CN109073789A - Hard coat film - Google Patents
Hard coat film Download PDFInfo
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- CN109073789A CN109073789A CN201680085288.4A CN201680085288A CN109073789A CN 109073789 A CN109073789 A CN 109073789A CN 201680085288 A CN201680085288 A CN 201680085288A CN 109073789 A CN109073789 A CN 109073789A
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- hard conating
- hard
- coat film
- 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
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Liquid Crystal (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of hard coat film (1), it has base material film (2), it is layered in the first hard conating (3) of at least one main surface side of base material film (2), and it is layered in the second hard conating (4) of the main surface side opposite with base material film (2) side of the first hard conating (3), base material film (2) is polyimide film, first hard conating (3) and the second hard conating (4) are made of material different from each other, the refractive index of first hard conating (3) and the specific refractivity of the second hard conating (4) are calculated as 0.04 or less with absolute value, the thickness of the thickness and the second hard conating (4) of first hard conating (3) adds up to 7 μm or more, 35 μm or less.The hard coat film (1) has the resistance to bend(ing) for standing repeated flex, while warpage being less likely to occur, and then do not allow to be also easy to produce interference fringe.
Description
Technical field
The present invention relates to a kind of hard coat films for having base material film and hard conating, are suitble to be used in flexibility more particularly to one kind
The hard coat film of display.
Background technique
In various e-machines, widely using have liquid crystal display (LCD), organic el display (OELD) so touching
Control the various displays such as panel.It damages in order to prevent, the surface of these various displays is provided with mostly to be arranged on base material film
There is the hard coat film of hard conating.
However, in recent years, as display as described above, flexible display, i.e. so-called soft is being developed
Property display.The extensive use of flexible display expected, such as the peace of cylindric pillar is arranged in as it is bent
Escope is set to use or as bending or round and the Leading format device that can carry is used.As flexible display with firmly
Film proposes the hard coat film disclosed in patent document 1 and 2.
Herein, flexible display does not instead of only carry out 1 curved surface forming sometimes, as documented by patent document 3
It carries out repeated flex (bending).
Existing technical literature
Patent document
Patent document 1: No. 5468167 bulletins of Japanese Patent Publication No.
Patent document 2: Japanese Unexamined Patent Publication 2015-69197 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2016-2764 bulletin
Summary of the invention
The technical problem to be solved in the present invention
However, can generate makes its repetition if existing hard coat film to be used for the flexible display of purposes as described above
Curved part, which leads to the problem of bending trace or albefaction, causes appearance to be deteriorated while reducing as the visual of display.
In addition, when pursuit stands the resistance to bend(ing) of repeated flex as described above, according to the type of the base material film used
Become problem Deng, optical characteristics such as the colorings such as yellowing or the transparency.Moreover, reducing the film of base material film in order to improve this problem
When thick, the ratio that hard conating accounts for hard coat film entirety becomes larger relatively, leads to the problem of when forming hard coat film and warpage occurs.
On the other hand, interference fringe is generated in hard coat film because of various major reasons sometimes.If being generated in hard coat film
Interference fringe then still leads to the problem of appearance and is deteriorated and reduces as the visual of display.
The present invention in view of such actual situation completes, and its purpose is to provide a kind of with standing repeated flex
Resistance to bend(ing) is not susceptible to warpage and is not likely to produce the hard coat film of interference fringe simultaneously.
Solve the technological means of technical problem
In order to achieve the above objectives, first, the present invention provides a kind of hard coat film, has base material film, is layered in the base
First hard conating of at least one main surface side of material film and it is layered in the opposite with the base material film side of first hard conating
Second hard conating of main surface side, which is characterized in that the base material film is polyimide film, first hard conating and described second
Hard conating is formed by material different from each other, the specific refractivity of the refractive index of first hard conating and second hard conating
With absolute value be calculated as 0.04 hereinafter, first hard conating thickness and second hard conating thickness add up to 7 μm with
Above, 35 μm or less (invention 1).
The hard coat film of foregoing invention (invention 1), by making base material film polyimide film, while making the thickness of the first hard conating
Degree and the second hard conating thickness it is total within the above range, resistance to bend(ing) is excellent.In addition, the folding by making the first hard conating
It penetrates the specific refractivity of rate and the second hard conating within the above range, while making the thickness and the second hard conating of the first hard conating
Thickness adds up to above range, which does not allow to be also easy to produce interference fringe.Further, by making the first hard conating and second
Hard conating is formed by material different from each other, while making being aggregated in for the thickness of the first hard conating and the thickness of the second hard conating
It states in range, which warpage and excellent scratch resistance are less likely to occur.
In foregoing invention (invention 1), preferably described first hard conating and second hard conating are by making containing active-energy
Material made of the composition solidification of ray-curable ingredient is formed, and first hard conating is by more soft than second hard conating
Material form (invention 2).
In foregoing invention (invention 1,2), preferably: first hard conating material as made of solidifying composition is formed,
The composition contains the active energy ray-curable ingredient modified through alkylene oxide (alkylene oxide)；Described second hard painting
Layer material as made of solidifying composition is formed, and the composition contains the active energy ray-curable modified without alkylene oxide
Ingredient (invention 3).
In foregoing invention (invention 2,3), the preferably described active energy ray-curable ingredient is multi-functional (methyl) third
Olefin(e) acid esters monomer (invention 4).
In foregoing invention (invention 1~4), the refractive index of preferably described first hard conating is 1.40 or more, 1.80 or less (hairs
It is bright 5).
In foregoing invention (invention 1~5), the refractive index of preferably described second hard conating is 1.40 or more, 1.80 or less (hairs
It is bright 6).
In foregoing invention (invention 1~6), preferably described first hard conating with a thickness of 3 μm or more, 30 μm or less (inventing 7).
In foregoing invention (invention 1~7), preferably described second hard conating (is sent out with a thickness of 0.75 μm or more, 10 μm or less
It is bright 8).
In foregoing invention (invention 1~8), the preferably described polyimide film with a thickness of 5 μm or more, 300 μm or less (inventing 9).
It is preferred that the hard coat film of foregoing invention (invention 1~9) is used as constituting the flexible member (invention 10) of flexible display
In foregoing invention (invention 1~10), sticker preferably is laminated at least one main surface side of the base material film
Layer (invention 11).
Invention effect
The excellent scratch resistance of hard coat film of the invention, with standing the resistance to bend(ing) of repeated flex, while being not easy to send out
It gives birth to warpage and is not likely to produce interference fringe.
Detailed description of the invention
Fig. 1 is the sectional view of the hard coat film of an embodiment of the invention.
Fig. 2 is the sectional view of the hard coat film of another embodiment of the present invention.
Specific embodiment
Hereinafter, embodiments of the present invention will be described.
Fig. 1 is the sectional view of the hard coat film of an embodiment of the invention.The hard coat film 1 of present embodiment has substrate
Film 2, be layered in base material film at least one main surface side (upside in Fig. 1) the first hard conating 3 and be layered in the first hard conating
Second hard conating 4 of 3 main surface side (upside in Fig. 1) opposite with 2 side of base material film and constitute.In addition, the first hard conating 3 and
Second hard conating 4 is formed by material different from each other.
In above-mentioned hard coat film 1, base material film 2 is polyimide film.By making 2 polyimide film of base material film, by the hard painting
Film 1 be applied to flexible display and when carrying out repeated flex, be able to suppress generated on base material film 2 bending trace or albefaction and
Resistance to bend(ing) is excellent.Thus, repeated flex is carried out in defined part using the flexible display of the hard coat film 1 of present embodiment
When, the appearance for being able to suppress the bending part is deteriorated or visual reduction.
