the functional layer may be another optical interference layer having optical characteristics different from those of the above optical interference layer.
• the functional layer may be a combination of two or more other optical interference layers having characteristics different from those of the above optical interference layer.
• the preferable functional layer is, for example, at least one of an optical interference layer having a high refractive index and an optical interference layer having a medium refractive index.
• the thickness of the other optical interference layer is not particularly limited.
• the thickness of each of the other optical interference layers may be 10 nm or more and 300 nm or less.
• the thickness of each of the optical interference layers is preferably 15 nm or more, more preferably 40 nm or more, and particularly preferably 60 nm or more.
• the thickness of each of the optical interference layers is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.
• the functional layer forming composition forming the functional layer may contain the same components as those contained in the above composition HC or composition R.
• the functional layer forming composition forming another light interference layer may contain the same components as those contained in the composition R.
• the components contained in the plurality of optical interference layers may be the same or different.
• the resin components contained in the plurality of optical interference layers may be the same or different.
• the high refractive index layer and the medium refractive index layer may contain a resin component other than the active energy ray-curable type.
• resin components include thermoplastic resins such as alkyd resins, polyester resins, and acrylic resins; and thermocurable properties such as epoxy resins, phenolic resins, melamine resins, urethane resins, and silicon resins.
• Resin; Polyisocyanate can be mentioned.
• the laminated film may have a protective film on the surface of the uncured optical interference layer opposite to the uncured hard coat layer.
• the protective film protects the optical interference layer and the laminated film, and also functions as a release paper for forming the composition R into a film.
• the protective film may have an adhesive layer on the coated surface.
• a protective film known in the art is used without particular limitation.
• the protective film may be colorless or colored.
• the protective film may be transparent.
• the thickness of the protective film is not particularly limited.
• the thickness of the protective film may be 20 ⁇ m or more and 100 ⁇ m or less. As a result, the protective effect of the uncured optical interference layer tends to be enhanced.
• the thickness of the protective film is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, further preferably 33 ⁇ m or more, and particularly preferably 35 ⁇ m or more.
• the thickness of the protective film is preferably 85 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 65 ⁇ m or less.
• the thickness of the protective film is a value that does not include the thickness of the adhesive layer.
• the protective film is made of resin, for example.
• the resin film include polyolefin films such as polyethylene films and polypropylene films (including non-stretched polypropylene films (CPP films) and biaxially stretched polypropylene films (OPP films)), and modifications obtained by modifying these polyolefins to add further functions.
• Polyethylene film, polyethylene terephthalate, polyester film such as polycarbonate and polylactic acid, polystyrene film, polystyrene resin film such as AS resin film and ABS resin film, nylon film, polyamide film, polyvinyl chloride film and polyvinylidene chloride film, polymethyl Penten film can be mentioned.
• Additives such as an antistatic agent and an ultraviolet ray inhibitor may be added to the resin film, if necessary.
• the surface of the resin film may be subjected to corona treatment or low temperature plasma treatment.
• At least one selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film is preferable.
• At least one selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film having a thickness of 30 ⁇ m or more and 100 ⁇ m or less is preferable.
• the laminated member according to the present embodiment is obtained by curing the above-mentioned laminated film.
• the laminated member is a completely cured product of the laminated film.
• the laminated member has a transparent support base material, a cured hard coat layer, and a cured optical interference layer in this order.
• the laminated member may further have at least one cured functional layer between the cured hard coat layer and the cured optical interference layer.
• the laminated member may or may not have a protective film.
• the protective film is used according to the purpose of use.
• the laminated member is obtained, for example, by irradiating the laminated film with active energy rays to cure the uncured hard coat layer and the uncured optical interference layer.
• the laminated member is particularly suitable as a protective material for the display and various sensors arranged around it.
• the display include a liquid crystal display, an organic EL display, and a plasma display.
• the laminated member is particularly suitable as a protective material for an in-vehicle touch panel display and its surroundings.
• the laminated member is arranged so that the light interference layer is outside the hard coat layer.
• the laminated member may further include a decorative layer.
• the laminated members include, for example, a transparent support base material, a hard coat layer and an optical interference layer arranged on one main surface of the transparent support base material, and a decorative layer arranged on the other main surface of the transparent support base material. And.
• the decorative layer may be provided on a part of the other main surface of the transparent support substrate.
