CN106959477A - Optical film, the manufacture method of optical film, polarizer and image display device - Google Patents

Optical film, the manufacture method of optical film, polarizer and image display device Download PDF

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Publication number
CN106959477A
CN106959477A CN201710010492.6A CN201710010492A CN106959477A CN 106959477 A CN106959477 A CN 106959477A CN 201710010492 A CN201710010492 A CN 201710010492A CN 106959477 A CN106959477 A CN 106959477A
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China
Prior art keywords
optical film
film
polarizer
surface roughness
display device
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CN201710010492.6A
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CN106959477B (en
Inventor
岩间翔太
高木隆裕
梅田博纪
田坂公志
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Konica Minolta Inc
Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Dispersion Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention relates to optical film, the manufacture method of optical film, polarizer and image display device.The present invention provides a kind of optical film that transporting is good and mist degree is low.The optical film of the present invention is the optical film containing cyclic olefin resins, particulate and surface conditioner, above-mentioned surface conditioner contains the surface roughness Ra in the high face of surface roughness Ra at least one in organosilicon material, fluorine system material, vinyl based material and acrylic material, film two sides in the range of 3.0~50.0nm.

Description

Optical film, the manufacture method of optical film, polarizer and image display device
Technical field
The present invention relates to optical film, the manufacture method of optical film, polarizer and image display device.The present invention is more particularly directed to Transporting is good and mist degree is low optical film, the manufacture method of this optical film, the polarizer and image for possessing this optical film Display device.
Background technology
In the past, polarizer was carried in the image display devices such as TV, notebook computer and smart mobile phone, polarizer tool Constituted for the polarizer and diaphragm etc..
As the material for constituting diaphragm, for example, as it is known that cellulose ester resin, makrolon and cyclic olefin resins etc..This Among a little, from the viewpoint of with high heat resistance and moisture-proof, cyclic olefin resins are preferably used.
In addition, in recent years, the optical component used in image display device carries out filming, and cycloolefin resin film is also thin Used in the state of film.The cycloolefin resin film of film is when manufacturing the film and when manufacture uses the polarizer of the film, in order to protect Film quality is held, conveying in the state of diaphragm is fitted with one side in film two sides sometimes.
If however, using diaphragm, during the diaphragm existing defects, there is the defect can be transferred to cycloolefin resin film The problem of.And then, there is also the coefficient of thermal expansion differences due to diaphragm and cycloolefin resin film, by real when manufacturing polarizer The problem of heat straightening applied and cycloolefin resin film are deformed.
Therefore, if being conveyed in the state of diaphragm of not fitted on cycloolefin resin film and making polarizer, in conveying When on cycloolefin resin film produce surface irregularity or corrugation, fracture etc., can be remarkably decreased the yield of polarizer.This is Because because cycloolefin resin film is not slided on conveying roller, becoming excessive to the conveyance tension that cycloolefin resin film applies.
As making cycloolefin resin film relative to the method that conveying roller is slided, it is known that add dioxy in cycloolefin resin film SiClx particulate and the method for adjusting surface roughness Ra.However, in the case of cyclic olefin resins, in order to which film surface is set into rule Fixed surface roughness Ra is, it is necessary to add substantial amounts of silicon dioxide microparticle, thus, due to be incident to the light of film occur scattering etc. and Mist degree rises.If the cycloolefin resin film that mist degree rises is used for into image display device, front contrast decline can be produced Problem, causes the decline of quality.Additionally it is believed that for example, by by the hard conating containing metal particle be arranged at film surface (for example, With reference to patent document 1), film can also slided relative to conveying roller, but due to being laminated hard conating on the surface of the film, thus film is overall Thickness increase, mist degree rise.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-219485 publications
The content of the invention
The present invention in view of the above problems situation and complete, it solves problem and is to provide that a kind of transporting is good and mist The low optical film of degree, the manufacture method of this optical film, the polarizer and image display device for possessing this optical film.
Studied in order to solve above-mentioned problem involved in the present invention, the reason for above mentioned problem etc., its result hair It is existing, make to contain particulate and surface conditioner on the optical film containing cyclic olefin resins, by surface roughness in the optical film two sides The surface roughness Ra in face high Ra is set in the range of specified value, can provide the optical film that transporting is good and mist degree is low.
That is, problem involved in the present invention is solved by the following method.
1. a kind of optical film, it is characterised in that containing cyclic olefin resins, particulate and surface conditioner,
Above-mentioned surface conditioner contains in organosilicon material, fluorine system material, vinyl based material and acrylic material At least one,
The surface roughness Ra in the high face of surface roughness Ra is in the range of 3.0~50.0nm in film two sides.
2. the optical film as described in the 1st, it is characterised in that
The surface roughness Ra in the low face of surface roughness Ra is in the range of 2.0~20.0nm in film two sides,
The difference of the surface roughness Ra on film two sides is more than 1.0nm.
