CN102207557B - Hard coating film, polarized sheet, and image display device - Google Patents
Hard coating film, polarized sheet, and image display device Download PDFInfo
- Publication number
- CN102207557B CN102207557B CN201110081887.8A CN201110081887A CN102207557B CN 102207557 B CN102207557 B CN 102207557B CN 201110081887 A CN201110081887 A CN 201110081887A CN 102207557 B CN102207557 B CN 102207557B
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- film
- base material
- energy ray
- hard coat
- mold
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- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
- B29C39/18—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Polarising Elements (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
The invention relates to a hard coating film, a polarized sheet, and an image display device. The hard coating film (31) is provided with a base material film (312), a coating layer (311) laminated at one surface of the base material film (312), wherein the hard coating layer (311) is formed by curing one side of an active energy ray curing resin composition comprising an active energy ray curing resin, a polymerization initiator, and a surfactant in a contact with on side of a mold, and the contact angle Theta of the hard coating layer (311) and water satisfies the following formula (1). In the formula (1), Theta 0 represents contact angle of water and a hard coating layer formed by, at a surface of the base material film, curing of the active energy ray curing resin composition in a 25 DEG gas and made to be in no contact with the mold. |Theta 0-Theta|<= 15 DEG (1).
Description
Technical field
The present invention relates to hard coat film.Further, the present invention relates to the polaroid employing this hard coat film and image display device.
Background technology
The image display devices such as liquid crystal display, plasma display, Brown tube (cathode-ray tube (CRT): CRT) display, organic electroluminescent (EL) display are in most cases designed with the scratch that hard coat film causes to prevent various external force.And generally implement non-glare treated to such hard coat film, described non-glare treated makes incident light scattering by forming micro concavo-convex on surface thus swoon to mirror image.
As the method obtaining described hard coat film, such as in International Publication No. 2008/020613 pamphlet, disclose a kind of method, wherein, resin combination for the formation of hard conating is coated on dandy roll, then make base material film contact while irradiate ionizing radiation with this dandy roll, but do not adjust Contact Temperature especially, make above-mentioned resin composition thus, base material film forms hard conating, then peels off this film from this roller.And, in Japanese Unexamined Patent Publication 2007-76089 publication, disclose a kind of method, wherein, the resin combination for the formation of hard conating is coated on base material film, then, while make this coated face contact with dandy roll, irradiate active energy beam, do not adjust Contact Temperature especially, make above-mentioned resin composition thus, base material film forms hard conating, then, peels off this film from this roller.
Summary of the invention
But in above-mentioned existing hard coat film, hard conating is peeled off from base material film sometimes, hard conating may not be abundant from the peel resistance base material film.Therefore, the object of the present invention is to provide hard conating from the hard coat film of the peel resistance excellence base material film.
The invention provides a kind of hard coat film, it possesses base material film and lamination in the hard conating of this base material film one side, described hard conating is by making the actinic energy ray curable resion composition containing active energy ray-curable resin, polymerization initiator and surfactant while with mold contact while be solidified to form, and the contact angle θ of described hard conating to water meets following formula (1).
|θ
0-θ|≤15°(1)
(in formula, θ
0represent the one side of base material film make described actinic energy ray curable resion composition not with mold contact the hard conating that is solidified to form in the gas of 25 DEG C to the contact angle of water.)
And, the invention provides a kind of manufacture method of hard coat film, it is the manufacture method of above-mentioned hard coat film, comprises following operation: the operation containing the actinic energy ray curable resion composition of active energy ray-curable resin, polymerization initiator and surfactant at the coated on one side of base material film; The mold contact of itself and less than 55 DEG C is made while irradiate active energy beam to the described actinic energy ray curable resion composition of coating, thus described actinic energy ray curable resion composition is solidified, form the operation of hard conating; With the operation peeling off described hard conating from described mold.
And then, the invention provides a kind of polaroid, it possesses the light polarizing film of above-mentioned hard coat film and the another side lamination at the above-mentioned base material film of above-mentioned hard coat film, and, a kind of image display device is provided, it possesses this polaroid and image-displaying member, and above-mentioned polaroid is configured at the visuognosis side of above-mentioned image-displaying member closer to the mode of above-mentioned image-displaying member than above-mentioned hard conating with above-mentioned light polarizing film.
According to the present invention, the hard coat film from the peel resistance excellence base material film of hard conating can be provided.Further, this hard coat film can perform well in polaroid and image display device.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section representing the example that the Primary layer of image display device of the present invention is formed.
(symbol description)
10... backlight, 20,30... polaroid, 31... hard coat film, 311... hard conating, 312... base material film, 33... light polarizing film, 40... image-displaying member, 50... light diffusing sheet, 60... liquid crystal panel, 100... liquid crystal indicator
Embodiment
< hard coat film >
Hard coat film possesses base material film and lamination in the hard conating of this base material film one side, above-mentioned hard conating is by making the actinic energy ray curable resion composition containing active energy ray-curable resin, polymerization initiator and surfactant while with mold contact while be solidified to form, and the contact angle θ of above-mentioned hard conating to water meets following formula (1).
|θ
0-θ|≤15°(1)
In formula, θ
0represent the one side of base material film make above-mentioned actinic energy ray curable resion composition not with mold contact the hard conating that is solidified to form in the gas of 25 DEG C to the contact angle of water, be that the hard conating that formed under air ambient is to the contact angle of water.
Hard coat film of the present invention is by meeting above-mentioned formula (1), and the peel resistance from base material film of hard conating is excellent.
As base material film, as long as through can make the active energy beam of active energy ray-curable resin solidification, the film with optical transparence, be just not particularly limited, various transparent resin film can be used.Specifically can illustrate by cellulose-based resins such as cellulose acetate such as triacetyl cellulose, diacetyl cellulose, cellulose-acetate propionates; Polycarbonate-based resin; Polyacrylate, polymethylmethacrylate etc. (methyl) acrylic resin; The polyester based resins such as poly-para Toluic Acid's glycol ester, PEN; The chain such as tygon, polypropylene polyolefin-based resins; Cyclic polyolefin hydrocarbon system resin; Phenylethylene resin series; Polysulfones; Polyethersulfone; Polyvinylchloride; Deng the film formed.In above example, from the viewpoint of the transparency, physical strength, thermal stability, low-moisture permeability, isotropy etc., the film preferably formed by cellulose acetate, polyethylene terephthalate, polymethylmethacrylate etc., from the viewpoint of transparent, physical strength, the film more preferably formed by cellulose acetate.