• the decorative layer is a layer that imparts decoration such as a pattern, characters, or metallic luster to the laminated member. The decorative layer enhances the design of the laminated member.
• the decorative layer examples include at least one of a printing layer and a thin-film deposition layer.
• the print layer and the vapor deposition layer are each one or more layers, and may include a plurality of layers.
• the thickness of the decorative layer is not particularly limited, and is appropriately set according to the design and the like.
• the print layer is formed of, for example, a colored ink containing a binder resin and a colorant.
• the binder resin is not particularly limited.
• the binder resin include polyvinyl-based resins such as vinyl chloride / vinyl acetate-based copolymers, polyamide-based resins, polyester-based resins, polyacrylic resins, polyurethane-based resins, polyvinyl acetal-based resins, polyester urethane-based resins, and cellulose.
• Examples thereof include ester resins, alkyd resins, and chlorinated polyolefin resins.
• the colorant is not particularly limited, and examples thereof include known pigments or dyes.
• the yellow pigment include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as titanium nickel antimony oxide.
• the red pigment include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as valve stems.
• the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue.
• the black pigment include organic pigments such as aniline black.
• the white pigment include inorganic pigments such as titanium dioxide.
• the vapor deposition layer is formed of, for example, at least one metal selected from the group of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof. Will be done.
• the laminated member may further include a molding resin layer.
• the molded resin layer supports the hard coat layer and the optical interference layer together with the transparent supporting base material.
• the laminated members include, for example, a transparent support base material, a hard coat layer and a light interference layer arranged on one main surface of the transparent support base material, and a molding resin layer arranged on the other main surface of the transparent support base material. And.
• the shape of the molded resin layer is not limited. Therefore, the degree of freedom in designing the laminated member is increased.
• the resin that forms the molding resin layer is not particularly limited.
• the molded resin layer contains, for example, a thermosetting resin and / or a thermoplastic resin.
• the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester, and thermosetting polyimide.
• the thermoplastic resin include so-called engineering plastics. Examples of engineering plastics include polyamide, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polysulfone, polyether sulfone, polyphenylene sulfide, and liquid crystal polymer.
• the laminated members include a transparent support base material, a hard coat layer and an optical interference layer arranged on one main surface of the transparent support base material, and a decorative layer arranged on the other main surface of the transparent support base material.
• a molding resin layer may be provided.
• the decorative layer is arranged so as to be sandwiched between the transparent supporting base material and the molding resin layer.
• the laminated member according to the present embodiment is manufactured by a method including, for example, a step of preparing the above-mentioned laminated film and a step of irradiating the laminated film with active energy rays. After the step of preparing the laminated film, a decoration step, a preform step, and a main molding step are performed as necessary. The decorating step is preferably performed before the preform step.
• the step of irradiating the active energy ray may be performed a plurality of times.
• semi-curing may be performed by irradiating an active energy ray so as to cure a part of the laminated film.
• the main curing step of irradiating the active energy rays so as to cure the rest of the laminated film is performed.
• the type of active energy ray is not particularly limited.
• the active energy ray is appropriately selected according to the type of resin component contained in the layer forming composition.
• the active energy ray is not particularly limited, and may be ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays. Of these, ultraviolet rays having a wavelength of 380 nm or less are preferable. Ultraviolet rays are irradiated using, for example, a high-pressure mercury lamp or an ultra-high pressure mercury lamp.
• the laminated film includes a transparent support base material, an uncured hard coat layer formed on at least one surface of the transparent support base material, and an uncured optical interference layer formed on the uncured hard coat layer. Have.
• the laminated film is a method including a step of forming an uncured hard coat layer on at least one surface of a transparent support base material and a step of laminating an uncured optical interference layer on the uncured hard coat layer. Manufactured by.
• the method of forming an uncured hard coat layer is not particularly limited.
• the uncured hard coat layer is formed by, for example, applying the composition HC on at least one surface of the transparent supporting substrate. After coating, a drying step may be performed.
• the drying conditions are not particularly limited, and are appropriately set so that at least a part of the solvent contained in the composition HC is removed.
• the composition HC can be prepared by a method usually used by those skilled in the art. For example, it can be prepared by mixing each of the above components using a commonly used mixing device such as a paint shaker or a mixer.
• the method for applying the composition HC is not particularly limited, and is carried out by a method usually used by those skilled in the art.