3. the optical film as described in the 1st or the 2nd, it is characterised in that above-mentioned particulate contains silicon compound.
4. a kind of manufacture method of optical film, it is characterised in that be to manufacture the light any one of the 1st~the 3rd The manufacture method of the optical film of film is learned,
Manufactured by using the solution-casting method of more than two kinds of solvent.
5. a kind of polarizer, it is characterised in that possess：
The polarizer and
Optical film any one of 1st~the 3rd.
6. the polarizer as described in the 5th, it is characterised in that the above-mentioned polarizer is adhered to table in the two sides of above-mentioned optical film Face low surface roughness Ra.
7. a kind of image display device, it is characterised in that possess the optical film any one of the 1st~the 3rd.
According to the present invention it is possible to provide the optical film, the manufacture method of this optical film, tool that transporting is good and mist degree is low The polarizer and image display device of standby this optical film.
For the expression mechanisms or the mechanism of action of the effect of the present invention, although not yet clearly, but be presumed as follows.
In general, by the way that the coating of the composition containing optical film is poured on supporter and makes solvent from the film Shape thing dry and obtain film solution-casting method manufacture optical film when, from by membranoid substance from supporter peel off when fissility sight Point is set out, and low boiling point solvent is preferably contained in coating as good solvent.
Speculate when making optical film by this method, above-mentioned particulate and the surface conditioner shape in coating, membranoid substance Into association body, the compatibility of the association body and good solvent is high.Therefore, the process dried in the membranoid substance that will be poured on supporter In, above-mentioned association body is moved to the surface of the Air Interface side of membranoid substance together with the good solvent volatilized from membranoid substance, in the shape Immobilization under state and manufacture optical film.Thus, it is possible to make particulate and surface conditioner one be polarized be optical film one side, by light Learn one side (surface of Air Interface side) in the two sides of film optionally to chap, as a result, embodying significant sliding.Pass through To optical film assign sliding, transporting improve, and can be not provided with diaphragm, hard conating and suppress surface irregularity, rise The generation of wrinkle, and to make polarizer in high yield.In addition, by containing particulate together with surface conditioner, particulate can be made inclined It is the one side of optical film and optionally assigns sliding, therefore the content of particulate can be reduced, mist degree can be made low Optical film.And then, by also assigning sliding to the one side of optical film in the coiling process when manufacturing optical film, it can suppress The generation of wrapping offset etc..
Embodiment
The optical film of the present invention, it is characterised in that be the optical film containing cyclic olefin resins, particulate and surface conditioner, Above-mentioned surface conditioner contains at least one in organosilicon material, fluorine system material, vinyl based material and acrylic material, The surface roughness Ra in the high face of surface roughness Ra is in the range of 3.0~50.0nm in film two sides.This feature is and each power Profit requires common or corresponding technical characteristic.
In the present invention, the surface roughness Ra in the low face of surface roughness Ra is 2.0~20.0nm's preferably in film two sides In the range of, the difference of the surface roughness Ra on film two sides is more than 1.0nm.Thus, the polarizer is made to fit in above-mentioned rough surface When spending the low faces of Ra and making polarizer, due to concavo-convex few compared with another side, it is difficult to produce with the bonding interface of the polarizer Gap and the scattering that light can be suppressed, the problems such as effectively can suppressing light leak when being equipped on image display device.In addition, passing through The surface roughness Ra in the low face of above-mentioned surface roughness Ra within the above range, sliding is also embodied in the face, can enter one Step improves transporting.In addition, it is poor by there is the surface roughness Ra on film two sides, haze value can be kept as relatively low and carried The transporting of high optical film.
In addition, in the present invention, above-mentioned particulate preferably comprises silicon compound.Thus, the compatibility of particulate and surface conditioner Improve, optical film can be such that particulate is more reliably moved in film when being film-made, and can more reliably obtain good transporting.
The manufacture method of the optical film of the present invention is the manufacture method for the optical film for manufacturing above-mentioned optical film, and its feature exists In being manufactured by using the solution-casting method of more than two kinds of solvent.Thus, it is possible to manufacture, transporting is good and mist degree is low Optical film.
The polarizer of the present invention is characterised by possessing the polarizer and above-mentioned optical film.Thus, it is possible to which it is low that mist degree is made Polarizer.
In the present invention, the above-mentioned polarizer is preferably adhered to the low face of surface roughness Ra in the two sides of above-mentioned optical film.By This, the transporting of optical film is may insure when polarizer makes, can be to obtain polarizer in high yield.
The image display device of the present invention is characterised by possessing above-mentioned optical film.Thus, it is possible to improve visuality.
Hereinafter, said in detail to the present invention and its inscape and for the form mode for implementing the present invention It is bright.It should illustrate, in this application, "~" is to be used as lower limit and the meaning of higher limit comprising numerical value described before and after it Come what is used.
