WO2021020301A1 - 積層フィルムおよび積層部材 - Google Patents
積層フィルムおよび積層部材 Download PDFInfo
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- WO2021020301A1 WO2021020301A1 PCT/JP2020/028548 JP2020028548W WO2021020301A1 WO 2021020301 A1 WO2021020301 A1 WO 2021020301A1 JP 2020028548 W JP2020028548 W JP 2020028548W WO 2021020301 A1 WO2021020301 A1 WO 2021020301A1
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- uncured
- layer
- optical interference
- laminated film
- hard coat
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- 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
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- 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
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- 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
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- 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
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- 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
- B32B27/06—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
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- 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
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- 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
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- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- 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
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- 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
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/77—Uncured, e.g. green
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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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Abstract
Description
[1]
透明支持基材と、
前記透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、
前記未硬化のハードコート層上に形成された未硬化の光干渉層と、を有し、
前記未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含み、
前記未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含み、
前記透明支持基材の厚さは、50μm以上600μm以下であり、
前記未硬化の光干渉層側から測定した、正反射光を含む視感反射率は、0.1%以上4.0%以下であり、
160℃における延伸率は、50%以上である、積層フィルム。
[2]
前記未硬化の光干渉層の厚さは、15nm以上200nm以下である、上記[1]に記載の積層フィルム。
[3]
前記未硬化のハードコート層の厚さは、2μm以上30μm以下である、上記[1]または[2]に記載の積層フィルム。
[4]
前記未硬化の光干渉層側から、ナノインデンテーション法によって測定された硬度は、0.1GPa以上0.5GPa以下である、上記[1]~[3]のいずれかに記載の積層フィルム。
[5]
積算光量500mJ/cm2の活性エネルギー線が照射された前記積層フィルムの前記光干渉層側から、ナノインデンテーション法によって測定された硬度は、0.5GPa超1.2GPa以下である、上記[1]~[4]のいずれかに記載の積層フィルム。
[6]
前記積層フィルムに積算光量500mJ/cm2の活性エネルギー線を照射した後、垂直荷重4.9Nをかけながら前記光干渉層の表面を5000回摩擦したとき、前記光干渉層に傷が視認されない、上記[1]~[5]のいずれかに記載の積層フィルム
[7]
前記未硬化のハードコート層と前記未硬化の光干渉層との間に、さらに、少なくとも1つの未硬化の機能層を有する、上記[1]~[6]のいずれかに記載の積層フィルム
[8]
硬化された上記[1]~[7]のいずれかに記載の積層フィルムを含む、積層部材。
本実施形態に係る積層フィルムは、透明支持基材と、透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、未硬化のハードコート層上に形成された未硬化の光干渉層と、を有する。未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含む。未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含む。
積層フィルムの未硬化の光干渉層側から測定した、正反射光を含む視感反射率は、0.1%以上4.0%以下である。言い換えれば、積層フィルムの上記視感反射率の下限値が0.1%であり、上限値が4.0%である。つまり、積層フィルムは、優れた反射防止性を有する。積層フィルムを硬化して得られる積層部材もまた、優れた反射防止性を有する。よって、積層部材には外光による映り込みが少なく、積層部材は、良好な表示特性および良好な視認性を有している。積層部材の上記視感反射率もまた、0.1%以上4.0%以下であり得る。
透明支持基材の、未硬化のハードコート層とは反対側の面に、黒色塗料(例えば、品名:CZ-805 BLACK(日弘ビックス社製)を、バーコーターを用い、乾燥膜厚が3μm以上6μm以下となるように塗布する。その後、室温環境下で5時間放置して乾燥させることにより、評価サンプルMを作成する。
上記で作成された評価サンプルMに、積算光量500mJ/cm2の活性エネルギー線を照射することにより、評価サンプルNを作成する。得られた評価サンプルNの光干渉層側から、上記と同様にして視感反射率を測定する。活性エネルギー線の照射前に、積層フィルムの80℃、1時間の熱処理を行ってもよい。
積層フィルムの160℃における延伸率は、50%以上である。この場合、積層フィルムは150℃以上190℃以下の成形温度において十分に延伸する。よって、積層フィルムを、クラックを生じることなく、複雑な立体形状に賦形することができる。特に、プレフォーム工程において、積層フィルムの損傷が抑制され易くなる。そのため、ハードコート層および光干渉層の機能を備え、かつ、複雑な立体形状を有する積層部材を得ることができる。プレフォーム工程後、積層フィルムは、要求される物性、形状等に応じて、例えば、インサートモールド成形等により本成形される。
チャック間距離が150mmである引張り試験機、および、長さ200mm×幅10mmに切り出した評価サンプルを準備する。160℃雰囲気下、引張力5.0Kgf、引張速度300mm/分の条件にて、評価サンプルの長辺を50%延伸する。延伸された評価サンプルを、倍率1000倍またはそれ以上の顕微鏡を用いて観察し、長さ100μm、幅1μmを超えるクラックの有無を確認する。
透明支持基材の厚さは、50μm以上600μm以下である。これにより、積層フィルムを延伸させた場合にも、積層フィルムは剛性を保持できる。また、積層フィルムおよび積層部材の反りが抑制され易い。さらに、透明支持基材および積層フィルムをロール状に巻き取ることが可能となるため、ロールtoロール加工を行うことができる。透明支持基材の厚さは、100μm以上が好ましく、200μm以上がより好ましい。透明支持基材の厚さは、500μm以下が好ましく、480μm以下がより好ましく、450μm以下がさらに好ましく、400μm以下が特に好ましい。