The thickness of base material film is preferably 20 μm ~ 250 μm, is more preferably 30 μm ~ 150 μm.When the thickness of base material film is less than 20 μm, be sometimes difficult to obtain the sufficient hardness as hard coat film.Further, from aspects such as the nearest requirement to image display device slimming and costs, the thickness of preferred substrates film is not more than 250 μm.From the view point of making, the thickness of hard coat film entirety is thin, and the thickness of base material film is more preferably less than 150 μm, more preferably less than 120 μm.
Further, antistatic layer, easily adhesive linkage also can be set at the coated face of the actinic energy ray curable resion composition of base material film and/or the surface of its opposition side.Antistatic layer and easy adhesive linkage are only otherwise the coating of actinic energy ray curable resion composition and adaptation are reduced, or do not cause and exceed necessary painted or atomization, the transmitance of active energy beam is not made significantly to reduce, just be not particularly limited, existing known antistatic layer and easy adhesive linkage can be used.
Hard coat film of the present invention is used for optical applications, in particular as form liquid crystal display (LCD) optical component time; such as, when being used as the diaphragm of polaroid; in order to protect other optical components such as light polarizing film or liquid crystal cells from ultraviolet infringement, base material film is preferably containing UV absorbing agent.
Actinic energy ray curable resion composition contain be polymerized by the irradiation of active energy beam, the active energy ray-curable resin solidified, the polymerization initiator being produced free radical by the irradiation of active energy beam and surfactant.Active energy ray-curable resin such as can contain multifunctional (methyl) acrylate based compound.Multifunctional (methyl) acrylate based compound refers in molecule the compound with at least 2 (methyl) acryloxies.Active energy ray-curable resin, polymerization initiator and surfactant also can be commercially available product.In most cases, actinic energy ray curable resion composition as containing active energy ray-curable resin, polymerization initiator, other the adjuvant such as the surfactant added as required goods and be commercially available.
Enumerate the concrete example of multifunctional (methyl) acrylate based compound, such as there is ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, five polyglycereol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three ((methyl) acrylyl oxy-ethyl) isocyanuric acid ester, the phosphonitrile ring of phosphazene compound has imported phosphonitrile system (methyl) acrylate compounds of (methyl) acryloxy, carbamate (methyl) acrylate compounds that obtains by the polyisocyanates in molecule with at least 2 isocyanate group and the reaction of polyol compound with at least 1 (methyl) acryloxy and hydroxyl, by there are in molecule at least 2 carboxylic acid halides and there is the reaction of polyol compound of at least 1 (methyl) acryloxy and hydroxyl and polyester (methyl) acrylate compounds that obtains, and the oligomer etc. such as 2 aggressiveness of above-mentioned each compound, 3 aggressiveness.These compounds individually use or mix two or more and use.
Active energy ray-curable resin, except above-mentioned multifunctional (methyl) acrylate based compound, also can contain simple function (methyl) acrylic ester resin.As simple function (methyl) acrylate based compound, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid 2-hydroxyl-3-phenoxy-propyl, (methyl) glycidyl acrylate etc. can be enumerated such as.These compounds individually use or mix two or more use.The content of simple function (methyl) acrylate based compound is preferably less than 10 % by weight in the resin solid content of actinic energy ray curable resion composition.
Further, active energy ray-curable resin also can contain polyreactive oligomers.By containing polyreactive oligomers, the hardness of hard conating can be adjusted.As polyreactive oligomers, the macromonomer such as end (methyl) acrylate polymethylmethacrylate, end styryl poly-(methyl) acrylate, end (methyl) acrylate polystyrene, end (methyl) acrylate polyglycol, end (methyl) acrylate acrylonitritrile-styrene resin, end (methyl) acrylate styrene-(methyl) methyl acrylate copolymer can be enumerated.The content of polyreactive oligomers is preferably 5 ~ 50 % by weight in the resin solid content of Actinic-radiation curable composition.
As the polymerization initiator contained in actinic energy ray curable resion composition, such as acetophenone can be enumerated, acetophenone benzyl ketals, anthraquinone, 1-(4-isopropyl phenyl-2-hydroxy-2-methyl propane-1-ketone, carbazole, xanthone, 4-chlorobenzophenone, 4,4 '-diaminobenzophenone, 1,1-dimethoxy deoxybezoin, desoxybenzoin, 3,3 '-dimethyl-4-methoxy benzophenones, thioxanthones, 2,2-dimethoxy-2-phenyl acetophenone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinopropane-1-ketone, triphenylamine, TMDPO, two (2,4,6-the trimethylbenzoyl)-phosphine oxide of phenyl, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, Fluorenone, fluorenes, benzaldehyde, benzoin ethyl ether, benzoin iso-propylether, benzophenone, Michler's keton, 3-methyl acetophenone, 3,3 ', 4,4 '-four (tert-butyl peroxy carbonic acyl radical) benzophenone (BTTB), 2-(dimethylamino)-1-(4-(morpholinyl) phenyl)-2-phenyl methyl)-1-butanone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, benzil and their derivant etc.These polymerization initiators both can be used alone, and also can mix several as required and use.Above-mentioned illustrative polymerization initiator is the Photoepolymerizationinitiater initiater being produced free radical by the irradiation of active energy beam.
Polymerization initiator also can combinationally use with dye-sensitized dose.As dye-sensitized dose, such as xanthene, thioxanthene, cumarin, coumarin ketone etc. can be enumerated.As the combination of polymerization initiator and dye-sensitized dose, the combination etc. of the combination of such as BTTB and xanthene, the combination of BTTB and thioxanthene, the combination of BTTB and cumarin, BTTB and coumarin ketone can be enumerated.
The content of polymerization initiator is preferably the scope of 1 ~ 10 % by weight relative to active energy ray-curable resin, is more preferably the scope of 3 ~ 6 % by weight.If polymerization initiator containing quantity not sufficient 1 % by weight, then curing reaction does not fully carry out, and sometimes uncured active energy ray-curable resin is attached on mold or can not get having the hard coat film of excellent hardness.Further, if the content of polymerization initiator is more than 10 % by weight, then the degree of polymerization of active energy ray-curable resin reduces, and sometimes can not get the hard coat film with excellent hardness.