《1. the summary of optical film》
The optical film of the present invention, it is characterised in that be the optical film containing cyclic olefin resins, particulate and surface conditioner, Surface conditioner contains at least one in organosilicon material, fluorine system material, vinyl based material and acrylic material, film two The surface roughness Ra in the high face of surface roughness Ra is in the range of 3.0~50.0nm in face.In addition, the optical film of the present invention The solvent used when various additives described later, film film can also further be contained as residual solvent.
1-1. cyclic olefin resins
The cyclic olefin resins contained in the optical film of the present invention are preferably the polymer or cycloolefin monomers of cycloolefin monomers With the copolymer of the co-polymerized monomer in addition to it.
Cycloolefin monomers are used as, it is however preferred to have the cycloolefin monomers of ENB skeleton, more preferably with by following The cycloolefin monomers for the structure that formula (A-1) or (A-2) are represented.
Formula (A-1)
In formula (A-1), R1~R4Hydrogen atom, the alkyl or polar group of carbon number 1~30 are represented independently of one another. P represents 0~2 integer.Wherein, all R1~R4Earth's surface shows hydrogen atom, R when different1And R2Earth's surface shows hydrogen atom, R when different3With R4Earth's surface shows hydrogen atom when different.
As in formula (A-1) by R1~R4The alkyl of the carbon number 1~30 of expression, for example, it is preferable to be carbon number 1 The alkyl of~10 alkyl, more preferably carbon number 1~5.The alkyl of carbon number 1~30 for example can also further have Include the connecting group of halogen atom, oxygen atom, nitrogen-atoms, sulphur atom or silicon atom.The example of this connecting group includes carbonyl The polar group of the divalents such as base, imino group, ehter bond, silyl ether bond, thioether bond.The example bag of the alkyl of carbon number 1~30 Containing methyl, ethyl, propyl group and butyl etc..
By R in formula (A-1)1~R4The example of the polar group of expression includes carboxyl, hydroxyl, alkoxy, alkoxy carbonyl Base, aryloxycarbonyl, amino, amide groups and cyano group.Wherein, preferably carboxyl, hydroxyl, alkoxy carbonyl and aryloxycarbonyl, From the viewpoint of dissolubility when ensuring solution film-forming, preferably alkoxy carbonyl and aryloxycarbonyl.
From the viewpoint of the heat resistance for improving optical film, the preferred expressions 1 or 2 of p in formula (A-1).Because, if P represents 1 or 2, then the volume increase of the polymer of gained, and glass transition temperature is easily improved.
Formula (A-2)
In formula (A-2), R5Represent hydrogen atom, the alkyl of carbon number 1~5 or the alkyl with carbon number 1~5 AIkylsilyl groups.R6Represent carboxyl, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, amide groups, cyano group or halogen Atom (fluorine atom, chlorine atom, bromine atoms or iodine atom).The integer of p tables 0~2.
R in formula (A-1)5It is preferred that representing the alkyl of carbon number 1~5, the hydrocarbon of carbon number 1~3 is more preferably represented Base.
R in formula (A-2)6It is preferred that represent carboxyl, hydroxyl, alkoxy carbonyl and aryloxycarbonyl, from ensuring solution system From the viewpoint of dissolubility during film, more preferably alkoxy carbonyl and aryloxycarbonyl.
From the viewpoint of the heat resistance for improving optical film, the preferred expressions 1 or 2 of p in formula (A-2).Because, if P is 1 or 2, then the volume increase of the polymer of gained, and glass transition temperature is easily improved.
Cycloolefin monomers with the structure represented by formula (A-2) are in terms of in organic solvent deliquescent is improved Set out to be preferred.In general, organic compound reduces crystallinity by destroying symmetry, therefore in organic solvent molten Solution property is improved.R in formula (A-2)5And R6Symmetry axis relative to molecule is only substituted in the ring structure carbon atom of one side, therefore The symmetry of molecule is low, thus, and the dissolubility of the cycloolefin monomers with the structure represented by formula (A-2) is high, is suitable for leading to Cross the situation that solution-casting method manufactures optical film.
The content ratio of the cycloolefin monomers with the structure represented by formula (A-2) in the polymer of cycloolefin monomers 70 moles of more than % can be for example set to relative to the total of whole cycloolefin monomers for constituting cyclic olefin resins, 80 are preferably set to Mole more than %, is more preferably set to 100 moles of %.If containing certain ring with the structure represented by formula (A-2) above Olefinic monomer, then the orientation of resin is improved, therefore phase difference value easily rises.
Hereinafter, will have by formula (A-1) represent structure cycloolefin monomers particular instantiation in exemplary compounds 1~ 14, there will be the particular instantiation of cycloolefin monomers of the structure represented by formula (A-2) in exemplary compounds 15~34.