積層フィルムの硬度は特に限定されない。後工程における損傷が抑制され易い点で、積層フィルムの光干渉層側から測定されたナノインデンテーション法による硬度Hbは、0.1GPa以上が好ましい。硬度Hbが0.1GPa以上であると、スキージ痕あるいは吸引痕等の不具合が抑制されて、歩留まりが向上し易くなる。
積層部材は、耐摩耗性に優れることが望ましい。例えば、積層フィルムに、活性エネルギー線を積算光量500mJ/cm2照射して、積層部材を得る。その後、垂直荷重4.9Nで光干渉層の表面を5000回摩擦する。この摩耗試験後の積層部材には傷が視認されないことが好ましい。傷が視認されないということは、外観変化による視認性低下が抑制されるということである。
透明支持基材は、透明である限り特に限定されない。これにより、積層部材に後述する加飾層が設けられた場合、意匠性がより高まる。透明であるとは、具体的には、全光線透過率が80%以上であることをいう。透明支持基材の全光線透過率は、80%以上であって、90%以上が好ましい。全光線透過率は、JIS K 7361-1に準拠する方法により測定することができる。透明支持基材としては、当分野において公知のものが、特に制限されることなく用いられる。透明支持基材は、無色であってもよく、有色であってもよい。
未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物(以下、組成物HCと称す場合がある。)を含む。組成物HCは、活性エネルギー線により硬化する。
ハードコート層は未硬化の状態で、未硬化の光干渉層と積層される。さらに、積層フィルムは、未硬化の状態で種々の加工に供される。そのため、未硬化のハードコート層には、高い硬度を有すること、低タックであって汚染され難いこと、加工の際の損傷および外観変化が抑制されること、他の層との熱収縮性の違いによるカールが抑制されること等が求められる。
組成物HCは、活性エネルギー線硬化型の樹脂成分を含む。活性エネルギー線硬化型の樹脂成分は、活性エネルギー線により架橋して硬化するモノマー、オリゴマー、あるいはポリマーを含む。
シリカ粒子(コロイダルシリカ)の市販品を以下に例示する。
日産化学工業社製 : IPA-ST、MEK-S TM、 IBK-S T 、PGMST、XBA-S T 、MEK-AC-2101、MEK-AC-2202、MEKAC-4101M I B K-SD
扶桑化学工業社製 : PL-1-IPA 、PL-1-TOL 、PL-2-IPA 、PL-2-MEK 、PL-3-TOL
日揮触媒化成社製 :OSCALシリーズ、ELECOMシリーズ
ビックケミー ジャパン社製 : NANOBYK-3605
アルミナ粒子の市販品を以下に例示する。
住友大阪セメント社製 :AS-15 0 I 、AS-150T
ビックケミー ジャパン社製 : NANOBYK-3601 、NANOBYK -3602 、NANOBYK -3610
酸化ジルコニア粒子の市販品を以下に例示する。
堺化学工業製:SZR-K、SZR-KM
CIKナノテック製:ZRANB15WT%-P02、ZRMIBK15WT%-P01、ZRMIBK15WT%-F85
ソーラー製:NANON5ZR-010、NANON5ZR-020
多官能(メタ)アクリレートモノマーまたはオリゴマーの市販品を以下に例示する。
DPHA(ダイセル オルネクス社製)、PETRA(ダイセル オルネクス社製:ペンタエリスリトールトリアクリレート)、PETIA(ダイセル オルネクス社製)、アロニックスM-403(東亞合成社製:ジペンタエリスリトールペンタおよびヘキサアクリレート)、アロニックスM-402(東亞合成社製:ジペンタエリスリトールペンタおよびヘキサアクリレート)、アロニックスM-400(東亞合成社製:ジペンタエリスリトールペンタおよびヘキサアクリレート)、SR-399(アルケマ社製:ジペンタエリスリトールヒドロキシペンタアクリレート)、KAYARAD DPHA(日本化薬社製)、KAYARAD DPHA-2C(日本化薬社製)、アロニックスM-404、M-405、M-406、M-450、M-305、M-309、M-310、M-315、M-320、TO-1200、TO-1231、TO-595、TO-756(以上、東亞合成社製)、KAYARD D-310、D-330、DPHA、DPHA-2C(以上、日本化薬社製)、ニカラックMX-302(三和ケミカル社製)
多官能ウレタン(メタ)アクリレートモノマーまたはオリゴマーの市販品を以下に例示する。