As mentioned above, base material film is preferably containing UV absorbing agent, and usual UV absorbing agent absorbs 360nm ~ less than the ultraviolet of 380nm wavelength.In addition, in (first) of the present invention curing process, as described later in detail, preferably irradiating active energy beam from base material film side makes actinic energy ray curable resion composition solidify.Therefore, at least a kind in the polymerization initiator contained by preferred actinic energy ray curable resion composition has absorbing wavelength at more than 380nm.As such polymerization initiator, TMDPO (TPO), two (2,4,6-the trimethylbenzoyl)-phosphine oxides of phenyl etc. can be enumerated.Polymerization initiator contained by actinic energy ray curable resion composition is all only when having the polymerization initiator of absorbing wavelength less than 380nm, after above-mentioned (first) curing process terminates, likely a large amount of active energy ray-curable resin is still uncured and residual, uncured active energy ray-curable resin so is also attached on mold after peeling base film, then become the reason of pollution or hinder the surface configuration of correctly transfer printing mold, so be not suitable for.
Herein, " having absorbing wavelength at more than 380nm " refers to when the active energy beam of more than illumination wavelength 380nm, produces the free radical of the necessary substantial amount of initiated polymerization, effectively plays a role as polymerization initiator.
In addition, as the UV absorbing agent contained by base material film, there is by being used in lower wavelength side the UV absorbing agent of absorbing wavelength, the polymerization initiator that more than 380mm does not have absorbing wavelength can be used only in.This method the hard coat film obtained by manufacture method of the present invention is configured at the optical components such as liquid crystal cells in image display device visuognosis side opposition side, namely rear side (in such as liquid crystal display, the backlight source of liquid crystal panel) time be effective.But; hard coat film is being configured at visuognosis side, the i.e. front side of the optical components such as liquid crystal cells in image display device (in such as liquid crystal display; the front side of liquid crystal panel) time; from the view point of optical component such as protection light polarizing film and liquid crystal cells etc. not by ultraviolet damage; preferably add in base material film and absorb 360nm ~ less than the ultraviolet UV absorbing agent of 380nm wavelength, and at least a kind contained by active energy ray-curable resin is set as the polymerization initiator at more than 380mm with absorbing wavelength.
As the surfactant contained by actinic energy ray curable resion composition, can enumerate the levelling agent for improving flatness, for improve with the release agent of the release property of mold, for show soil resistance or show resistance to fingerprint tack anti fouling agent, for preventing the conductive agent etc. of film strips electricity.These adjuvants only otherwise hinder the polyreaction of active energy ray-curable resin, do not make polyreaction after hardness or reduce with the adaptation of base material film be just not particularly limited, existing known adjuvant can be used.
As surfactant, choice for use can be suitable for from hydrocarbon system surfactant, fluorine system surfactant, silicon system surfactant etc., and, two or more these surfactant can be share as required.Wherein, from functional aspect, more preferably fluorine system surfactant, silicon system surfactant or the surfactant containing both.
As the example of fluorine system surfactant, the surfactant etc. the metal carboxylate containing perfluoroalkyl, the Sulfonates containing perfluoroalkyl, the phosphoric acid salt containing perfluoroalkyl, the carboxylic acid esters containing perfluoroalkyl, the sulfonic acid esters containing perfluoroalkyl, the phosphoric acid ester containing perfluoroalkyl, the oligomer class containing perfluoroalkyl-lipophilic group, oligomer class containing perfluoroalkyl-hydrophilic radical-lipophilic group can enumerated or above-mentioned perfluoroalkyl is replaced into perfluor and obtains.
As the example of silicon system surfactant, organic modified polyorganosiloxane and the derivant etc. thereof such as Siloxane-Oxyalkylene Copolymers class, polyester-modified polysiloxanes class, alkyl-modified polysiloxane-based, aralkyl modified polysiloxane-based, higher fatty acid modified polysiloxane-based, epoxy-modified polysiloxane class, amino modified polysiloxane class, carboxy-modified polysiloxane-based, alcohol modified polyorganosiloxane class can be enumerated.
Further, also can use the surfactant containing fluorine atom and these two kinds of atoms of silicon atom, as its example, part or all hydrogen fluorine that the alkyl of above-mentioned silicon system surfactant can be enumerated replace obtain, fluorinated modified polysiloxane-based etc.
Actinic energy ray curable resion composition also can improve to make its coating containing solvent.As solvent, can from the such as aliphatic hydrocarbon such as hexane, octane; The aromatic hydrocarbon such as toluene, dimethylbenzene; The alcohols such as ethanol, 1-propyl alcohol, isopropyl alcohol, n-butyl alcohol; The ketone such as methyl ethyl ketone, methyl isobutyl ketone; The ester classes such as ethyl acetate, butyl acetate, isobutyl acetate; The dibasic alcohol ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; Suitable choice for use in the esterification such as ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate dibasic alcohol ethers etc.These organic solvents both can be used alone, and also can mix several as required and use.After painting process, before (first) curing process, preferably make solvent evaporate and carry out drying, so the boiling point of solvent is preferably the scope of 60 ~ 160 DEG C.Further, the saturated vapour pressure of 20 DEG C is preferably the scope of 0.1 ~ 20kPa.The kind of solvent and content are according to suitable selections such as the thickness of the material of the kind of active energy ray-curable compound used and content, base material film, shape, coating process, object hard conating.
To give internal haze to alleviate for the purpose of twinkling grade, in actinic energy ray curable resion composition, also can add light transmission particulate.As light transmission particulate, be not particularly limited, existing known material can be used.The organic fine particles formed by acrylic resin, melamine resin, tygon, polystyrene, organic siliconresin, acrylic-styrene copolymer etc. or inorganic particles of being formed by calcium carbonate, silicon dioxide, aluminium oxide, barium carbonate, barium sulphate, titanium dioxide, glass etc. etc. such as can be used as light transmission particulate.The hollow ball (balloon) of organic polymer, glass hollow pearl can also be used.These light transmission particulates can be used alone one, also can mix two or more use.The shape of light transmission particulate can be spherical, arbitrary shape such as flat, tabular, needle-like, amorphous.