In addition, the specific refractivity of the refractive index of the first hard conating 3 and the second hard conating 4 with absolute value be calculated as 0.04 with
Under, the thickness of the thickness of the first hard conating 3 and the second hard conating 4 adds up to 7 μm or more, 35 μm or less.It is first hard by making
The specific refractivity of the refractive index of coating 3 and the second hard conating 4 is calculated as 0.04 hereinafter, to be able to suppress light hard first with absolute value
The interface of coating 3 and the second hard conating 4 generates reflection, it is not easy to generate interference with the reflected light on the surface of the second hard conating 4.This
Outside, 7 μm or more are added up to by make the thickness of the first hard conating 3 and the thickness of the second hard conating 4, the thickness is compared to light
Wavelength it is considerably big, be not easy the surface with the second hard conating 4 in the light that the interface of the first hard conating 3 and base material film 2 is reflected
Reflected light generate interference.Moreover, because the intensity in the first hard conating 3 and the light of the interface reflection of base material film 2 (reflects strong
Degree) it dies down when through the first hard conating 3 and the second hard conating 4, therefore be not easy to generate and the second hard conating 4 from the side
The interference of the reflected light on surface.It is acted on by these, the generation of interference fringe is able to suppress in hard coat film 1.In addition, this is said
The measurement wavelength of refractive index in bright book is set as 589nm, measuring temperature is set as 25 DEG C.The measuring method of detailed refractive index is as after
Shown in the test example stated.
From the angle for the generation for inhibiting interference fringe, the refraction of the refractive index of the first hard conating 3 and the second hard conating 4
The difference of rate is preferably 0.02 in terms of absolute value hereinafter, particularly preferably 0.01 or less.
In addition, 7 μm or more are added up to by make the thickness of the first hard conating 3 and the thickness of the second hard conating 4, hard coat film
1 marresistance also becomes excellent.From inhibit interference fringe generation and marresistance angle, the first hard conating 3
Total preferably 9 μm or more of the thickness of thickness and the second hard conating 4, particularly preferably 10m or more.
On the other hand, by make the thickness of the first hard conating 3 and the thickness of the second hard conating 4 add up to 35 μm hereinafter,
Hard coat film 1 becomes easy bending, and resistance to bend(ing) becomes excellent.From the angle, the thickness of the first hard conating 3 and the second hard painting
Total preferably 30 μm of the thickness of layer 4 are hereinafter, particularly preferably 25 μm or less.
In addition, by make the thickness of the first hard conating 3 and the thickness of the second hard conating 4 it is total within the above range, and
It forms the first hard conating 3 and the second hard conating 4 by material different from each other, especially makes the first hard conating 3 by harder than second
The soft material of coating 4 is formed, and does not allow that warpage occurs when manufacturing the hard coat film 1.
(1) member of formation of hard coat film
(1-1) base material film
The base material film 2 of the hard coat film 1 of present embodiment is polyimide film, in the case where being used for display, preferably clear
And the polyimide film that yellowing is few.Thereby, it is possible to obtain the display for the image that display is clear and color reprodubility is high (especially
Flexible display).
Specifically, as polyimide film used in present embodiment, from the angle of the transparency, wavelength
Transmitance at 550nm is preferably 75% or more, and more preferably 80% or more, particularly preferably 85% or more.In this specification
Transmitance measuring method embodiment as be described hereinafter shown in.
In addition, as polyimide film used in present embodiment, from the angle for reducing yellowing, based on through survey
The absolute value for determining the b* of the L*a*b* color specification system of method is preferably 10 hereinafter, more preferably 5 hereinafter, particularly preferably 3 or less.This theory
Shown in the measuring method of b* in bright book embodiment as be described hereinafter.
Polyimide film in this specification refer to preferably comprise 50 mass % or more, particularly preferably containing 80 mass % with
The upper, polyimides of further preferably 90 mass % or more, have on main chain imide bond polymer film.Separately
Outside, do not have imide bond on main chain due to poly- (methyl) acrylimide, be not polyimides, if making such poly-
(methyl) acrylimide film repeated flex, then can generate albefaction.
Polyimide film usually can be obtained by following manner, and but not limited to this: keep tetracarboxylic anhydride (preferably fragrant
Fragrant race tetracarboxylic dianhydride) polymerize in the solution with diamines (preferably aromatic diamine) and generate polyamic acid after, by the polyamides
Amino acid be shaped to it is membranaceous, then to polyamic acid position carry out dehydration closed-loop.
Polyimides in polyimide film can also be modified.For example, the aromatic rings usually contained in polyimides can quilt
Aliphatic hydrocarbon is modified, and base material film 2 and the adherence of the second hard conating 4 become excellent as a result,.
The lower limit value of the refractive index of polyimide film is usually 1.50 or more, and preferably 1.55 or more, further preferably
More than 1.60.In addition, the upper limit value of the refractive index of polyimide film be usually 1.85 hereinafter, preferably 1.80 hereinafter, further
Preferably 1.75 or less.
In above-mentioned polyimide film, for layer (the second hard conating 4 or the aftermentioned sticker for being promoted with its surface being arranged in
Layer etc.) adherence purpose, can utilize prime treatment, oxidizing process, further provided for contouring method etc. real to one or both sides as needed
Apply surface treatment.As oxidizing process, for example, can enumerate Corona discharge Treatment, chromic acid processing, flame treatment, hot wind processing, it is smelly
Oxygen UV treatment etc., as further provided for contouring method, such as blasting process, solvent treatment method can be enumerated etc..
The lower limit value of the thickness of above-mentioned polyimide film is preferably 5 μm or more, and particularly preferably 7.5 μm or more, further
Preferably 10 μm or more.By make polyimide film with a thickness of more than above-mentioned, hard coat film 1 plays defined mechanical strength, i.e.,
Just make also to be not easy to produce fracture when its repeated flex.On the other hand, the upper limit value of the thickness of above-mentioned polyimide film is preferred
For 300 μm hereinafter, particularly preferably 90 μm hereinafter, further preferably 50 μm hereinafter, most preferably 30 μm or less.Due to polyamides
Imines film is easy coloring, thus by make polyimide film with a thickness of above-mentioned following, it can be ensured that the transparency and can will be upper
State b* value be suppressed to it is lower, can be suitable for optics use.In addition, if polyimide film with a thickness of it is above-mentioned hereinafter, if hard coat film 1
Defined flexibility can be played and be easy to make its bending.
(1-2) first hard conating
The main surface side that first hard conating 3 of the hard coat film 1 of present embodiment is layered in base material film 2 is (upper in Fig. 1
Side), as described above, playing the effect and marresistance for inhibiting the generation of interference fringe jointly with the second hard conating 4.
As long as with the refringence of the refractive index of the second hard conating 4 within the above range and with the second hard conating 4 hair jointly
Required marresistance is waved, then the material of the first hard conating 3 is not particularly limited.First hard conating 3 is preferably by making containing work
Property energy ray-curable ingredient composition solidification made of material formed, particularly preferably by more soft than the second hard conating 4
Material is formed.Specifically, it is preferable that the material as made of solidifying composition is formed, the composition contains modified through alkylene oxide
Active energy ray-curable ingredient.By constituting the first hard conating 3 by the material more soft than the second hard conating 4, thus bending resistance
Song becomes excellent.Moreover, the cure shrinkage of the first hard conating 3 becomes smaller, even if the first hard conating 3 and the second hard conating 4
Aggregate thickness is thicker, is also able to suppress and warpage occurs when manufacturing hard coat film 1.
(1-2-1) active energy ray-curable ingredient
As active energy ray-curable ingredient, multi-functional (methyl) acrylic ester monomer, (first can be enumerated
Base) esters of acrylic acid prepolymer, active energy ray-curable polymer etc., wherein preferred multi-functional (methyl) acrylic acid
Esters monomer and/or (methyl) esters of acrylic acid prepolymer, more preferable multi-functional (methyl) acrylic ester monomer.It is multifunctional
Property (methyl) acrylic ester monomer and (methyl) esters of acrylic acid prepolymer can respectively be used alone, and also can be used simultaneously two
Person.In addition, (methyl) acrylate refers to both acrylate and methacrylate in this specification.Other similar use
Language is also the same.