2官能ウレタン(メタ)アクリレート(日本化薬社製の「UX-2201」、「UX-8101」、「UX-6101」、共栄社化学社製の「UF-8001」、「UF-8003」、ダイセル オルネクス社製の「Ebecryl244」、「Ebecryl284」、「Ebecryl2002」、「Ebecryl4835」、「Ebecryl4883」、「Ebecryl8807」、「Ebecryl6700」)、3官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「Ebecryl254」、「Ebecryl264」、「Ebecryl265」)、4官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「Ebecryl8210」)、6官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「Ebecryl1290k」、「Ebecryl5129」、「Ebecryl220」、「KRM-8200」、「Ebecryl1290N」)、9官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「KRM-7804」)、10官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「KRM-8452」、「KRM-8509」)、15官能ウレタン(メタ)アクリレート(ダイセル オルネクス社製の「KRM-8655」)
多官能シリコン(メタ)アクリレートモノマーまたはオリゴマーの市販品を以下に例示する。
・メタクリロイル基およびアクリロイル基を有する化合物
BYK社製 : BYK-UV3500、BYK-UV3570
信越化学工業社製 : 信越シリコーン X-22-164、信越シリコーン X-22-164AS、信越シリコーン X-22-164A、信越シリコーン X-22-164B、信越シリコーン X-22-164C、信越シリコーン X-22-164E、信越シリコーン X-22-174DX、信越シリコーン X-22-2426、信越シリコーン X-22-2475、KER-4000-UV、KER-4700-UV、KER-4710-UV、KER-4800-UV
JNC社製 : FM-0711、FM-0721、FM-0725、TM-0701、FM-7711、FM-7721、FM-7725
エボニックジャパン : TEGO(登録商標) Rad 2010、TEGO(登録商標) Rad 2011
三菱ケミカル社製 : 紫光 UV-AF305
T&K TOKA社製 : ZX-212、ZX-214-A
信越化学工業社製 : KY-1203
組成物HCは、光重合開始剤を含むのが好ましい。これにより、活性エネルギー線硬化型の樹脂成分の重合が進行し易くなる。
組成物HCは、溶媒を含んでもよい。溶媒は特に限定されず、組成物に含まれる成分、透明支持基材の種類および塗布方法等を考慮して、適宜選択される。
組成物HCは、必要に応じて、種々の添加剤を含むことができる。添加剤としては、例えば、帯電防止剤、可塑剤、界面活性剤、酸化防止剤、紫外線吸収剤、表面調整剤、レベリング剤および光安定剤(例えば、ヒンダードアミン系光安定剤(HALS))が挙げられる。
未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物(以下、組成物Rと称す場合がある。)を含む。組成物Rは、活性エネルギー線により硬化する。組成物Rは、組成物HCと同種の活性エネルギー線により硬化することが好ましい。
光干渉層は未硬化の状態で、未硬化のハードコート層と積層される。さらに、上記の通り、積層フィルムは、未硬化の状態で種々の加工に供される。そのため、光干渉層には、反射防止性能に加えて、ハードコート層と同様の性能が要求される。特に、光干渉層には、優れた反射防止性能、低タックであって汚染され難いこと、加工の際の損傷、外観変化が抑制されることが求められる。加工の際の外観変化としては、例えば、保護フィルムが剥離される際に生じるジッピング痕と呼ばれるスジが挙げられる。
組成物Rは、活性エネルギー線硬化型の樹脂成分を含む。活性エネルギー線硬化型の樹脂成分は、活性エネルギー線により架橋して硬化するモノマー、オリゴマー、あるいはポリマー(反応性樹脂)を含む。組成物Rに含まれる活性エネルギー線硬化型の樹脂成分としては、上記の組成物HCに含まれる活性エネルギー線硬化型の樹脂成分と同様のものが例示できる。
無機酸化物微粒子としては、上記の組成物HCに含まれる無機酸化物微粒子と同様のものが例示できる。
DIC社製 : メガファックRS-72-K、メガファックRS-75、メガファックRS-76-E、メガファックRS-76-NS、メガファックRS-77
ダイキン工業社製 : オプツール DAC-HP
ソルベイソレクシス社製 : FLUOROLINK MD700、FLUOROLINK AD1700
ネオス社製 : フタージェント601ADH2
組成物Rは、光重合開始剤を含むのが好ましい。これにより、活性エネルギー線硬化型の樹脂成分の重合が進行し易くなる。光重合開始剤の例として、例えば、上記組成物HCに関して例示したものを選択できる。