The particle diameter of light transmission particulate and refractive index are not particularly limited, but from effectively showing the aspect of internal haze, particle diameter is preferably the scope of 0.5 μm ~ 20 μm.Further, from the same reason, the difference of the refractive index after the solidification of active energy ray-curable resin and the refractive index of light transmission particulate is preferably the scope of 0.04 ~ 0.15.Relative to active energy ray-curable resin 100 weight portion, the content of light transmission particulate is 3 ~ 60 weight portions, is preferably 5 ~ 50 weight portions.The content of light transmission particulate relative to 100 parts by weight of activated energy ray-curable resins less than 3 weight portion time, can not get fully for alleviating twinkling internal haze.On the other hand, if the content of light transmission particulate is more than 60 weight portions, then the transparency of hard coat film is sometimes impaired, and, when hard coat film being configured in the visuognosis side in liquid crystal indicator, because light scattering is excessively strong, so such as in black display, due to the light that spills oblique relative to the frontal of liquid crystal panel by hard conating consumingly to reasons such as frontal scatterings, contrast reduces sometimes.
Mold, for giving hard coating surface with desired shape, has the surface configuration formed by the transfer printing structure of this desired shape.The surface configuration of mold both can be the even surfaces such as minute surface, also can for the concaveconvex shape for giving hard coat film anti-glare.The pattern of concaveconvex shape both can be the pattern of rule, also can be the accurate random patterns of random patterns or more than the a kind random patterns being paved with specific dimensions, but from preventing from causing reflected image with the aspect of iridescence because of the interference of the reflected light caused by the surface configuration of hard coat film, be preferably random patterns or accurate random patterns.
Being not particularly limited the shape of mold, both can be tabular, also can be cylindric or cylindric roller, but from the aspect of continuous production, is preferably the mold that mirror roller or dandy roll etc. are cylindric or cylindric.In this case, the surface configuration of regulation is formed in the side of cylindric or cylindric mold.
The material of the base material of mold is not particularly limited, can be suitable for selecting from metal, glass, carbon, resin or their compound, but from the viewpoint of the preferable alloy of processability etc.As the metal material preferably used, from the viewpoint of cost, aluminium, iron or the alloy etc. based on aluminium or iron can be enumerated.
As the method obtaining mold, can enumerate such as: grinding base material, after implementing sandblasting processing, implement chemical nickel plating and make the method (Japanese Unexamined Patent Publication 2006-53371 publication) of roller mould; After implementing copper facing or nickel plating to base material, grinding, after implementing sandblasting processing, implements the method (Japanese Unexamined Patent Publication 2007-187952 publication) of chromium plating; After implementing copper facing or nickel plating, grinding, after implementing sandblasting processing, implements etching work procedure or copper facing operation, then implements the method (Japanese Unexamined Patent Publication 2007-237541 publication) of chromium plating; After copper facing or nickel plating are implemented in the surface of mould base material, grinding, face coating after grinding forms photosensitive resin film, on this photosensitive resin film by pattern exposure after, development, using development after photosensitive resin film carry out etch processes as mask, peel off photosensitive resin film, and then carry out etch processes, after making male and fomale(M&F) rust, the male and fomale(M&F) formed is implemented to the method for chromium plating; With work mechanism such as use lathe etc., the method utilizing cutting tool to cut the base material becoming mold (International Publication No. 2007/077892 pamphlet) etc.
The surface unevenness profile of the mold formed by random patterns or accurate random patterns can be formed in the following way: such as, will by FM sieve method, DLDS (Dynamic Low-DiscrepancySequence, dynamic low deviation sequence) method, the random patterns that utilizes the method for the microphase-separated pattern of segmented copolymer or bandpass filter method etc. to generate be exposed on photosensitive resin film, and develop, photosensitive resin film after development is used as mask and carries out etch processes, thus form described concave-convex surface proterties.
In the present invention, as benchmark, the one side being determined at base material film make above-mentioned actinic energy ray curable resion composition not with mold contact the hard conating that is solidified to form in the gas of 25 DEG C to the contact angle θ of water
0, this θ
0with make above-mentioned actinic energy ray curable resion composition while with above-mentioned mold contact while the contact angle θ of the hard conating of the present invention be solidified to form to water meets above-mentioned formula (1).It should be noted that, alleged by formula (1) | θ
0-θ | mean θ
0with the absolute value of the difference of θ.| θ
0-θ | value more than 15 ° time, hard conating is sometimes easy to be peeled off from base material film.
Make | θ
0-θ | value when being below 15 °, such as suitably can adopt the method controlling mold temperature, use the method for the surfactant that surface tension reduction effectiveness is low, reduce the method for the addition of surfactant, the special surface process such as mold enforcement fluorine coating are reduced to the method etc. of the surface free energy of mold, but obtain levelability from the addition unduly reducing surfactant, the flatness of the film after solidification, the abundant effect that hydrophobicity etc. produce because adding surfactant, the manufacture ratio of mold and manufacturing installation to be easier to etc. set out, to preferably by the temperature controlling mold | θ
0-θ | value be adjusted to the method for less than 15 °.Specifically, such as can make by the temperature of mold is controlled below 55 DEG C | θ
0-θ | value be less than 15 °.
The manufacture method > of < hard coat film
Secondly, the manufacture method of hard coat film of the present invention is described.Hard coat film of the present invention can by comprising the manufacture method manufacture of following operation: the operation containing the actinic energy ray curable resion composition of active energy ray-curable resin, polymerization initiator and surfactant at the coated on one side of base material film; The mold contact of itself and less than 55 DEG C is made while irradiate active energy beam to the above-mentioned actinic energy ray curable resion composition of coating, above-mentioned actinic energy ray curable resion composition is solidified, form the operation of hard conating; With the operation peeling off above-mentioned hard conating from above-mentioned mold.That is, comprise (1) painting process, (2) curing process, (3) stripping process successively, below describe in detail.
(1) painting process
At the active energy ray-curable resin that the coated on one side of above-mentioned base material film is above-mentioned, form coating layer.As described rubbing method, can be suitable for selecting known method, specifically can enumerate coiling rod method, rolling method, gravure coating process, scraper for coating method, slit-type die head rubbing method, spin-coating method, spraying process, slope stream rubbing method, curtain coating method, ink-jet method etc.Wherein, consider from doing one's utmost to be mixed into the aspects such as foreign matter when preventing coating to actinic energy ray curable resion composition, preferred slit-type die head rubbing method.
(2) curing process (the first curing process)
Next, make above-mentioned coating layer be less than 55 DEG C with above-mentioned mold with the surface temperature of mold and contact, irradiate active energy beam simultaneously, above-mentioned coating layer is solidified.Further, thus, the surface configuration of mold is transferred on coating layer, forms hard conating.Like this, by the surface temperature of Contact Temperature, i.e. mold is set as less than 55 DEG C, make coating layer with mold contact while solidify, thus the desired contact angle to water can be obtained, hard conating can be improved from the peel resistance base material film.On the other hand, when above-mentioned Contact Temperature is lower than 20 DEG C, the surface of mold likely condenses.