As multi-functional (methyl) acrylic ester monomer, such as 1,4-butanediol two (methyl) acrylic acid can be enumerated
Ester, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid
Ester, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (methyl) dicyclopentanyl acrylates, two (first of caprolactone modification
Base) acrylic acid dicyclopentenyl ester, di(2-ethylhexyl)phosphate (methyl) acrylate, allylation two (methyl) cyclohexyl acrylate, two (first
Base) acrylic acid isocyanuric acid ester, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate,
Propionic acid is modified dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (acryloxy second
Base) isocyanuric acid ester, the modified dipentaerythritol five (methyl) acrylate of propionic acid, dipentaerythritol six (methyl) acrylate,
Dipentaerythritol four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate and their alkylene oxide
Multi-functional (methyl) acrylate such as modifier.They can be used alone one kind, also can be used in combination two or more.
Among above-mentioned, from the resistance to bend(ing) of obtained hard coat film and the angle of inhibition warpage, preferably change through alkylene oxide
The multifunctional (methyl) acrylate class monomer of property.For example, specifically, preferably enumerating the modified trihydroxy methyl third of alkylene oxide
The modified dipentaerythritol six (methyl) acrylate of alkane three (methyl) acrylate, alkylene oxide and the modified dipentaerythritol of alkylene oxide
Four (methyl) acrylate particularly preferably enumerate ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy
Propane be modified trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified dipentaerythritol six (methyl) acrylate,
Epoxy pronane modification dipentaerythritol six (methyl) acrylate, ethylene-oxide-modified dipentaerythritol four (methyl) acrylate
And epoxy pronane modification dipentaerythritol four (methyl) acrylate, further preferably enumerate ethylene-oxide-modified two season penta 4
(methyl) acrylate of alcohol six and ethylene-oxide-modified dipentaerythritol four (methyl) acrylate.Through the modified more officials of alkylene oxide
Distance between the crosslinking points of energy property (methyl) acrylate is elongated, and relatively soft physical property, cure shrinkage quantitative change are presented after hardening
It is small.By constituting the first hard conating 3 by the material, even if the aggregate thickness of the first hard conating 3 and the second hard conating 4 is thicker,
Resistance to bend(ing) is also excellent, and can effectively inhibit and warpage occurs when manufacturing hard coat film 1.
Relative to 1 mole of multi-functional (methyl) acrylate, alkylene oxide is relative to multi-functional (methyl) acrylic acid
The import volume of ester is preferably 2 moles or more, particularly preferably 6 moles or more, further preferably 20 moles or more.In addition, should
Import volume be preferably 50 moles hereinafter, particularly preferably 45 moles hereinafter, further preferably 40 moles or less.By making epoxy
The import volume of alkane is 2 moles or more, and the cure shrinkage of modified multi-functional (methyl) acrylate of the alkylene oxide is smaller.This
Outside, by making 50 moles of the import volume of alkylene oxide hereinafter, making modified multi-functional (methyl) acrylate cures of the alkylene oxide
When, required hardness can be obtained.
In addition, the alkylene oxide from resistance to bend(ing) and the angle of inhibition warpage, in active energy ray-curable ingredient
The ratio of modified multi-functional (methyl) acrylate is preferably 30 mass % or more, more preferably 50 mass % or more, especially
Preferably 80 mass % or more, further preferably 90 mass % or more.In addition, the ratio may be 100 mass %.
On the other hand, as (methyl) esters of acrylic acid prepolymer, such as polyester acrylates, epoxy third can be enumerated
The prepolymers such as olefin(e) acid esters, urethane acrylate class, polyalcohol acrylate class.
It as polyester acrylates prepolymer, such as can be obtained by following manner: use (methyl) acrylic acid, it will
There is obtained from condensation through polybasic carboxylic acid and polyalcohol in two ends the hydroxy esterification of the polyester oligomers of hydroxyl；Alternatively,
(methyl) acrylic acid is used, alkylene oxide is additional to the hydroxy esterification of the end of oligomer obtained from polybasic carboxylic acid.
Epoxy Acrylates prepolymer can for example be obtained by following manner: make (methyl) acrylic acid and molecular weight compared with
The oxirane ring of low bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin is reacted and is esterified.
Urethane acrylate class prepolymer can for example be obtained by following manner: (methyl) acrylic acid is used,
The polyurethane oligomer as obtained from the reacting of polyether polyol or polyester polyol and polyisocyanate is esterified.
Polyalcohol acrylate class prepolymer for example can be by using (methyl) acrylic acid by the hydroxyl of polyether polyol
It is esterified and obtains.
Above prepolymer can be used alone one kind, also can be used in combination two or more.
(1-2-2) Photoepolymerizationinitiater initiater
It is formed in the first hard conating 3 material as made of solidifying the composition containing active energy ray-curable ingredient
In the case where, when using ultraviolet light as active energy beam, the composition preferably comprises Photoepolymerizationinitiater initiater.By with this side
Formula contains Photoepolymerizationinitiater initiater, and active energy ray-curable can be made to polymerize well at component efficiency, and can reduce poly-
Close curing time and ultraviolet irradiation amount.
As such Photoepolymerizationinitiater initiater, such as benzoin, benzoin methylether, benzoin ethyl ether, benzene idol can be enumerated
Relation by marriage isopropyl ether, benzoin n-butylether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2- dimethoxy -2- phenyl
Acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- hydroxy-cyclohexyl benzene
Base ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholine-propane-1- ketone, 4- (2- hydroxyl-oxethyl) phenyl-2- (hydroxyl-
2- propyl) ketone, benzophenone, to phenyl benzophenone, 4,4 '-lignocaine benzophenone, dichloro benzophenone, 2- methyl anthracene
Quinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2-chlorothioxanthone, 2,
4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-(dimethylamino)-benzoic acid
Ester, oligomerization [2- hydroxy-2-methyl -1 [4- (1- methyl ethylene) phenyl] acetone], 2,4,6- trimethylbenzoyl-hexichol
Base-phosphine oxide etc..They can be used alone, and also can be used in combination two or more.
Relative to 100 mass parts of active energy ray-curable ingredient, the content of the Photoepolymerizationinitiater initiater in composition
Lower limit value is preferably 0.01 mass parts or more, more than particularly preferably 0.1 mass parts, more than further preferably 1 mass parts.This
Outside, upper limit value is preferably that 20 below the mass, particularly preferably 10 below the mass, and further preferably 5 below the mass.
(1-2-3) nano SiO 2 particle
The composition for constituting the first hard conating 3 can also contain nano SiO 2 particle.Thereby, it is possible to further decrease
The cure shrinkage of one hard conating 3.
The lower limit value of the average grain diameter of nano SiO 2 particle is preferably 2nm or more, particularly preferably 6nm or more, into
One step is preferably 8nm or more.In addition, upper limit value is preferably 300nm hereinafter, particularly preferably 100nm is hereinafter, further preferably
50nm or less.If the average grain diameter of nano SiO 2 particle is 2nm or more, it can more easily obtain reduction first and apply firmly
The effect of the cure shrinkage of layer 3.In addition, the average grain diameter if nano SiO 2 particle be 300nm hereinafter, if obtaining
First hard conating 3 is not allowed to be also easy to produce the scattering of light, the transparency of the first hard conating 3 is got higher.In addition, nano SiO 2 particle
Average grain diameter is measured by Zeta potential measuring method.
Nano SiO 2 particle usually has silanol group on surface, reduces sometimes with the silanol group low in polarity
Organic solvent or resin in dispersibility.For the purpose of promoting dispersibility, which can also be organic
Object modification.Furthermore it is preferred that using nano SiO 2 particle in the form of organosol (colloidal).By with organosol
Form uses, and the dispersibility of nano SiO 2 particle becomes well, the homogeneity and light transmission of obtained first hard conating 3
Property is promoted.
Conventional method is able to use using the modification of organic matter to carry out.For example, by by CH2=C (CH3)COO(CH2)3Si
(OCH3)3The silane coupling agent of such structure is added to the organosol of nano SiO 2 particle, is heated up to 50 DEG C or so,
A few hours are stirred, are modified so as to the surface to silica dioxide granule.The structure and amount energy of the silane coupling agent used
The requirement degree of enough dispersibilities according to nano SiO 2 particle suitably selects.