• the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a bar coating method (for example, a wire bar coating method), a die coating method, an inkjet method, a gravure coating method or an extrusion coating method. (US Pat. No. 2,681294).
• Step of Laminating the Uncured Hard Coat Layer and the Uncured Optical Interference Layer The method of laminating the uncured hard coat layer and the uncured optical interference layer is not particularly limited, and the coating method is used. It may be a laminating method.
• the uncured optical interference layer is laminated by applying the composition R on the uncured hard coat layer.
• a drying step may be performed.
• the drying conditions are not particularly limited, and are appropriately set so that at least a part of the solvent contained in the composition R is removed.
• the other functional layer forming composition is applied onto the uncured hard coat layer by the above method before the composition R is applied onto the uncured hard coat layer.
• a laminated film in which another uncured functional layer is arranged between the uncured hard coat layer and the uncured optical interference layer can be obtained.
• the other functional layer forming composition and the composition R can be prepared by the above-mentioned method.
• an uncured optical interference layer formed on another supporting base material typically, the above-mentioned protective film
• an uncured hard coat layer formed on the transparent supporting base material are formed. Can be pasted together.
• the multiphase of the uncured hard coat layer and the uncured optical interference layer is particularly likely to be suppressed.
• the uncured optical interference layer is formed by applying the composition R on another supporting base material.
• the method for applying the composition R is the same as that for the composition HC, which is usually performed by those skilled in the art. After coating, a drying step may be performed. After the two are bonded together, the other supporting base material may be peeled off.
• Other functional layers can also be laminated by laminating.
• the other functional layers are bonded by, for example, the following steps. Lamination that includes the transparent support base material, the uncured hard coat layer, the uncured light interference layer (first light interference layer), and the other support base material in this order obtained by the above laminating step.
• the other supporting substrate is peeled off from the object to expose the uncured optical interference layer. Separately, another uncured functional layer is formed on the new supporting base material.
• the uncured functional layer supported by the new supporting base material is attached to the exposed uncured optical interference layer. If necessary, these steps may be repeated.
• the above decoration layer is formed on the other main surface of the transparent support base material before the forming step. You may.
• the decoration step may be performed before the preparatory step or after the preparatory step. From the viewpoint of productivity, it is desirable that the decoration process is performed after the preparatory process.
• the method of forming the print layer is not particularly limited.
• Examples of the method for forming the print layer include an offset printing method, a gravure printing method, a screen printing method, a roll coating method and a spray coating method.
• the method for forming the thin-film deposition layer is also not particularly limited.
• Examples of the method for forming the vapor-deposited layer include a vacuum vapor deposition method, a sputtering method, an ion plating method and a plating method.
• the laminated film is molded into a shape according to a desired three-dimensional shape after the preparatory step (further, the decoration step) and before the main molding step. You may. By molding the laminated film into a shape close to a three-dimensional shape in advance, cracks, wrinkles, and the like are more likely to be suppressed when the laminated film is subsequently molded into a three-dimensional shape.
• a trimming step may be performed to remove unnecessary portions of the laminated film.
• the preform method is not particularly limited.
• the preform is performed by, for example, a vacuum forming method, a compressed air forming method, or a vacuum compressed air forming method.
• the mold and the laminated film are installed in the same processing room.
• the laminated film is installed so that the transparent supporting base material faces the mold.
• the laminated film is heated to put the processing chamber in a vacuum and / or pressurized state. As a result, the laminated film is deformed along the mold.
• the laminated film is then cooled and removed from the mold.
• the laminated film may be heat-treated at a temperature of 90 ° C. or higher and 150 ° C. or lower. Since the laminated film according to this embodiment is hard to be cured by heat treatment, the stretch ratio is hard to decrease, but the surface of each layer can be smoothed.
• the semi-curing step is usually performed after the preform.
• the draw ratio required for the preform step and / or the main molding step can be obtained.
• the integrated light intensity of the active energy rays is, for example, 1 mJ / cm 2 or more and less than 100 mJ / cm 2 .
• a trimming step of removing unnecessary portions of the laminated film may be performed.
• main molding step for example, insert molding is performed.
• the optical interference layer is opposed to the mold, and the molding resin is injected toward the transparent supporting base material.