In order to be set as above-mentioned Contact Temperature, and then in order to protect mold not overheated because of the irradiation of active energy beam, preferably on above-mentioned mold, cooling body is installed.As described cooling body, can enumerate and such as cooling tube is set in the inside of mold, the cooling tube of mold inside is connected with the refrigeration unit being arranged on outside, make the structure of refrigerant circulation.By this cooling body, by the surface cool of mold, above-mentioned Contact Temperature can be adjusted to thus.
To making coating layer and the closely sealed method of mold be not particularly limited, but between coating layer and mold, being mixed into bubble in order to preventing, preferably using the compression bonding apparatus such as niproll.When using niproll, clamp pressure is not particularly limited, but is preferably 0.05MPa ~ 1.0MPa.If clamp pressure is less than 0.05MPa, then between coating layer and mold, be easily mixed into bubble.On the other hand, if clamp pressure is more than 1.0MPa, then sometimes cause base material film to break because of the deviation slightly when base material film transmits, or coating layer expose from the end of base material film and become the reason of pollution sometimes.
As active energy beam, can be suitable for selecting from gamma-rays, X ray, ultraviolet, near ultraviolet ray, luminous ray, near infrared ray, infrared ray, electron ray etc. according to the kind of active energy ray-curable resin and polymerization initiator, but preferred ultraviolet, electron ray in these, particularly from due to easy and simple to handle, that high-energy and curability and throughput rate excellence can be obtained aspect, preferred ultraviolet.
As ultraviolet light source, such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon arc lamp etc. can be used, but be not limited to these, just be not particularly limited as long as produce ultraviolet light source.Further, ArF excimer laser, KrF excimer laser, Excimer lamp or synchrotron radiating light etc. can also be used.Wherein, ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, xenon arc lamp, metal halide lamp can preferably be utilized.
As the example for the ultraviolet lamp of irradiation ultraviolet radiation and the combination of light source, the UV irradiation unit " F600 " of Fusion UV SYSTEMS society manufacture or the combination of " LH10 " and H vacuum tube (being equivalent to mercury lamp) or D vacuum tube or V vacuum tube (being equivalent to metal halide lamp) can be enumerated; " CS series " that GS Yuasa Co., Ltd. manufactures and the combination of mercury lamp or metal halide lamp; The combination of UV irradiation units such as " QRM-2288 " or " QRM-2300 " manufactured by ORC makes and metal halide lamp or high-pressure sodium lamp; The combination of " Unicure system " that USHIO Electric Co., Ltd manufactures and metal halide lamp or high-pressure sodium lamp.Ultraviolet lamp and light source both can be used alone one or more like combinations, also can use multiple various combination.
The integration light quantity of ultraviolet UVA is preferably 40mJ/cm
2above, 70mJ/cm is more preferably
2above.If integration light quantity is less than 40mJ/cm
2, then insufficient during being solidified with of uv curing resin, uncured uv curing resin is attached on mold.On the other hand, for the upper limit of integration light quantity, as long as in the scope of above-mentioned Contact Temperature, be just not particularly limited.
Ultraviolet irradiation only can carry out 1 time, also can carry out more than 2 times.Further, the number for the light source used in curing process (ultraviolet lamp) is not particularly limited, and both can be 1 lamp, also can be more than 2 lamps.
(3) stripping process
After above-mentioned curing process, peel off hard coat film (laminate of base material film and hard conating) from mold.As stripping means, be not particularly limited, such as, when mold is roll shape, the burble point being preferably used in hard coat film and mold arranges the compression bonding apparatus such as niproll, using the method for this compression bonding apparatus as fulcrum from stripping film mold.Thus, effectively can prevent film in the irradiation of active energy beam from peeling off from mold, maintain the closed state of mold and film, efficiently by the film of the above-mentioned fulcrum of arrival and stably peel off simultaneously.
Like this, hard coat film of the present invention can be obtained, but and then, for the purpose of the curing reaction promoting hard conating further, preferably irradiate active energy beam further from hard conating side.This operation is called the second curing process, is below described.
(4) second curing process
Second curing process active energy beam used can be suitable for selecting from gamma-rays, X ray, ultraviolet, near ultraviolet ray, luminous ray, near infrared ray, infrared ray, electron ray etc., but preferred ultraviolet, electron ray in these, particularly from the viewpoint of due to easy and simple to handle, high-energy can be obtained and curability and throughput rate excellence, preferred ultraviolet.Further, active energy beam preferably uses the ray of the same race with the active energy beam used during the first above-mentioned curing process.When using different types of active energy beam, correspondingly need to use various kinds of resin, polymerization initiator, being designed with of resin combination may become complicated.
As the light source of the second curing process ultraviolet irradiation device used, such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon arc lamp etc. can be used, but be not limited to these, be just not particularly limited as long as produce ultraviolet light source.Further, ArF excimer laser, KrF excimer laser, Excimer lamp or synchrotron radiating light etc. can also be used.Wherein, ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, xenon arc lamp, metal halide lamp is preferably used.Ultraviolet lamp and light source both can use independent one or more like combinations, also can use multiple various combination.
In addition, the ultraviolet irradiation device used for the second curing process and the kind of light source, as long as make the ultraviolet that the polymerization initiator contained by hard conating effectively plays a role, also can be different from the ultraviolet of the first curing process.Such as, in the first curing process, use metal halide lamp, in the second curing process, also can use high-pressure sodium lamp.
The integration light quantity of the ultraviolet UVA of the second curing process is preferably 200mJ/cm
2above, 300mJ/cm is more preferably
2above.The upper limit of integration light quantity is not particularly limited.
Ultraviolet irradiation in second curing process only can carry out 1 time, also can carry out more than 2 times.Further, being not particularly limited the number of ultraviolet lamp used in the second curing process and light source, both can be 1 lamp, also can be more than 2 lamps.In addition, when carrying out the Ultraviolet radiation of more than 2 times in the second curing process, above-mentioned integration light quantity is the aggregate value of the ultraviolet above-mentioned integration light quantity to the second curing process.