Compatibility as organic solvent used in above-mentioned organosol, preferably with active energy ray-curable ingredient
And excellent methyl ethyl ketone, the methyl iso-butyl ketone (MIBK) etc. of volatility when forming the first hard conating 3.
When first hard conating 3 of present embodiment contains nano SiO 2 particle, in the first hard conating 3, content
Lower limit value be preferably 5 mass % or more, particularly preferably 10 mass % or more, further preferably 30 mass % or more.It is logical
Cross the 5 mass % of content or more for making nano SiO 2 particle, can easily make the cure shrinkage of the first hard conating 3 into
One step reduces.On the other hand, in the first hard conating 3, the upper limit value of the content of nano SiO 2 particle is preferably 80 matter
% is measured hereinafter, particularly preferably 75 mass % are hereinafter, further preferably 70 mass % or less.By making silica nanometer
The content of grain is 80 mass % hereinafter, being easy to be set as connecing with the refractive index of the second hard conating 4 by the refractive index of the first hard conating 3
Close value, while the layer easy to form for having used composition for hard coat.
In addition, the content of nano SiO 2 particle can be acquired according to mix proportions, the indefinite situation of mix proportions
Under, it can acquire as described below.That is, using a part of the first hard conating 3 of hard coat film 1 as part etc. from base material film 2
Separation, by the part of the first hard conating 3 of separation according to JIS 7250-1 come the organic principle that burns.It then, can be by obtaining
Ash content finds out the quality % of nano SiO 2 particle.
(1-2-4) other ingredients
The composition for constituting the first hard conating 3 of present embodiment can also contain various additions in addition to the above ingredients
Agent.As various additives, such as ultraviolet absorbing agent, antioxidant, light stabilizer, antistatic agent, silane idol can be enumerated
Join agent, age resister, thermal polymerization inhibitor, colorant, surfactant, preserving stabilizer, plasticizer, lubricant, defoaming agent,
Organic packing material, wettability modifying agent, coating surface modifying agent etc..
(1-2-5) physical property
The lower limit value of the refractive index of first hard conating 3 is preferably 1.40 or more, and particularly preferably 1.43 or more, it is further excellent
It is selected as 1.45 or more.In addition, the upper limit value of the refractive index of the first hard conating 3 be preferably 1.80 hereinafter, particularly preferably 1.70 with
Under, further preferably 1.60 or less.By making the refractive index of the first hard conating 3 within the above range, can easily by with
The refringence of the refractive index of second hard conating 4 is set as above-mentioned range.
The thickness of first hard conating 3 is preferably 3 μm or more, particularly preferably 4 μm or more, further preferably 5 μm or more.
In addition, the thickness of the first hard conating 3 be preferably 30 μm hereinafter, particularly preferably 20 μm hereinafter, further preferably 15 μm or less.
By make the first hard conating 3 with a thickness of 3 μm or more, can easily suppress and warpage, Er Qie occur when manufacturing hard coat film 1
The marresistance of one hard conating 3 becomes more excellent.In addition, if the first hard conating 3 with a thickness of 30 μm hereinafter, if hard coat film 1
It is easily bent, resistance to bend(ing) becomes more excellent.
(1-3) second hard conating
Second hard conating 4 of the hard coat film 1 of present embodiment assigns higher surface hardness to hard coat film 1, makes scratch resistance
Property is excellent.As long as the refractive index of second hard conating 4 and the first hard conating 3 meets above-mentioned relationship and has defined hardness
It is not particularly limited.It is preferred that second hard conating 4 is by solidifying the composition containing active energy ray-curable ingredient
Material formed, especially from the angle of superior marresistance is obtained, preferably as make composition solidify made of material
Material is formed, and the composition contains the active energy ray-curable ingredient modified without alkylene oxide.
As active energy ray-curable ingredient, it is able to use and above-mentioned active-energy used in the first hard conating 3
The identical active energy ray-curable ingredient of ray-curable ingredient.Wherein, it is preferable to use the activity modified without alkylene oxide
Energy ray-curable ingredient.Specifically, it is preferable that without modified multi-functional (methyl) acrylate of alkylene oxide, amino first
Acid esters esters of acrylic acid prepolymer and their mixture etc., especially from resistance to bend(ing) is obtained without damaging marresistance
Angle is set out, preferably the aliphatic categories such as dipentaerythritol six (methyl) acrylate, dipentaerythritol four (methyl) acrylate
Multifunctional (methyl) acrylate, urethane acrylate class prepolymer or their mixture etc..
In addition, the second hard conating 4 containing the active-energy through the modified multifunctional (methyl) acrylate of alkylene oxide by penetrating
When the formation of line curability composition, the active energy ray-curable used in the angle of marresistance, the second hard conating 4
Property ingredient entirety in the content of the multifunctional (methyl) acrylate modified through alkylene oxide be preferably 60 mass % hereinafter, more excellent
30 mass % are selected as hereinafter, particularly preferably 10 mass % or less.In addition, lower limit value is 0 mass %.
It is excellent when ultraviolet light to be used as to the active energy beam irradiated to solidify active energy ray-curable ingredient
Above-mentioned composition is selected to contain Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, be able to use with used in the first hard conating 3 on
State the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
The second hard conating 4 in present embodiment can also contain filler.It is higher thereby, it is possible to be assigned to the second hard conating 4
Surface hardness, marresistance can be made more excellent.
It can be any one of organic filler, inorganic filler as filler, from can be assigned to the second hard conating 4
The angle for giving higher surface hardness is set out, it is preferable to use inorganic filler, particularly preferably uses using with by active energy
Inorganic filler made of amount radiation exposure and the organic compound of polymerizable functional group polymerizeing are chemically modified.In addition,
Filler can be used alone one kind or be applied in combination two or more.
As inorganic filler, such as can enumerate by silica, aluminium oxide, zirconium oxide, titanium oxide, zinc oxide, oxidation
The metal oxides such as germanium, indium oxide, tin oxide, tin indium oxide (ITO), antimony oxide, cerium oxide；The metals such as magnesium fluoride, sodium fluoride
The filler of the formation such as fluoride.Wherein, from the viewpoint of the influence to optical characteristics is few, preferably silica and aluminium oxide,
Particularly preferred silica.
Filler, particularly silica filler surface can also be modified by sulphation, and particularly preferably had and pass through active-energy
Radiation exposure and the organic compound chemical modification of polymerizable functional group polymerizeing.The specific structure of chemical modification does not limit,
As an example, the structure that polymerizable functional group is attached with via silane coupling agent etc. can be enumerated.For such knot
In the case where structure, irradiated by active energy beam, filler is bonded with active energy ray-curable Components Chemical, they two
Do not allow to be also easy to produce removing between person, the hardness of the second hard conating 4 is easy to get higher.It will be by this method by having with polymerizable functional group
Filler made of machine compound chemical modification is known as reactive filler, if such as the type of filler is silica, be known as anti-
Answering property silica filler.
The shape of filler can be spherical, can also be non-spherical.In the case where for non-spherical, can be unsetting, can also for it is needle-shaped,
The high shape of the draw ratio of flakey etc.From the angle for the transparency for ensuring the second hard conating 4, filler is preferably spherical.
The lower limit value of the average grain diameter of filler is preferably 1nm or more, particularly preferably 3nm or more, further preferably 5nm
More than.By making the average grain diameter 1nm or more of filler, dispersibility is promoted.In addition, the upper limit value of the average grain diameter of filler
Preferably 500nm hereinafter, particularly preferably 200nm hereinafter, further preferably 50nm or less.By the average grain diameter for making filler
For 500nm or less, it is not easy to generate the scattering of light in the second obtained hard conating 4, the transparency of the second hard conating 4 is got higher.
In addition, the average grain diameter of filler is the primary particle size measured by Zeta potential measuring method.
When the second hard conating 4 of present embodiment contains filler, the lower limit value of content is preferably 5 mass % or more,
Particularly preferably 20 mass % or more, further preferably 50 mass % or more.By make the 5 mass % of content of filler with
On, it can effectively promote the hardness of the second hard conating 4.On the other hand, in the second hard conating 4, the upper limit of the content of filler
It is worth preferably 90 mass % hereinafter, particularly preferably 80 mass % are hereinafter, further preferably 70 mass % or less.By making to fill out
The content of material is 90 mass % hereinafter, layer formation becomes easy.