組成物Rは、溶媒を含んでもよい。溶媒は特に限定されず、組成物に含まれる成分、透明支持基材の種類および塗布方法等を考慮して、適宜選択される。溶媒としては、上記組成物HCに関して例示したものを選択できる。なかでも、エステル系溶媒、エーテル系溶媒、アルコール系溶媒およびケトン系溶媒が好ましい。
低屈折率層を形成する組成物Rは、硬化された光干渉層の屈折率を低下させる屈折率低下成分を含むことが好ましい。屈折率低下成分は、例えば粒子状である(以下、屈折率低下粒子と称する場合がある。)。
積層フィルムは、未硬化のハードコート層と、未硬化の光干渉層との間に、さらに、少なくとも1つの未硬化の機能層を有していてもよい。機能層により、積層フィルムの光学的機能が補強されたり、新たな光学的機能が付与されたりする。
積層フィルムは、未硬化の光干渉層の、未硬化のハードコート層とは反対側の面に、保護フィルムを有していてもよい。
本実施形態に係る積層部材は、上記の積層フィルムが硬化されることにより得られる。積層部材は、積層フィルムの完全硬化物である。積層部材は、透明支持基材と、硬化されたハードコート層と、硬化された光干渉層と、をこの順で有する。積層部材は、硬化されたハードコート層と硬化された光干渉層との間に、さらに、少なくとも1つの硬化された機能層を有していてもよい。積層部材は、さらに、保護フィルムを有していてもよいし、有していなくてもよい。保護フィルムは、使用目的に応じて、使用される。
積層部材は、さらに加飾層を備えていてもよい。積層部材は、例えば、透明支持基材と、透明支持基材の一方の主面に配置されたハードコート層および光干渉層と、透明支持基材の他方の主面に配置された加飾層と、を備える。加飾層は、透明支持基材の他方の主面の一部に設けられてもよい。加飾層は、模様、文字または金属光沢等の装飾を積層部材に与える層である。加飾層により、積層部材の意匠性が高まる。
積層部材は、さらに成形樹脂層を備えていてもよい。成形樹脂層は、透明支持基材とともにハードコート層および光干渉層を支持する。積層部材は、例えば、透明支持基材と、透明支持基材の一方の主面に配置されたハードコート層および光干渉層と、透明支持基材の他方の主面に配置された成形樹脂層と、を備える。成形樹脂層の形状は制限されない。そのため、積層部材のデザインの自由度が高まる。
本実施形態に係る積層部材は、例えば、上記の積層フィルムを準備する工程と、積層フィルムに、活性エネルギー線を照射する工程と、を含む方法により製造される。積層フィルムを準備する工程の後、必要に応じて、加飾工程、プレフォーム工程、本成形工程が行われる。加飾工程は、プレフォーム工程の前に行われることが好ましい。
積層フィルムを準備する。積層フィルムは、透明支持基材と、透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、未硬化のハードコート層上に形成された未硬化の光干渉層と、を有する。
未硬化のハードコート層を形成する方法は特に限定されない。未硬化のハードコート層は、透明支持基材の少なくとも一方の面上に、例えば、組成物HCを塗布することにより形成される。塗布後、乾燥工程を行ってもよい。乾燥条件は特に限定されず、組成物HCに含まれる溶剤の少なくとも一部が除去されるように、適宜設定される。
未硬化のハードコート層と未硬化の光干渉層とを積層する方法は特に限定されず、コーティング法であってよく、ラミネート法であってよい。
他の機能層は、例えば、以下の工程により貼り合わされる。上記のラミネート工程により得られた、透明支持基材と、未硬化のハードコート層と、未硬化の光干渉層(第1の光干渉層)と、他の支持基材とをこの順に含む積層物から、他の支持基材を剥離して、未硬化の光干渉層を露出させる。別途、他の未硬化の機能層を、新たな支持基材上に形成する。次いで、露出した未硬化の光干渉層に、新たな支持基材で支持された未硬化の機能層を貼り合わせる。必要に応じて、これらの工程を繰り返してもよい。
ハードコート層が透明支持基材の一方の主面に配置されている場合、形成工程の前に、透明支持基材の他方の主面に、上記の加飾層を形成してもよい。加飾工程は、準備工程の前に行われてもよいし、準備工程の後に行われてもよい。生産性の観点から、加飾工程は、準備工程の後に行われることが望ましい。
立体形状を有する積層部材を製造する場合、準備工程(さらには加飾工程)の後、本成形工程の前に、積層フィルムを所望の立体形状に沿った形状に成型してもよい。積層フィルムを、予め立体形状に近い形状に成型することにより、その後、立体形状に成型する際にクラックおよびシワ等が発生することがさらに抑制され易くなる。プレフォーム工程の後、積層フィルムの不要な部分を除去するトリミング工程を行ってもよい。
本成形工程の前に、積層フィルムの一部が硬化するように、活性エネルギー線を照射してもよい。これにより、半硬化状態の積層フィルムが得られる。