In second curing process, in order to prevent the solidification of active energy ray-curable resin from being hindered by oxygen, preferably between the laminate formed by base material film and hard conating and irradiation unit, fill inert gas.Inert gas is suitable from nitrogen, argon, neon etc. to be selected, but from the viewpoint of the simplification of operation and cost, preferred nitrogen.Further, oxygen concentration now preferably less than 0.1%.
The concrete illuminating method of the active energy beam in the second curing process is not particularly limited, such as, both can irradiate in the state making base material film be sealed on the rollers such as backing roll, also active energy beam irradiation unit can be set irradiate by the hollow space between guide roller and guide roller.Further, when carrying out the irradiation of more than 2 times active energy beams, illuminating method respectively can be identical, also can be different illuminating methods.Such as, both backing roll all can be used to irradiate active energy beam the 1st time and the 2nd time, also backing roll can be used for the 1st time to irradiate active energy beam, and the 2nd hollow space between guide roller and guide roller arranges active energy beam irradiation unit and irradiates active energy beam.
In order to prevent active energy beam from causing pyrolytic damage or hotbox prediction to base material film, preferably use the illuminating method possessing the backing roll of cooling body.Surface temperature through the backing roll of cooling is generally the scope of 10 DEG C ~ 70 DEG C, is preferably the scope of 20 DEG C ~ 60 DEG C.When using backing roll, also the gauffer removal device for preventing gauffer in base material film strips can be set at the entrance side of the second curing process or at entrance side and outlet side both sides.
In order to protect hard conating and base material film, as required also can at the one or two sides laminating diaphragm of the laminate of base material film and hard conating.
Hard coat film of the present invention can be used as various optical component, such as, be preferably used as the diaphragm of polaroid.Further, its polaroid can be used for image display device.
< polaroid >
Polaroid of the present invention has the light polarizing film of above-mentioned hard coat film and the another side lamination at the above-mentioned base material film of above-mentioned hard coat film.Light polarizing film has the function of taking out rectilinearly polarized light from incident light, is not particularly limited its kind.As the example of preferred light polarizing film, can enumerate and be adsorbed with dichromatism pigment and the light polarizing film of this dichromatism pigment generation orientation on polyvinyl alcohol resin.As polyvinyl alcohol resin, except as except the saponified polyvinyl alcohol (PVA) of vinyl acetate, also can enumerate part formalizing polyvinyl alcohol (PVA), ethylene/vinyl acetate saponified etc.Further, as dichromatism pigment, iodine or dichromatic organic dyestuff is used.The polyene alignment films of the processed thing of polyvinyl alcohol (PVA) and the desalination acid treatment thing of Polyvinylchloride also can become light polarizing film.The thickness of light polarizing film is generally about 5 ~ 80 μm.
Polaroid of the present invention, can at the one or two sides of above-mentioned light polarizing film (being generally one side) lamination hard coat film of the present invention, also can at a laminated protective clear layer of above-mentioned light polarizing film, at another side lamination hard coat film of the present invention.Now, hard coat film also has the function of the protective clear layer as light polarizing film.When imparting surface unevenness profile to the hard conating of hard coat film, this hard conating also has the function as antiglare layer.By using the lamination protective clear layers such as the method for laminating film or the method for applied coating solution such as bonding agent.Equally, bonding agent etc. can be used to be fitted in light polarizing film by hard coat film of the present invention.
Protective clear layer is preferably the excellent layer such as the transparency, physical strength, thermal stability, moisture shielding, as such protective seam, can illustrate such as by cellulose-based resins such as cellulose acetate such as triacetyl cellulose, diacetyl cellulose, cellulose-acetate propionates; Polycarbonate-based resin; Polyacrylate, polymethylmethacrylate etc. (methyl) acrylic resin; The polyester based resin such as polyethylene terephthalate, PEN; The chain such as tygon, polypropylene polyolefin-based resins; Cyclic polyolefin hydrocarbon system resin; Phenylethylene resin series; Polysulfones; Polyethersulfone; The film that Polyvinylchloride etc. are formed.These films can be optical isotropy, in order to compensate wide viewing angle when being installed to image display device, also can have optical anisotropy.
When polaroid configuration of the present invention is manufactured liquid crystal panel on liquid crystal cell, when the one or two sides of liquid crystal cells is configured with polaroid, configure polaroid than the hard conating (or antiglare layer) of the present invention polaroid closer to the mode of liquid crystal cells with light polarizing film.Now, polaroid both can be configured in visuognosis side, also can be configured in backlight source, or also can be configured in these both sides.When polaroid being configured at visuognosis side, the scratch etc. that hard conating prevents external force from causing, and when also playing a role as antiglare layer, prevents from dazzling or the mirroring of outer light.On the other hand, when polaroid being configured at backlight source, hard conating prevents the scratch that producible external force causes in the assembling procedure of liquid crystal panel, such as with the contact of diffuser plate etc. and the scratch that produces, and when also playing function as antiglare layer, the effect preventing the diffuser plate of ripple etc. is played to the light injecting liquid crystal panel from backlight.
< image display device >
Image display device of the present invention is obtained by the hard coat film manufactured by method of the present invention, with various information presentation being combined to the image display device of picture.In image display device of the present invention, the kind of image display device is not particularly limited, except using the liquid crystal display (LCD) of above-mentioned liquid crystal panel, also can enumerate the screen etc. of Brown tube (cathode-ray tube (CRT): CRT) display, plasma scope (PDP), field-emitter display (FED), Surface conducting electronic emitting component display (SED), OLED display, laser writer, projection TV.
The hard coat film that the present invention relates to is preferably configured in the visuognosis side surface of the image-displaying member of these displays, now, as image display device, possess polaroid and image-displaying member, above-mentioned polaroid is configured in the visuognosis side of above-mentioned image-displaying member closer to the mode of above-mentioned image-displaying member than above-mentioned hard conating with above-mentioned light polarizing film.But the hard coat film that the present invention relates to also can be arranged on the inside of image display device in the mode of the backlight source being configured in image-displaying member.Image display device of the present invention, owing to possessing the hard coat film that the present invention relates to, so be difficult to produce scratch, has excellent intensity.