Second hard conating 4 of present embodiment in addition to the above ingredients, containing in the first above-mentioned hard conating 3
Used in the same various additives of various additives.
The lower limit value of the refractive index of second hard conating 4 is preferably 1.40 or more, and particularly preferably 1.43 or more, it is further excellent
It is selected as 1.45 or more.In addition, the upper limit value of the refractive index of the second hard conating 4 be preferably 1.80 hereinafter, particularly preferably 1.70 with
Under, further preferably 1.60 or less.By making the refractive index of the second hard conating 4 within the above range, can easily by with
The refringence setting of the refractive index of first hard conating 3 is within the above range.
The thickness of second hard conating 4 is preferably 0.75 μm or more, particularly preferably 1 μm or more, further preferably 1.5 μm
More than.In addition, the thickness of the second hard conating 4 be preferably 10 μm hereinafter, particularly preferably 8 μm hereinafter, further preferably 6 μm with
Under.By make the second hard conating 4 with a thickness of 0.75 μm or more, the marresistance of the second hard conating 4 becomes more excellent.This
Outside, if the second hard conating 4 with a thickness of 10 μm hereinafter, if can further suppress the warpage of hard coat film 1 and generate.
The ratio between thickness of the thickness of first hard conating 3 and the second hard conating 4 is preferably 10:90~90:10, particularly preferably
40:60~80:20, further preferably 50:50~80:20.By making this than within the above range, obtained hard coat film 1
Marresistance and resistance to bend(ing) it is more excellent, while the generation of warpage can be further suppressed.
(2) manufacturing method of hard coat film
The hard coat film 1 of present embodiment can it is preferable to use the following method to manufacture.In addition, in this method, as one
Example uses the composition containing active energy ray-curable ingredient in the formation of the first hard conating 3 and the second hard conating 4.
Firstly, preparation is containing the composition (the first composition of hard conating 3) for constituting the first hard conating 3 and according to need
Will further the first composition of hard conating 3 containing solvent coating fluid.In addition, benefit is prepared in a like fashion containing composition
The composition (the second composition of hard conating 4) of second hard conating 4 and as needed further the second painting firmly containing solvent
The coating fluid of the composition of layer 4.
As solvent, such as the aliphatic hydrocarbons such as hexane, heptane can be enumerated, the aromatic hydrocarbons such as toluene, dimethylbenzene, dichloromethane
The halogenated hydrocarbons such as alkane, dichloroethanes, the alcohol such as methanol, ethyl alcohol, propyl alcohol, butanol, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl
The ketone such as isobutyl ketone, 2 pentanone, isophorone, cyclohexanone, the esters such as ethyl acetate, butyl acetate, the cellosolves such as ethyl cellosolve
Class solvent etc..Solvent can only use one kind, can also be used in mixed way two or more.As the concentration viscosity of coating fluid, only
It to be then not particularly limited for the range that can be coated with, it can be suitably selected according to situation.
The coating fluid of first composition of hard conating 3 is coated on an interarea of base material film 2 and after making it dry, benefit
Active energy beam is irradiated with aftermentioned condition.The curing of coating of first hard conating 3 composition and the painting firmly of formation first as a result,
Layer 3.Then, the coating fluid of the second composition of hard conating 4 is coated on obtained first hard conating and after making it dry,
Active energy beam is irradiated according to aftermentioned condition.The curing of coating of second composition of hard conating 4 as a result, and form second
Hard conating 4.In addition, the forming method of the first hard conating 3 and the second hard conating 4 is not limited to above-mentioned method, it also can be by two
The coating fluid of layer is successively coated and dried, and is irradiated using an active energy beam, is formed simultaneously the first hard conating 3 and second
Hard conating 4.
The coating of coating fluid is carried out using conventional method, such as stick coating method, scraper for coating method, Meyer stick can be used
Method, rolling method, scraper coating method, die coating method, gravure coating process carry out.The drying of film for example can be by 40~180 DEG C
It heats 30 seconds~5 minutes or so and carries out.
As active energy beam, it is able to use ultraviolet light, electron beam etc..Ultraviolet light irradiation is able to use high-pressure mercury
Lamp, photocuring H lamp (fusion H lamp), xenon lamp etc. carry out, ultraviolet irradiation amount with illumination photometer be preferably 50~
1000mW/cm2, with quantometer be preferably 50~1000mJ/cm2Left and right.On the other hand, electron beam irradiation is able to use electron beam
Accelerator etc. carries out, and the exposure of electron beam is preferably 10~1000krad or so.
In addition, when ultraviolet light is used as active energy beam, the film and the second hard conating of the first hard conating 3 composition
4 preferably carry out ultraviolet light irradiation in the state that oxygen is isolated with the film of composition.It not will receive as a result, caused by oxygen
Solidification hinders, and can be effectively formed the hard coat film that resistance to bend(ing) is excellent and surface hardness is high.
In order to make the film of above-mentioned first hard conating 3 composition and the film isolation from oxygen of the second composition of hard conating 4
Emulsion sheet is preferably layered on above-mentioned film or is maintained under the lower environment of oxygen concentration, under such as nitrogen environment by gas.
(3) physical property of hard coat film
(3-1) maximum reflectivity is poor
As described above, being able to suppress the generation of interference fringe in the hard coat film 1 of present embodiment.This point except through
Other than visually being evaluated, it can also be determined by the measured value of maximum reflectivity difference.It is poor for measurement maximum reflectivity,
Film normal direction is set as 0 ° first, from 8 ° of direction irradiation lights of incidence angle, light optically focused after being reflected using integrating sphere by
This is detected in a manner of reflected light.In addition, the irradiation of light carries out and making wavelength change, and detect the anti-of corresponding each wavelength
Penetrate light.
Reflected light is set as 100 the relative value (" reflection hereinafter, be referred to as with reflected light caused by crystallizing barium sulfate
Rate ") mode, corresponding each measurement wavelength and detect.That is, horizontal axis can be obtained as measurement wavelength, the longitudinal axis is the chart of reflectivity.
The chart is usually the shape with the fluctuating of multiple minimums and maximum.
Herein, in the chart of reflectivity that measurement wavelength is 500~600nm, the maximum that will abut against and minimum
Maximum difference measurement is used as " maximum reflectivity is poor " in difference.The maximum reflectivity difference is preferably 1.5 hereinafter, particularly preferably 1.1
Hereinafter, further preferably 0.6 or less.By making reflectivity 1.5 hereinafter, being able to suppress the generation of interference fringe.
(3-2) image vividness
The hard coat film 1 of present embodiment does not pass through setting by adding the particle of small grade (micro order)
There is the first hard conating 3 and the second hard conating 4 of regulation refringence and thickness to solve the problems, such as to prevent interference fringe.Cause
This, compared to the particle by adding small grade come the case where preventing interference fringe, the hard coat film 1 of present embodiment can make
Image vividness is more excellent.
The excellent hard coat film of image vividness is applied in display, can obtain displaying contrast excellent image
Display.From such angle, image vividness is preferably 400% or more, and more preferably 430% or more, particularly preferably
It is 450% or more.
In addition, image vividness can according to JIS K7374, with the slit of 5 types (slit width: 0.125mm,
0.25mm, 0.5mm, 1mm and 2mm) mode of the aggregate value of each image vividness that is measured acquires.
(3-3) haze value
When applied to display, from the angle for showing distincter image, it will preferably be measured according to JIS K7136
The haze value of hard coat film 1 be set as 1% hereinafter, being more preferably set as 0.8% hereinafter, being particularly preferably set as 0.5% or less.
(3-4) 60 ° of glossiness
When applied to display, from the angle for showing distincter image, preferably by the second hard painting in hard coat film 1
60 ° of glossiness (Gloss value) of the foundation JIS Z8741-1997 of 4 side of layer are set as 100% or more value, are more preferably set as
120% or more value is particularly preferably set as 140% or more value.