本成形工程では、例えば、インサートモールド成形が行われる。インサートモールド法では、例えば、金型に光干渉層を対向させるとともに、透明支持基材に向かって成形用樹脂が射出される。これにより、積層フィルムが立体形状に賦形されるとともに、透明支持基材の他方の主面に成形樹脂層が形成される。
積層フィルムに活性エネルギー線を照射して、積層フィルムを完全硬化させる。これにより、積層部材が得られる。活性エネルギー線の積算光量は、例えば、100mJ/cm2以上である。活性エネルギー線の積算光量は、5000mJ/cm2以下であってよく、3000mJ/cm2以下であってよい。活性エネルギー線は、半硬化工程と同種であってよく、異なっていてもよい。
(反応性アクリル樹脂)
(1)品名:KRM-9322、ダイセルオレネクス社製、Tg:60℃、Mw:50,000
(2)品名:WEL-355、DIC社製、Tg:85℃、Mw:45,000
品名 :KRM-8452、ダイセル オルネクス社製、Mw:3884、アクリレート当量 :120g/eq
品名 :紫光 UV-AF305、三菱ケミカル社製、Mw:18000
品名:H-7M40、根上工業社製、Mw:10000~15000
品名:CN-9893、アルケマ社製
品名:アロニックスM-315、東亞合成社製、Mw:450、アクリレート当量 :150g/eq
品名:スルーリア4320、日揮触媒社製、中空状シリカ微粒子
(1)品名:OSCAL 1842、日揮触媒化成工業社製、粒子径10nm、反応性シリカオルガノゾル
(2)品名:HX-204 IP、日産化学社製、リンドープ酸化スズゾル、粒子径5nmから20nm
品名:Omnirad 184、IGM RESINS社製、α-ヒドロキシアルキルフェノン
TB1-TB4:品名 AW-10U、ウェーブロック・アドバンスト・テクノロジー社製、PMMAおよびPCからなる2層(PMMA/PC)フィルム、TB1:厚さ300μm、TB2:厚さ200μm、TB3:厚さ500μm、TB4:厚さ800μm、TB5:厚さ100μm
品名:トレファン#40-2500、東レ社製、二軸延伸ポリプロピレンフィルム(OPP)、厚さ40μm
メチルイソブチルケトン185部を含む容器に、KRM-9322(反応性アクリル樹脂)47.6質量部、KRM-8452(多官能ウレタンアクリレートオリゴマー)33.3質量部、OSCAL 1842(無機酸化物微粒子)14.3質量部、および、Omnirad184(光重合開始)4.8質量部を混合して、固形分濃度35%の、透明な組成物HC1を調整した。
表1Cに示す配合にしたこと以外は、組成物HC1と同様にして、固形分濃度35%の、透明な組成物HC2-HC6を調整した。
プロピレングリコールモノメチルエーテル1203部を含む容器に、KRM-9322(反応性アクリル樹脂)24.8質量部、KRM-8452(多官能ウレタンアクリレートオリゴマー)13.3質量部、紫光 UV-AF305(フッ素原子を含む多官能シリコンアクリレートオリゴマー)13.3質量部、および、Omnirad184(光重合開始)4.8質量部を混合した。さらに、スルーリア4320(屈折率低下成分)43.8質量部を配合した。これにより、樹脂固形分濃度3.0%の、透明な組成物LR1を調整した。
表1Aに示す配合にしたこと以外は、組成物LR1と同様にして、固形分濃度35%の、透明な組成物LR2-LR5を調整した。
表1Bに示す配合にしたこと以外は、組成物LR1と同様にして、固形分濃度35%の、透明な他の機能層形成組成物HR1、MR1を調整した。
(1)積層フィルムの製造
(1-1)未硬化のハードコート層の形成
透明支持基材TB1のPMMAの面に、グラビアコーターにより、組成物HC1を乾燥後の厚さが8μmになるよう塗布した。その後、80℃で1分間乾燥させて溶媒を揮発させて、未硬化のハードコート層を形成した。
以下、ハードコート層を「HC層」と表記する場合がある。
OPPフィルム(保護フィルム)に、組成物LR1を、グラビアコーターにより、乾燥後の厚さが95nmになるよう塗布した。その後、80℃で1分間乾燥させて溶媒を揮発させて、未硬化の光干渉層を形成した。得られた未硬化の光干渉層の表面もタックフリーであった。未硬化の光干渉層が形成された保護フィルムを、ロール状に巻き取った。
以下、低屈折率を有する組成物LR1により形成された光干渉層を「LR層」と表記する場合がある。
ロール状に巻き取られた保護フィルムを巻き出しながら、透明支持基材TB1で支持された未硬化のHC層表面と、保護フィルムで支持された未硬化のLR表面とを貼り合わせた。これにより、透明支持基材と、未硬化のHC層と、未硬化のLR層と、保護フィルムと、をこの順で有する積層フィルムを製造した。
(2-1)印刷層の形成
積層フィルムの透明支持基材の、未硬化のHC層とは反対側の面に、スクリーン印刷により印刷層を形成し、乾燥温度80℃で10分間乾燥させた。この印刷工程を5回繰り返し、その後、90℃で1時間乾燥させた。印刷層の形成には、黒色塗料(品名:CZ-805 BLACK(日弘ビックス社製)を用いた。