Fig. 1 is the schematic cross-section representing the example that the Primary layer of image display device of the present invention is formed.Enclose the image display device 100 shown in 1 and possess backlight 10, light diffusing sheet 50 and liquid crystal panel 60 successively.The polaroid 20 that liquid crystal panel 60 possesses image-displaying member 40, is configured in the backlight source of image-displaying member 40 negative direction of z-axis (in the Fig. 1) and be configured in the polaroid 30 of the visuognosis side positive dirction of z-axis (in the Fig. 1) of image-displaying member 40.The polaroid 30 being configured in the visuognosis side of image-displaying member 40 possesses hard coat film 31 and light polarizing film 33.Hard coat film 31 possesses base material film 312 and lamination in the hard conating 311 of the one side of base material film 312, is laminated with light polarizing film 33 at the another side of base material film 312.In image display device 100, polaroid 30 is configured in the visuognosis side of image-displaying member 40 closer to the mode of image-displaying member 40 than hard conating 311 with light polarizing film 33.Vertical line and the Z axis of the light-emitting face of backlight 10 are almost parallel.Further, the vertical line of the light entrance face of light diffusing sheet 50, polaroid 20, image-displaying member 40, polaroid 30 and Z axis almost parallel.
The polaroid 30 of image display device 100 of the present invention hard coat film of the present invention 31 used possesses base material film 312 and lamination in the hard conating 311 of the one side of base material film 312, hard conating 311 is by making the actinic energy ray curable resion composition containing active energy ray-curable resin, polymerization initiator and surfactant while with mold contact while be solidified to form, and the contact angle θ of hard conating 311 pairs of water meets above-mentioned formula (1).Described hard coat film of the present invention 31 is in the excellence in the peel resistance of base material film 312 of hard conating 311.
It should be noted that, image display device of the present invention is not limited to the formation shown in Fig. 1, can various distortion in addition.Such as, the polaroid 20 being configured in the backlight source of the image-displaying member 40 of Fig. 1 also can be the polaroid 30 possessing hard coat film 31 of the present invention, now, polaroid 30 can be configured in visuognosis side and these both sides of backlight source of image-displaying member 40, also can only be configured in backlight source one-sided.When polaroid 30 is configured in backlight source, preferably become the mode of backlight source relative to light polarizing film 33 with hard conating 311, namely with light polarizing film 33 than the mode of hard conating 311 closer to image-displaying member 40, configuration polaroid 30.Further, light diffusing sheet 50 and backlight 10 are not necessarily necessary, also can omit.
Below, provide embodiment, more specifically the present invention is described, but the invention is not restricted to these examples.
[hard coat film is to the mensuration of the contact angle of water]
For hard coat film described later, the CA-X type contact angle meter using consonance surface chemistry Co., Ltd. to manufacture, measures the contact angle to water.
[mensuration of the peel resistance of hard coat film]
For hard coat film described later, according to JIS K5400, carry out gridiron pattern test, evaluate the peel resistance from base material film of hard conating.Evaluate and carry out as follows: as leading, rule are cut to the CCJ-1 that the hard conating of this hard coat film uses COTEK society to manufacture, it is 100 pieces that the square mode of 1mm cuts into 10 pieces × 10 pieces with 1 piece, Cellotape (registered trademark) CT-24 using meter Qi Bang society to manufacture carries out 3 disbonded tests, the state that harder coating is peeled off from base material film.
[embodiment 1]
As actinic energy ray curable resion composition, use following ultra-violet solidified resin composition.
Uv curing resin: trade name " NK Hard KCR2803-50A " (urethane acrylate system resin, resin solid content concentration that KCC of Xin Zhong village manufactures: 60 % by weight, diluting solvent: ethyl acetate, to contain relative to the resin solid content of ultra-violet solidified resin composition 5.0 % by weight polymerization initiator: TPO (chemical name: 2; 4,6-trimethyl benzoyl diphenyl base phosphine oxide).)
Surfactant: trade name " Megafac F-477 "
(add relative to the resin solid content of LJV curable resin composition be 0.5 % by weight containing perfluoroalkyl, hydrophilic radical, lipophilic group oligomer.)
Be coated with machine with mould and be coated with in the mode that dried thickness is 5 μm triacetyl cellulose (TAC) film (trade name " TDY80UL ", Fuji Photo Film Co., Ltd. manufacture) of thickness 80 μm is upper, to be set as in the dryer of 60 DEG C drying 20 seconds.Next, the mode clamping roll-in at the laminate of the coating layer of the TAC film obtained and ultra-violet solidified resin composition around temperature 25 DEG C with coating layer being dandy roll side is attached to surface temperature control on the dandy roll of 38 DEG C, makes itself and dandy roll closely sealed.In this condition, use the UV irradiation unit of ORC society manufacture as ultraviolet lamp, use metal halide lamp as light source, with the integration light quantity of UVA for 200mJ/cm
2mode irradiate 1 ultraviolet from TAC film side, coating layer is solidified, formed hard conating.
Then, by TAC film together with hard conating from dandy roll peel off after, use ORC society manufacture UV irradiation unit as ultraviolet lamp, use high-pressure sodium lamp as light source, with the integration light quantity of UVA for 500mJ/cm
2mode from hard conating side, 1 ultraviolet is irradiated to laminate, make hard coat film.The result of hard conating in this film to the contact angle θ of water and the peel resistance from base material film of hard conating is recorded in table 1.
[embodiment 2,3 and comparative example 1]
The surface temperature of dandy roll is changed to as shown in table 1, in addition, makes hard coat film similarly to Example 1.The result of hard conating in these films to the contact angle θ of water and the peel resistance from base material film of hard conating is recorded in table 1.
[authentic specimen]
Except not solidifying under room temperature (25 DEG C), air ambient contiguously with dandy roll, make hard coat film similarly to Example 1.By the contact angle θ of the hard conating in this film to water
0record in Table 1.
[table 1]
Claims (7)
1. a hard coat film, it possesses base material film and lamination in the hard conating of this base material film one side,
Described hard conating is by making the actinic energy ray curable resion composition containing active energy ray-curable resin, polymerization initiator and surfactant while with mold contact while be solidified to form, and
The contact angle θ of described hard conating to water meets following formula (1),
|θ
0-θ|≤15° (1)
In formula, θ
0represent the one side of base material film make described actinic energy ray curable resion composition not with mold contact the hard conating that is solidified to form in the gas of 25 DEG C to the contact angle of water.
2. hard coat film as claimed in claim 1, wherein, described surfactant is fluorine system surfactant and/or silicon system surfactant.
3. a manufacture method for hard coat film, comprises following operation:
The operation of the actinic energy ray curable resion composition of active energy ray-curable resin, polymerization initiator and surfactant is contained at the coated on one side of base material film;
The mold contact of itself and less than 55 DEG C is made while irradiate active energy beam to the described actinic energy ray curable resion composition of coating, thus described actinic energy ray curable resion composition is solidified, form the operation of hard conating; With
The compression bonding apparatus arranged by burble point at described hard conating and described mold, as fulcrum, peels off the operation of described hard conating from described mold.