• the laminated film is shaped into a three-dimensional shape, and a molding resin layer is formed on the other main surface of the transparent support base material.
• the laminated film is completely cured by irradiating the laminated film with active energy rays. As a result, a laminated member is obtained.
• the integrated light intensity of the active energy rays is, for example, 100 mJ / cm 2 or more. Integrated light quantity of the active energy ray may be at 5000 mJ / cm 2 or less, may be at 3000 mJ / cm 2 or less.
• the active energy rays may be of the same type as the semi-curing step or may be different.
• the above aspect is an example, and a known treatment, processing step, or the like may be introduced if desired.
• TB1-TB4 Product name AW-10U, manufactured by Wavelock Advanced Technology Co., Ltd., 2-layer (PMMA / PC) film consisting of PMMA and PC, TB1: Thickness 300 ⁇ m, TB2: Thickness 200 ⁇ m, TB3: Thickness 500 ⁇ m, TB4: thickness 800 ⁇ m, TB5: thickness 100 ⁇ m
• composition HC1 Preparation of composition HC1
• KRM-9322 reactive acrylic resin
• KRM-8452 polyfunctional urethane acrylate oligomer
• OSCAL 1842 inorganic oxide fine particles
• Omnirad 184 initiated photopolymerization
• composition HC2-HC6 A transparent composition HC2-HC6 having a solid content concentration of 35% was prepared in the same manner as the composition HC1 except that the formulations shown in Table 1C were used.
• composition LR1 Preparation of composition LR1
• KRM-9322 reactive acrylic resin
• KRM-8452 polyfunctional urethane acrylate oligomer
• purple light UV-AF305 fluorescent atom
• 13.3 parts by mass of polyfunctional silicon acrylate oligomer containing) and 4.8 parts by mass of Omnirad 184 (initiation of photopolymerization) were mixed.
• 43.8 parts by mass of thru rear 4320 (refractive index lowering component) was blended. Thereby, the transparent composition LR1 having a resin solid content concentration of 3.0% was prepared.
• composition LR2-LR5 A transparent composition LR2-LR5 having a solid content concentration of 35% was prepared in the same manner as in the composition LR1 except that the formulations shown in Table 1A were used.
• Example 1 (1) Production of Laminated Film (1-1) Formation of Uncured Hard Coat Layer
• the composition HC1 is applied to the PMMA surface of the transparent support base material TB1 with a gravure coater so that the thickness after drying is 8 ⁇ m. did. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to form an uncured hard coat layer.
• the hard coat layer After performing a touch test on the surface of the obtained uncured hard coat layer, its appearance was observed. There was no change in the appearance of the surface of the uncured hard coat layer, and it was evaluated as tack-free.
• the hard coat layer may be referred to as "HC layer”.
• composition LR1 was applied to an OPP film (protective film) with a gravure coater so that the thickness after drying was 95 nm. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to form an uncured optical interference layer. The surface of the obtained uncured optical interference layer was also tack-free. The protective film on which the uncured optical interference layer was formed was wound into a roll.
• LR layer the optical interference layer formed by the composition LR1 having a low refractive index
• a black paint (product name: CZ-805 BLACK (manufactured by Nikko Bics Co., Ltd.)) is applied to the surface of the transparent support base material of the laminated film opposite to the uncured HC layer. The film was applied so that the dry film thickness was 3 ⁇ m or more and 6 ⁇ m or less. Next, the laminated film coated with the black paint was left to stand for 5 hours in a room temperature environment and dried to obtain an uncured evaluation sample. Made.
• the visual reflectance was measured by the SCI method from the optical interference layer side of the evaluation sample. SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used for the measurement, and the measurement wavelength region was set to 380 nm or more and 780 nm or less.
• (E) Coating hardness The hardness was measured from the uncured LR layer side of the laminated film and the LR layer side of the laminated member, respectively. The hardness is determined by NANOMECHANICS, INC. It was measured by a continuous rigidity measurement method (method used: Advanced Dynamic E and H. NMT) using an iMicro Nanoindenter manufactured by Japan.
• a minute AC load was superposed on the surface of the evaluation sample on a quasi-static test load. The load was applied until the maximum load of 50 mN was reached.
• As an indenter a Berkovich type diamond indenter (tip radius of curvature of 20 nm) was used. From the vibration component of the generated displacement and the phase difference between the displacement and the load, the continuous stiffness with respect to the depth was calculated, and the hardness profile with respect to the depth was obtained. The maximum hardness of this profile at a depth of 50 nm to 100 nm was calculated.