次いで、保護フィルムを未硬化のLR層から5.0mm/秒の速度で剥離した。
印刷層を備える積層フィルムを190℃で30秒間加熱し、真空圧空成型法によりプレフォームを実施した。
プレフォームされた積層フィルムに、積算光量500mJ/cm2の活性エネルギー線を照射した。続いて、トリミングを実施した。
最後に、射出成形を行って、透明支持基材の印刷層側に成形樹脂層(ポリカーボネート)を備える積層部材を得た。なお、実施例において、特に言及のない限り、活性エネルギー線として、紫外線を使用している。
積層フィルムおよび積層部材に対して、以下の評価を行った。
(a)屈折率
組成物LR1からLR5、組成物HR1およびMR1を、乾燥厚さが5μmになるようにそれぞれ保護フィルム上に塗布した。続いて、塗膜に積算光量500mJ/cm2の活性エネルギー線を照射して、評価サンプルとした。アタゴ社製のアッペ屈折計DR-M2を用い、D線589nmでの評価サンプルの屈折率を測定した。評価サンプルはプリズム面の上にセットし、中間液は1-ブロモナフタレンを使用した。
積層部材から、10mm×10mmの評価サンプルを切り出した。評価サンプルの断面を、ミクロト-ム(LEICA RM2265)にて析出させた。析出させた断面を、レーザー顕微鏡(VK8700、KEYENCE社製)または透過型電子顕微鏡(JEM2100、日本電子社製)にて観察し、HC層およびLR層の各10点の厚みを測定した。その平均値をそれぞれ、HC層およびLR層の厚さとした。
積層フィルムの透明支持基材における、未硬化のHC層とは反対側の面に対し、黒色塗料(品名:CZ-805 BLACK(日弘ビックス社製)を、バーコーターを用い、乾燥膜厚が3μm以上6μm以下となるように塗布した。次いで、黒色塗料を塗布した積層フィルムを、室温環境下で5時間放置し、乾燥を行うことにより、未硬化の評価サンプルを作製した。
積層フィルムから長さ200mm×幅10mmの試験片を切り出した。この試験片を、チャック間距離が150mmである引張り試験機にセットして、160℃雰囲気下、引張力5.0Kgf、引張速度300mm/分の条件にて、評価サンプルの長辺を50%延伸した。延伸後の評価サンプルを、倍率1000倍またはそれ以上の顕微鏡を用いて観察し、長さ100μm、幅1μmを超える大きさのクラックの有無を確認した。
積層フィルムの未硬化のLR層側と、積層部材のLR層側とから、それぞれ硬度を測定した。
硬度は、NANOMECHANICS,INC.製のiMicro Nanoindenterを用いて、連続剛性測定法(使用メソッド:Advanced Dynamic E and H.NMT)により測定した。
プレフォームした積層フィルムに積算光量500mJ/cm2の活性エネルギー線を照射して評価サンプルとした。評価サンプルを射出成型の金型にセットする際のハンドリング性を評価した。
評価基準は以下のとおりである。
良:評価サンプルにコシがあり、射出成型の金型に容易に設置できる
可:評価サンプルのコシが弱く、取り扱いに若干の難があるが、金型に設置できる
不良:評価サンプルのコシが弱く、金型に設置できない。
積層フィルムから、200mm×200mmの評価サンプルを切り出し、積算光量500mJ/cm2の活性エネルギー線を照射した。次いで、評価サンプルを水平面に載置して、その四隅の水平面からの浮き上がり量(反り量)を定規を用いて計測し、平均化した。
評価基準は以下のとおりである。
最良:反り量の平均が10mm以下
良:反り量の平均が10以上15mm未満
可:反り量の平均が15mm以上20mm未満
不良:反り量の平均が20mm以上
保護フィルムの剥離(2-2)後、プレフォーム(2-3)前の積層フィルムを評価サンプルとした。評価サンプルの印刷工程に起因するスキージ痕および吸引痕の有無を、目視により確認した。
評価基準は、以下のとおりである。
最良:スキージ痕および吸引痕無し
良:スキージ痕および吸引痕が僅かにあるが、90℃以上に加熱することでレベリングし、消失する
可:スキージ痕および吸引痕が僅かにあるが、150℃以上に加熱することでレベリングし、消失する
不良:スキージ痕および吸引痕有り
透明支持基材と未硬化のハードコート層との積層フィルムと、保護フィルムと未硬化の光干渉層との積層フィルムとを、各層が対向するようにハンドローラーで押し付けながら貼り合わせて、貼り付きの程度を評価した。
評価基準は、以下のとおりである。
良:フィルム同士が貼り付いている
可:フィルム同士が貼り付いているが、密着が弱い
不良:フィルム同士が全く貼り付いていない
積層部材のLR層の鉛筆硬度を評価した。
測定は、JIS K5600-5-4(1999)、ひっかき硬度(鉛筆法)に従って行った。