4. method as claimed in claim 3, wherein, described mold is mirror roller or dandy roll.
5. a polaroid, it possesses the light polarizing film of the hard coat film described in claim 1 or 2 and the another side lamination at the described base material film of described hard coat film.
6. a polaroid, it possesses the light polarizing film by the hard coat film of method manufacture described in claim 3 or 4 and the another side lamination at the described base material film of described hard coat film.
7. an image display device, it possesses polaroid described in claim 5 or 6 and image-displaying member,
Described polaroid is configured at the visuognosis side of described image-displaying member closer to the mode of described image-displaying member than described hard conating with described light polarizing film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010077186 | 2010-03-30 | ||
| JP2010-077186 | 2010-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102207557A CN102207557A (en) | 2011-10-05 |
| CN102207557B true CN102207557B (en) | 2015-07-22 |
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ID=44696484
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110081887.8A Expired - Fee Related CN102207557B (en) | 2010-03-30 | 2011-03-29 | Hard coating film, polarized sheet, and image display device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5987268B2 (en) |
| KR (1) | KR101787106B1 (en) |
| CN (1) | CN102207557B (en) |
| TW (1) | TWI496691B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104937449B (en) | 2013-01-22 | 2017-08-11 | 旭硝子株式会社 | Optical element, optical system and camera device |
| KR20210136065A (en) * | 2019-04-12 | 2021-11-16 | 후지필름 가부시키가이샤 | A hard coat film and its manufacturing method, the article provided with a hard coat film, and an image display apparatus |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690805A (en) * | 2004-04-26 | 2005-11-02 | 住友化学株式会社 | Laminate polarizing plate, a method of producing the same and a liquid crystal display |
| JP2007076089A (en) * | 2005-09-13 | 2007-03-29 | Konica Minolta Opto Inc | Method for producing optical film having uneven surface and optical film having uneven surface |
| CN1973003A (en) * | 2004-05-07 | 2007-05-30 | 3M创新有限公司 | Article comprising fluorochemical surface layer |
| CN101052681A (en) * | 2004-11-08 | 2007-10-10 | 三菱化学株式会社 | Radiation curable composition and curing product thereof, and laminate including the same |
| CN101458357A (en) * | 2007-12-11 | 2009-06-17 | 住友化学株式会社 | Polarizing paltes, liquid crystal panal and liquid crystal display device using the same |
| CN101516620A (en) * | 2006-09-27 | 2009-08-26 | 3M创新有限公司 | Solar control multilayer film |
| WO2009114572A2 (en) * | 2008-03-11 | 2009-09-17 | 3M Innovative Properties Company | Phototools having a protective layer |
| TW201000547A (en) * | 2008-04-28 | 2010-01-01 | Mitsubishi Chem Corp | Active energy ray-curable resin composition, cured film, laminate, optical recording medium and process for producing cured film |
| JP2010049019A (en) * | 2008-08-21 | 2010-03-04 | Hoya Corp | Method of manufacturing plastic lens |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3975036B2 (en) * | 1998-09-22 | 2007-09-12 | 富士フイルム株式会社 | Method for manufacturing antireflection film |
| JP2003227932A (en) * | 2002-02-04 | 2003-08-15 | Fuji Photo Film Co Ltd | Method for manufacturing protective film for polarizing plate, polarizing plate and image display device |
| US8110128B2 (en) * | 2005-09-21 | 2012-02-07 | Konica Minolta Opto, Inc. | Method of manufacturing an anti-glare anti-reflection film |
| US20070104896A1 (en) * | 2005-11-04 | 2007-05-10 | Fujifilm Corporation | Optical film, polarizing plate and image display device |
| JP4923670B2 (en) | 2006-03-29 | 2012-04-25 | 住友化学株式会社 | Manufacturing method of high hardness hard coat film |
| US9493620B2 (en) * | 2008-08-29 | 2016-11-15 | Konica Minolta Opto, Inc. | Optical film, anti-reflection film, polarizing plate and liquid crystal display device |
-
2011
- 2011-03-29 CN CN201110081887.8A patent/CN102207557B/en not_active Expired - Fee Related
- 2011-03-29 JP JP2011072356A patent/JP5987268B2/en not_active Expired - Fee Related
- 2011-03-29 TW TW100110841A patent/TWI496691B/en not_active IP Right Cessation
- 2011-03-29 KR KR1020110027936A patent/KR101787106B1/en active IP Right Grant
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690805A (en) * | 2004-04-26 | 2005-11-02 | 住友化学株式会社 | Laminate polarizing plate, a method of producing the same and a liquid crystal display |
| CN1973003A (en) * | 2004-05-07 | 2007-05-30 | 3M创新有限公司 | Article comprising fluorochemical surface layer |
| CN101052681A (en) * | 2004-11-08 | 2007-10-10 | 三菱化学株式会社 | Radiation curable composition and curing product thereof, and laminate including the same |
| JP2007076089A (en) * | 2005-09-13 | 2007-03-29 | Konica Minolta Opto Inc | Method for producing optical film having uneven surface and optical film having uneven surface |
| CN101516620A (en) * | 2006-09-27 | 2009-08-26 | 3M创新有限公司 | Solar control multilayer film |
| CN101458357A (en) * | 2007-12-11 | 2009-06-17 | 住友化学株式会社 | Polarizing paltes, liquid crystal panal and liquid crystal display device using the same |
| WO2009114572A2 (en) * | 2008-03-11 | 2009-09-17 | 3M Innovative Properties Company | Phototools having a protective layer |
| TW201000547A (en) * | 2008-04-28 | 2010-01-01 | Mitsubishi Chem Corp | Active energy ray-curable resin composition, cured film, laminate, optical recording medium and process for producing cured film |
| JP2010049019A (en) * | 2008-08-21 | 2010-03-04 | Hoya Corp | Method of manufacturing plastic lens |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101787106B1 (en) | 2017-10-18 |
| TWI496691B (en) | 2015-08-21 |
| KR20110109965A (en) | 2011-10-06 |
| JP5987268B2 (en) | 2016-09-07 |
| TW201141704A (en) | 2011-12-01 |
| CN102207557A (en) | 2011-10-05 |
| JP2011227488A (en) | 2011-11-10 |
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