(4) other embodiment
As shown in Fig. 2, can the base material film 2 of hard coat film 1 another main surface side (be laminated with the first hard conating 3 and
The face of two hard conatings 4 is the surface side of opposite side) stacking adhering agent layer 5 (symbol of hard coat film shown in Fig. 2 is recorded as " 1A ").
By the way that such adhering agent layer 5 is laminated, hard coat film 1A can be simply attached to required adherend.
As the sticker for constituting adhering agent layer 5, it is not particularly limited, is able to use acrylic compounds sticker, rubber
Sticker well known to sticker, organic silicon sticker etc..The thickness of adhering agent layer 5 is not particularly limited, usually 5~100 μ
M, preferably 10~60 μm of range.
The hard coat film 1A of present embodiment can substantially be manufactured in the way of identical with above-mentioned hard coat film 1.Sticker
Layer 5 uses conventional method formation.
In addition, stripping film can also be laminated in the exposed surface (being the face of opposite side with 2 side of base material film) of adhering agent layer 5.
(5) other embodiment -2
Hard coat film 1, the 1A of present embodiment can also be laminated with other layers, such as pressure sensitive adhesive layer, barrier layer
(barrier layer), conductive layer, low reflection layer, easy printing layer, stain-proofing layer etc..
(6) purposes of hard coat film
Hard coat film 1, the 1A of above embodiment can for example be preferably used as various electronic equipments, particularly mobile electron
Flexible display in equipment is specifically preferably used as liquid crystal display (LCD), organic el display (OELD), Electronic Paper
The flexible member on the surface layer (protective film) of the various flexible displays such as module (membranaceous Electronic Paper).
In addition, when by the hard coat film 1,1A or flexible display bending of present embodiment, it preferably will be in hard coat film 1,1A
There are the sides of the first hard conating 3 and the second hard conating 4 to carry out bending as on the inside of.Thus, it is not easy in the first hard conating 3
And a problem that the second generation cracking of hard conating 4.
Embodiments described above be for easy understanding the present invention and records, be not intended to limit it is of the invention and
It records.Thus, each element disclosed in above embodiment is to become comprising belonging to whole designs of technical scope of the invention
More with the objective of equipollent.
As long as, can be between each layer in hard coat film 1,1A for example, do not hinder the function and effect of above-mentioned present embodiment
There are other layers.
Embodiment
Hereinafter, the present invention is further concretely demonstrated using embodiment etc., but the scope of the present invention does not limit
In these embodiments etc..
[Production Example 1] (manufacture of base material film)
In n,N-dimethylacetamide solvent, by 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, xenyl four
Carboxylic acid dianhydride and 2, bis- (3,4- dicarboxyphenyi) the hexafluoro propionic acid dianhydrides of 2- carry out mixed dissolution under cooling, then by
It is stirred 10 hours under room temperature, obtains polyamic acid solution.
Acetic anhydride and pyridine are added into obtained polyamic acid solution, after fully stirring, are coated on a glass,
180 DEG C are warming up to from room temperature at leisure.After reaching 180 DEG C, certain time is heated, is then vacuumized, thus be will volatilize into
Divide and completely removes.Finally, obtaining 25 μm of film thickness of polyimide film by being cooled to room temperature under vacuum.For polyamides Asia
Amine film is measured, and as a result b* is 0.61, refractive index 1.62, and the transmitance at wavelength 550nm is 90%.
In addition, according to JIS K7130, using level pressure thickness tester, (Teclock company is manufactured, name of product " PG-
02 ") film thickness of polyimide film is measured.
For above-mentioned b*, according to JIS Z8722, same fixed time testing plan beam splitting type colour difference meter (NIPPON DENSHOKU is used
INDUSTRIES CO., LTD. manufacture, name of product " SQ-2000 ") make as measurement device, using 2 ° of visuals field (C/2) of illuminant-C
For light source, the b* through measuring method measurement L*a*b* color specification system is utilized.
Transmitance at above-mentioned wavelength 550nm uses the visible near-infrared spectrophotometric transmittance meter (Shimadzu of ultraviolet light
Corporation manufacture, name of product " UV3600 ") it is measured.
[embodiment 1]
, than in the mixed solvent made of mixed methyl isobutyl ketone and cyclohexanone, active energy will be used as with the quality of 1:1
Measure ethylene-oxide-modified dipentaerythritol hexaacrylate (importing 12 moles of ethylene oxide) 100 mass of ray-curable ingredient
Part (solid component conversion；It is same as below) it is stirred with 5 mass parts of 1- hydroxycyclohexylphenylketone as Photoepolymerizationinitiater initiater
Mixing is mixed, the coating fluid of the first composition for hard coat is obtained.
In addition, than in the mixed solvent made of mixed methyl isobutyl ketone and cyclohexanone, will be used as and live with the quality of 1:1
40 mass parts of dipentaerythritol hexaacrylate of property energy ray-curable ingredient are filled out as the reactive silicon dioxide of filler
Expect the mixed of (average grain diameter: 15nm) 60 mass parts and 10 mass parts of 1- hydroxycyclohexylphenylketone as Photoepolymerizationinitiater initiater
It closes object to be stirred, obtains the coating fluid of the second composition for hard coat.
Then, the coating fluid of above-mentioned first composition for hard coat is coated on obtained in Production Example 1 using Meyer stick
In one side as the polyimide film of base material film, and in 70 DEG C heat drying 1 minute, form the first composition for hard coat
Film.Then, first hard by under the following conditions, from the film side of the first composition for hard coat irradiate ultraviolet light, making
The curing of coating of coating composition forms 5 μm of thickness of the first hard conating.
Then, the coating fluid of above-mentioned second composition for hard coat is coated on obtained first hard conating, in 70
DEG C heat drying 1 minute, form the film of the second composition for hard coat.Then, by under the following conditions, it is hard from second
Ultraviolet light is irradiated in the film side of coating composition, makes the curing of coating of the second hard coating composition, forms the second of 5 μm of thickness
Hard conating.It obtains being sequentially formed with the first hard conating (thickness on the polyimide film (25 μm of thickness) as base material film as a result,
Degree: 5 μm) and the second hard conating (thickness: 5 μm) hard coat film.
<ultraviolet light irradiation condition>
Ultraviolet lamp: the ultraviolet lamp of GS Yuasa Corporation corporation
Light source: high-pressure mercury-vapor lamp
Lamp electric power: 1.4kW
Illumination: 100mW/cm2
Light quantity: 240mJ/cm2
Convey tape speed: 1.2m/min
Ultraviolet light irradiation in a nitrogen environment (below oxygen concentration 1%)
[embodiment 2~5, comparative example 1~6]
Type and blending in addition to each ingredient of the first composition for hard coat and the second composition for hard coat will be constituted
Than, the first hard conating and the thickness of the second hard conating and the type and thickness of base material film change as shown in table 1 with
Outside, hard coat film is manufactured in the way of same as Example 1.
Herein, the thickness of the first hard conating and the aggregate thickness of thickness of the second hard conating and shown in table 1 are calculated.
In addition, that Details as Follows is described for breviary symbol recorded in table 1 etc..
A: ethylene-oxide-modified dipentaerythritol hexaacrylate (importing 12 moles of ethylene oxide)
B: ethylene-oxide-modified dipentaerythritol hexaacrylate (importing 6 moles of ethylene oxide)
C: ethylene-oxide-modified pentaerythritol tetraacrylate (importing 35 moles of ethylene oxide)
D: vinylester resin (manufacture of Hitachi Chemical Co., Ltd., name of product " Hitaloid7663 ")
E: dipentaerythritol hexaacrylate
F: nano SiO 2 particle (silicon dioxide gel) (Nissan Chemical Corporation manufacture, product
Title " MIBK-ST ", average grain diameter: 10nm)
G:1- hydroxycyclohexylphenylketone
H: 40 mass parts of dipentaerythritol hexaacrylate, reactive silicon dioxide filler (average grain diameter: 15nm) 60 matter
Measure the mixture of part and 10 mass parts of 1- hydroxycyclohexylphenylketone
50 mass parts of urethane acrylate class prepolymer, 50 mass of pentaerythritol tetraacrylate of 1:6 function
The mixture of part and 10 mass parts of 1- hydroxycyclohexylphenylketone
In addition, that Details as Follows is described for breviary symbol recorded in table 2 etc..