• the iMicro dedicated software was used to calculate the load and stiffness. In calculating the stiffness, the Poisson's ratio of the coating layer was set to 0.35. The load was controlled so that the strain rate ( ⁇ P / ⁇ t) / P was 0.2. In the analysis with the iMicro dedicated software, the point tentatively defined on the iMicro dedicated software at the time of measurement (the point where d (Force) / d (Disp) becomes about 500 N / m) was set as it is as the surface position of the coating layer. ..
• (F) Handleability after preform The preformed laminated film was irradiated with active energy rays having an integrated light intensity of 500 mJ / cm 2 to prepare an evaluation sample.
• the handleability when setting the evaluation sample in the injection molding mold was evaluated.
• the evaluation criteria are as follows. Good: The evaluation sample is stiff and can be easily installed in the injection molding mold. Possible: The evaluation sample is weak and there is some difficulty in handling, but it can be installed in the mold. Defect: The evaluation sample is weak. , Cannot be installed in the mold.
• (G) Warp of Laminated Member An evaluation sample of 200 mm ⁇ 200 mm was cut out from the laminated film and irradiated with active energy rays having an integrated light intensity of 500 mJ / cm 2 . Next, the evaluation sample was placed on a horizontal plane, and the amount of lift (warp amount) from the horizontal plane at the four corners was measured using a ruler and averaged.
• the evaluation criteria are as follows. Best: Average warpage amount is 10 mm or less Good: Average warpage amount is 10 or more and less than 15 mm Possible: Average warpage amount is 15 mm or more and less than 20 mm Poor: Average warp amount is 20 mm or more
• Pencil hardness The pencil hardness of the LR layer of the laminated member was evaluated. The measurement was performed according to JIS K5600-5-4 (1999), scratch hardness (pencil method).
• Examples 2 to 17 In the same manner as in Example 1, using the compositions prepared in the formulations shown in Tables 1A, 1B and 1C, laminated films and laminated members having the configurations shown in Tables 2A and 2B were prepared. The obtained laminated film and laminated member were evaluated in the same manner as in Example 1. The results are shown in Table 2A and Table 2B. In each of the examples, the surfaces of the obtained uncured hard coat layer and optical interference layer were tack-free.
• Example 1 An uncured HC layer was formed on the transparent support base material TB1 in the same manner as in Example 1 except that the composition HC4 was used. Next, the HC layer was irradiated with active energy rays having an integrated light intensity of 500 mJ / cm 2 , and the HC layer was cured. The composition LR3 was applied to the cured HC layer. Subsequently, the composition LR3 was dried to form an LR layer having a dry thickness of 95 nm. Finally, an active energy ray having an integrated light amount of 500 mJ / cm 2 was irradiated to obtain a precure type laminated film. Using this laminated film, a laminated member was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.
• Example 2 A laminated film and a laminated member were prepared and evaluated in the same manner as in Example 1 except that the uncured LR layer was not formed. The results are shown in Table 3.
• Example 3 A laminated film was obtained in the same manner as in Example 1 except that the composition LR4 was used instead of the composition LR1. Using this laminated film, a laminated member was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.
• TB4 was prepared in place of the transparent support base material TB1 to form an uncured hard coat layer in the same manner as in Example 1.
• the transparent support base material TB4 is too thick, the uncured hard coat layer and the uncured optical interference layer are poorly bonded, and the laminated film cannot be produced. Therefore, it was not possible to prepare and evaluate the laminated member.
• the laminated film according to this embodiment can be molded even in a complicated shape, and further suppresses the occurrence of defective products during molding. Further, the laminated member according to the present embodiment has excellent hard coat performance (for example, high hardness, abrasion resistance, chemical resistance, etc.) and excellent antireflection property.
• the laminated film of Comparative Example 1 is a precure type. Therefore, each layer is composed of a composition so that three-dimensional molding after curing is possible. Therefore, the crosslink density of the composition after curing is low, and the wear resistance and chemical resistance are inferior.
• the laminated films of Comparative Examples 2, 3, 5 and 6 have high visual reflectance and are inferior in antireflection performance.
• this laminated film is particularly preferably used for producing a protective material for a display.

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