積層部材のLR層の表面を、垂直荷重4.9Nをかけながら、綿布を固定した摩擦子により5000回摩擦した。積層部材のLR層の表面を目視により観察した。続けて、積算回数が7000回になるまで積層部材のLR層の表面を摩擦した。積層部材のLR層の表面を目視により観察した。評価基準は次のとおりである。
最良:7000回の摩擦後にも傷は視認されなかった
良:5000回の摩擦後に傷は視認されなかったが、7000回の摩擦後に傷が視認された
可:5000回の摩擦後、5本以下の傷が視認された
不良:5000回の摩擦後、傷が多数視認された
積層部材から、10cm×10cmの評価サンプルを切り出した。評価サンプルのLR層の一面全体に、ニュートロジーナ サンスクリーンSPF45(ジョンソン&ジョンソン社製)2gを、指で均一になるように塗布した。次いで、80℃×4時間加温した。その後、室温まで冷却し、水洗いを行って、LR層の外観を目視で評価した。
評価基準は以下のとおりである。
最良:外観異常無し
良:塗布した痕が確認できるがリフティングは確認されない
可:軽度のリフティングが確認される
不良:重度のリフティングが発生している
実施例1と同様にして、表1A、表1Bおよび表1Cに示す配合で調製された組成物を用いて、表2Aおよび表2Bに示す構成を有する積層フィルムおよび積層部材を作成した。得られた積層フィルムおよび積層部材を、実施例1と同様にして評価した。結果を表2Aおよび表2Bに示す。なお、いずれの実施例においても、得られた未硬化のハードコート層および光干渉層の表面はタックフリーであった。
組成物HC4を用いたこと以外は実施例1と同様にして、未硬化のHC層を透明支持基材TB1上に形成した。次いで、HC層に積算光量500mJ/cm2の活性エネルギー線を照射し、HC層を硬化させた。
硬化されたHC層に組成物LR3を塗布した。続いて、組成物LR3を乾燥させて、乾燥厚さ95nmのLR層を形成した。最後に、積算光量500mJ/cm2の活性エネルギー線を照射して、プレキュア型の積層フィルムを得た。この積層フィルムを用いて、実施例1と同様にして積層部材を作成し、評価した。結果を表3に示す。
未硬化のLR層を形成しなかったこと以外は、実施例1と同様にして、積層フィルムおよび積層部材を作成し、評価した。結果を表3に示す。
組成物LR1に替えて組成物LR4を用いたこと以外は、実施例1と同様にして、積層フィルムを得た。この積層フィルムを用いて、実施例1と同様にして積層部材を作成し、評価した。結果を表3に示す。
透明支持基材TB1に替えてTB4を準備し、実施例1と同様にして、未硬化のハードコート層を形成した。しかし、透明支持基材TB4が厚すぎるため、未硬化のハードコート層と未硬化の光干渉層の貼り合わせが不良となり、積層フィルムを作成できなかった。そのため、積層部材の作成および評価ができなかった。
未硬化の光干渉層の厚さを変えたこと以外は、実施例1と同様にして、積層フィルムおよび積層部材を作成し、評価した。結果を表3に示す。
Claims (8)
- 透明支持基材と、
前記透明支持基材の少なくとも一方の面上に形成された未硬化のハードコート層と、
前記未硬化のハードコート層上に形成された未硬化の光干渉層と、を有し、
前記未硬化のハードコート層は、活性エネルギー線硬化型のハードコート層形成組成物を含み、
前記未硬化の光干渉層は、活性エネルギー線硬化型の光干渉層形成組成物を含み、
前記透明支持基材の厚さは、50μm以上600μm以下であり、
前記未硬化の光干渉層側から測定した、正反射光を含む視感反射率は、0.1%以上4.0%以下であり、
160℃における延伸率は、50%以上である、積層フィルム。 - 前記未硬化の光干渉層の厚さは、15nm以上200nm以下である、請求項1に記載の積層フィルム。
- 前記未硬化のハードコート層の厚さは、2μm以上30μm以下である、請求項1または2に記載の積層フィルム。
- 前記未硬化の光干渉層側から、ナノインデンテーション法によって測定された硬度は、0.1GPa以上0.5GPa以下である、請求項1から3のいずれか1項に記載の積層フィルム。
- 積算光量500mJ/cm2の活性エネルギー線が照射された前記積層フィルムの前記光干渉層側から、ナノインデンテーション法によって測定された硬度は、0.5GPa超1.2GPa以下である、請求項1から4のいずれか1項に記載の積層フィルム。
- 前記積層フィルムに積算光量500mJ/cm2の活性エネルギー線を照射した後、垂直荷重4.9Nをかけながら前記光干渉層の表面を5000回摩擦したとき、前記光干渉層に傷が視認されない、請求項1から5のいずれか1項に記載の積層フィルム。
- 前記未硬化のハードコート層と前記未硬化の光干渉層との間に、さらに、少なくとも1つの未硬化の機能層を有する、請求項1から6のいずれか1項に記載の積層フィルム。
- 硬化された請求項1から7のいずれか1項に記載の積層フィルムを含む、積層部材。
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