PI: polyimide film
PET: polyethylene terephthalate film (Mitsubishi Plastics, Inc. manufacture, name of product
" Diafoil T-60 ", thickness: 50 μm)
[test example 1] (measurement of refractive index)
(1) refractive index of base material film
Measure wavelength be 589nm, measuring temperature is 25 DEG C under conditions of, using Abbe refractometer (ATAGO CO.,
LTD, manufacture, name of product " multi-wavelength Abbe refractometer DR-M2 "), embodiment and compare according to JIS K7142 (2008) measurement
The refractive index of base material film used in example.Show the result in table 2.
(2) refractive index of hard conating
In the way of identical with Examples and Comparative Examples, in polyethylene terephthalate of the one side through easy adhesion process
Shape on the untreated face of ester film (TOYOBO CO., LTD. manufacture, name of product " COSMOSHINE A4100 ", thickness: 50 μm)
At the first hard conating or the second hard conating of thickness 200nm.Then, using Sandpapering polyethylene terephthalate film
Easily bonding process face, and black is filled using oil pen's (ZEBRA Co., Ltd. manufactures, name of product " Mckee is black ").
Then, under conditions of measurement wavelength is 589nm, measuring temperature is 25 DEG C, light splitting ellipsometer test is used
(J.A.WOOLLAM CO. manufacture, name of product " M-2000 ") measures above-mentioned first hard conating according to JIS K7142 (2008)
And second hard conating refractive index.Show the result in table 2.
(3) calculating of refringence
The refractive index of the second hard conating is subtracted from the refractive index in the first hard conating of said determination, calculates refractive index
Difference.Show the result in table 2.
[test example 1] (evaluation of interference fringe)
(1) visual valuation
By the hard coat film manufactured in Examples and Comparative Examples via double-faced pressure-sensitive adhesive sheet (LINTEC CORPORATION manufacture,
Name of product " OPTERIA MO-3006C ", thickness: 25 μm) and it is attached at acrylic board (the MITSUBISHI RAYON of black
CO., LTD. is manufactured, name of product " Acrylight L502 ").At this point, contacted with the base material film of hard coat film with acrylic board
Mode is attached.
For obtained laminated body, by visual observation from hard conating side confirmation interference fringe under 3 wavelength fluorescent lamps, and according to
It is evaluated according to benchmark below.Show the result in table 2.
Well (◎): being hardly visible interference fringe
Substantially good (zero): it is not easily seen interference fringe
Slightly bad (△): see interference fringe
Bad (×): interference fringe can be clearly seen
(2) measurement of maximum reflectivity difference
For laminated body obtained in (1), under the following conditions, using spectrophotometric determination in reflectance spectrum
Maximum reflectivity between 500~600nm of wavelength is poor.Show the result in table 2.
<determination condition>
Spectrophotometer: Shimadzu Corporation. manufacture, " UV, visible light near-infrared is divided light to name of product
Degree meter UV-3600 "
Sample retainer (specimen holder): Shimadzu Corporation. manufacture, name of product are " large-scale
Sample room MPC-3100 "
Integrating sphere: Shimadzu Corporation. manufacture, name of product " integrating sphere auxiliary equipment ISR-3100 "
Incidence angle: 8 °
[test example 3] (evaluation of marresistance)
For the hard coating surface of the hard coat film manufactured in Examples and Comparative Examples, using the steel wool of #0000 with 125g
Weight/cm2Load reciprocating friction 10 times, the range of length 100mm, width 20mm are set as trial stretch.In 3 wavelength fluorescent lamps
Under confirm scar item number in the trial stretch by visual observation, and according to benchmark evaluation marresistance below.It shows the result in
Table 2.
Zero: scar item number is less than 20.
×: scar item number is 20 or more.
[test example 4] (warpage evaluation)
By the hard coat film manufactured in Examples and Comparative Examples with each side and the direction MD (production line when manufacture polyimide film
Direction) or after the direction TD (with the orthogonal direction in the direction MD) parallel mode severing is 100 × 100mm, glass is become with base material film
Hard coat film is positioned on flat glass plate by the mode of glass plate side.Then, measurement is from the upper surface of glass plate to hard coat film
Levitation height until each corner vertex, and it is based on judgement benchmark evaluation warpage below.Show the result in table 2.
Very good (◎): in 10 samples, the summation of the levitation height in each corner of 10 samples is respectively less than 20mm
Well (zero): in 10 samples, the summation floated in each corner of 9~6 samples is less than 20mm
Bad (×): in 10 samples, the summation floated in each corner of 5~0 samples is less than 20mm
[test example 5] (resistance to bend(ing) test)
For the hard coat film manufactured in Examples and Comparative Examples, durability-testing machines (YUASA SYSTEM Co., Ltd. is used
Manufacture, name of product " plane body zero load U-shaped elongation test machine DLDMLH-FS ") and hard conating is made to become outside, with test speed
60mm/s makes various changes test number (TN) (umber of reciprocation) and bending diameter and makes its repeated flex.Then, it is confirmed whether to produce
A problem that albefaction of the spalling, hard coat film of stiff coating is bent the generation of trace, and according to benchmark below
Evaluate resistance to bend(ing).Show the result in table 2.
◎: even if bending diameter is 5mm hereinafter, and test number (TN) is also not generate unfavorable condition 20,000 times or more.
Zero: even if bending diameter is 10mm hereinafter, and test number (TN) is also not generate unfavorable condition 20,000 times or more.
×: not up to zero benchmark.
[test example 6] (evaluation of image vividness)
For the hard coat film manufactured in Examples and Comparative Examples, image distinctiveness analyzer (Suga Test is used
The manufacture of Instruments Co., Ltd., name of product " ICM-10P "), the slit (slit of 5 types is measured according to JIS K7374
Width: 0.125mm, 0.25mm, 0.5mm, 1mm and 2mm) aggregate value as image vividness (%).Based on this as a result, by shadow
As vividness being assessed as less than 400% ×, zero will be assessed as more than and less than 450% for 400%, by 450% or more
It is assessed as ◎.Show the result in table 2.
(test example 7) (evaluation of haze value)
For the hard coat film manufactured in Examples and Comparative Examples, haze meter (NIPPON DENSHOKU is used
INDUSTRIES CO., LTD. manufacture, name of product " NDH5000 "), haze value (%) is measured according to JIS K7136.It is based on
This as a result, by haze value greater than 1% be assessed as ×, by 1% or less and to be greater than 0.5% and being assessed as zero, by 0.5% or less
Be assessed as ◎.Show the result in table 2.
(test example 8) (evaluation of 60 ° of glossiness)
For the hard coat film manufactured in Examples and Comparative Examples, Grossmeters (NIPPON DENSHOKU is used
INDUSTRIES CO., LTD. manufacture), 60 ° of glossiness are measured according to JIS Z8741-1997.Based on this as a result, by 60 ° of gloss
Degree being assessed as less than 100% ×, it will be assessed as zero more than and less than 140% for 100%, 140% or more is assessed as
◎.Show the result in table 2.
According to table 2, hard coat film obtained in embodiment has excellent marresistance and optical characteristics, while bending resistance
Song is excellent and is not likely to produce interference fringe and warpage.
Industrial applicibility
Hard coat film of the invention is suitable as constituting the flexible member for the flexible display being bent repeatedly, is particularly suitable for making
For positioned at the protective film on surface layer.
Description of symbols
1,1A: hard coat film；2: base material film；3: the first hard conatings；4: the second hard conatings；5: adhering agent layer.
Claims (11)
1. a kind of hard coat film, have base material film, at least one main surface side for being layered in the base material film the first hard conating and
It is layered in the second hard conating of the main surface side opposite with the base material film side of first hard conating, which is characterized in that
The base material film is polyimide film,
First hard conating and second hard conating are formed by material different from each other,
The specific refractivity of the refractive index of first hard conating and second hard conating with absolute value be calculated as 0.04 hereinafter,
The thickness of the thickness of first hard conating and second hard conating adds up to 7 μm or more, 35 μm or less.
2. hard coat film according to claim 1, which is characterized in that
First hard conating and second hard conating are by solidifying the composition containing active energy ray-curable ingredient
Made of material formed,
First hard conating is formed by the material than the second hard conating softness.
3. hard coat film according to claim 1 or 2, which is characterized in that
First hard conating by making containing the composition solidification through the modified active energy ray-curable ingredient of alkylene oxide and
At material formed,
Second hard conating is solidified by making containing the composition without the modified active energy ray-curable ingredient of alkylene oxide
Made of material formed.
4. hard coat film according to claim 2 or 3, which is characterized in that the active energy ray-curable ingredient is more
Functionality (methyl) acrylic ester monomer.
5. hard coat film according to any one of claims 1 to 4, which is characterized in that the refractive index of first hard conating
It is 1.40 or more, 1.80 or less.
6. hard coat film according to any one of claims 1 to 5, which is characterized in that the refractive index of second hard conating
It is 1.40 or more, 1.80 or less.
7. hard coat film described according to claim 1~any one of 6, which is characterized in that first hard conating with a thickness of 3
μm or more, 30 μm or less.
8. hard coat film according to any one of claims 1 to 7, which is characterized in that second hard conating with a thickness of
0.75 μm or more, 10 μm or less.
9. hard coat film described according to claim 1~any one of 8, which is characterized in that the polyimide film with a thickness of 5
μm or more, 300 μm or less.
10. hard coat film described according to claim 1~any one of 9 is used as constituting the flexible member of flexible display.
11. hard coat film described according to claim 1~any one of 10, which is characterized in that at least the one of the base material film
Adhering agent layer is laminated in a main surface side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110239725.6A CN113009602B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/074567 WO2018037489A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110239725.6A Division CN113009602B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
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| Publication Number | Publication Date |
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| CN109073789A true CN109073789A (en) | 2018-12-21 |
| CN109073789B CN109073789B (en) | 2021-07-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110239725.6A Active CN113009602B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
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| CN202110239725.6A Active CN113009602B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
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| Country | Link |
|---|---|
| JP (1) | JP6216907B1 (en) |
| KR (1) | KR102619222B1 (en) |
| CN (2) | CN109073789B (en) |
| TW (1) | TWI759298B (en) |
| WO (1) | WO2018037489A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292541A (en) * | 2021-12-23 | 2022-04-08 | 南通纳尔材料科技有限公司 | Optically transparent anti-fouling scratch-resistant protective film composition |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7119424B2 (en) * | 2017-03-02 | 2022-08-17 | 大日本印刷株式会社 | Optical film and image display device |
| WO2018180304A1 (en) * | 2017-03-29 | 2018-10-04 | 大日本印刷株式会社 | Optical film and image display device |
| KR20230171478A (en) | 2017-10-27 | 2023-12-20 | 어플라이드 머티어리얼스, 인코포레이티드 | Flexible cover lens films |
| KR102638825B1 (en) * | 2018-01-24 | 2024-02-21 | 주식회사 동진쎄미켐 | Polyimide film and method for producing the same |
| KR20200142594A (en) | 2018-05-10 | 2020-12-22 | 어플라이드 머티어리얼스, 인코포레이티드 | Interchangeable cover lenses for flexible displays |
| JP2021536030A (en) | 2018-08-14 | 2021-12-23 | アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated | Multi-layer wet and dry hard coat for flexible cover lenses |
| JP7225767B2 (en) * | 2018-12-18 | 2023-02-21 | 三菱ケミカル株式会社 | laminated film |
| KR20230173748A (en) | 2019-06-26 | 2023-12-27 | 어플라이드 머티어리얼스, 인코포레이티드 | Flexible multi-layered cover lens stacks for foldable displays |
| JP7295769B2 (en) * | 2019-10-04 | 2023-06-21 | アイカ工業株式会社 | hard coat film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09176485A (en) * | 1995-12-27 | 1997-07-08 | Tomoegawa Paper Co Ltd | Resin composition for coating film and molded article of coating film using the same |
| JP2008116596A (en) * | 2006-11-02 | 2008-05-22 | Riken Technos Corp | Hard coat film and antireflection film |
| JP2011152681A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Hard coat film |
| WO2016076243A1 (en) * | 2014-11-10 | 2016-05-19 | 住友化学株式会社 | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4543441B2 (en) * | 1998-09-01 | 2010-09-15 | 凸版印刷株式会社 | Hard coat film or sheet |
| JP2005096298A (en) * | 2003-09-25 | 2005-04-14 | Dainippon Printing Co Ltd | Optical film and optical display device equipped with it |
| JP2006058574A (en) * | 2004-08-19 | 2006-03-02 | Nitto Denko Corp | Hard coat film |
| JP4526126B2 (en) * | 2004-12-17 | 2010-08-18 | 日東電工株式会社 | Hard coat film and method for producing the same |
| JP2010085501A (en) * | 2008-09-29 | 2010-04-15 | Fujifilm Corp | Liquid crystal display device |
| JP5713528B2 (en) * | 2008-11-18 | 2015-05-07 | 三菱化学株式会社 | Active energy ray-curable resin composition, hard coat cured film and laminate |
| TWI541534B (en) * | 2011-10-17 | 2016-07-11 | Dainippon Printing Co Ltd | Optical film, polarizing plate and image display device |
| JP2013117584A (en) * | 2011-12-01 | 2013-06-13 | Keiwa Inc | Hard coat film, transparent conductive laminate, and touch panel |
| JP5468167B1 (en) | 2013-05-20 | 2014-04-09 | 尾池工業株式会社 | Laminated body |
| JP6227321B2 (en) * | 2013-08-05 | 2017-11-08 | リンテック株式会社 | Transparent conductive film with protective film |
| JP2015069197A (en) | 2013-10-01 | 2015-04-13 | Dic株式会社 | Hard coat film and image display device |
| WO2015076566A1 (en) * | 2013-11-19 | 2015-05-28 | 주식회사 엘지화학 | Plastic film |
| JP2016002764A (en) | 2014-06-19 | 2016-01-12 | 日本合成化学工業株式会社 | Laminate, use thereof, and production method thereof |
| KR102277807B1 (en) * | 2014-10-17 | 2021-07-15 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resin composition, polyimide film and laminate |
-
2016
- 2016-08-23 JP JP2017507032A patent/JP6216907B1/en active Active
- 2016-08-23 KR KR1020187024967A patent/KR102619222B1/en active IP Right Grant
- 2016-08-23 WO PCT/JP2016/074567 patent/WO2018037489A1/en active Application Filing
- 2016-08-23 CN CN201680085288.4A patent/CN109073789B/en active Active
- 2016-08-23 CN CN202110239725.6A patent/CN113009602B/en active Active
-
2017
- 2017-05-04 TW TW106114771A patent/TWI759298B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09176485A (en) * | 1995-12-27 | 1997-07-08 | Tomoegawa Paper Co Ltd | Resin composition for coating film and molded article of coating film using the same |
| JP2008116596A (en) * | 2006-11-02 | 2008-05-22 | Riken Technos Corp | Hard coat film and antireflection film |
| JP2011152681A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Hard coat film |
| WO2016076243A1 (en) * | 2014-11-10 | 2016-05-19 | 住友化学株式会社 | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292541A (en) * | 2021-12-23 | 2022-04-08 | 南通纳尔材料科技有限公司 | Optically transparent anti-fouling scratch-resistant protective film composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190039466A (en) | 2019-04-12 |
| CN113009602A (en) | 2021-06-22 |
| TW201808607A (en) | 2018-03-16 |
| WO2018037489A1 (en) | 2018-03-01 |
| JP6216907B1 (en) | 2017-10-18 |
| CN109073789B (en) | 2021-07-13 |
| JPWO2018037489A1 (en) | 2018-08-23 |
| TWI759298B (en) | 2022-04-01 |
| CN113009602B (en) | 2023-05-23 |
| KR102619222B1 (en) | 2023-12-28 |
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