Can with the example of the co-polymerized monomer of cycloolefin monomers copolymerization comprising can be with cycloolefin monomers ring opening copolymer copolymerization Property monomer and can be with the co-polymerized monomer of cycloolefin monomers addition copolymerization etc..
Can ring opening copolymer co-polymerized monomer example include cyclobutane, cyclopentene, cycloheptene, cyclo-octene and two rings penta 2 The cycloolefins such as alkene.
Can addition copolymerization co-polymerized monomer example include compound containing unsaturated double-bond, ethene base system cyclic hydrocarbon monomer (methyl) acrylate etc..The example of the compound containing unsaturated double-bond includes the alkene of carbon number 2~12 (being preferably 2~8) Ethene, propylene and butylene etc. are included in hydrocarbon system compound, its example.The example of ethene base system cyclic hydrocarbon monomer includes 4- vinyl The vinylcyclopentene system monomer such as cyclopentene and 2- methyl -4- isopropenyl cyclopentene.The example of (methyl) acrylate is included The carbon number 1~20 such as (methyl) methyl acrylate, (methyl) 2-EHA and (methyl) cyclohexyl acrylate (methyl) alkyl acrylate.
The content ratio of cycloolefin monomers in the copolymer of cycloolefin monomers and co-polymerized monomer is relative to composition copolymerization The total of whole monomers of thing can for example be set to 20~80 moles of %, be preferably set to 30~70 moles of %.
As described above, cyclic olefin resins are the cycloolefin monomers with ENB skeleton, it is preferably to have by formula (A-1) or (A-2) represent structure cycloolefin monomers polymerization or copolymerization obtained from polymer, its example include following chemical combination Thing.
(1) ring-opening polymerization polymer of cycloolefin monomers
(2) cycloolefin monomers and ring-opening copolymer that can be with the co-polymerized monomer of its ring opening copolymer
(3) hydride of the open loop (co) polymer of above-mentioned (1) or (2)
(4) after the open loop (co) polymer of above-mentioned (1) or (2) is cyclized by Knut Fridell-Kerafyrm thatch reaction The (co) polymer hydrogenated
(5) cycloolefin monomers and the saturated copolymer of the compound containing unsaturated double-bond
(6) with the addition copolymer and its hydride of the ethene base system cyclic hydrocarbon monomer of cycloolefin monomers
(7) alternate copolymer of cycloolefin monomers and (methyl) acrylate
The polymer of above-mentioned (1)~(7) can for example pass through Japanese Unexamined Patent Publication 2008- by any known method Method described in No. 107534 publications, Japanese Unexamined Patent Publication 2005-227606 publications and obtain.For example, the open loop of above-mentioned (2) is total to The catalyst that is used in poly-, solvent for example can be used described in 0019~0024 section of Japanese Unexamined Patent Publication 2008-107534 publications Catalyst, solvent.Japanese Unexamined Patent Publication 2008-107534 for example can be used in the catalyst used in the hydrogenation of above-mentioned (3) and (6) Catalyst described in 0025~0028 section of publication.The acidification used in the Knut Fridell of above-mentioned (4)-Kerafyrm thatch reaction The acid compound described in 0029 section of Japanese Unexamined Patent Publication 2008-107534 publications for example can be used in compound.Above-mentioned (5)~ (7) 0058~0063 section of Japanese Unexamined Patent Publication 2005-227606 publications for example can be used in the catalyst used in addition polymerization Described in catalyst.The alternating copolymerization of above-mentioned (7) can for example pass through Japanese Unexamined Patent Publication 2005-227606 publications Method described in 0071 and 0072 section is carried out.
Wherein, the polymer of preferably above-mentioned (1)~(3) and (5), the polymer of more preferably above-mentioned (3) and (5).That is, From the glass transition temperature and raising light transmission aspect of the cyclic olefin resins that can improve gained, cyclic olefin resins are excellent Choosing is comprising the construction unit represented by following formulas (B-1) and by least one in the construction unit of following formulas (B-2) expression Person, more preferably only include by formula (B-2) represent construction unit, or comprising the construction unit represented by formula (B-1) and by Both construction units that formula (B-2) is represented.The construction unit represented by formula (B-1) is Lai freely above-mentioned formula (A-1) The construction unit of the cycloolefin monomers of expression, the construction unit represented by formula (B-2) represents Lai freely above-mentioned formula (A-2) Cycloolefin monomers construction unit.
Formula (B-1)
In formula (B-1), X represents-CH=CH- or-CH2CH2-。R1~R4With the R of p respectively with formula (A-1)1~R4And p It is synonymous.
Formula (B-2)
In formula (B-2), X represents-CH=CH- or-CH2CH2-.R5、R6With the R of p respectively with formula (A-2)5、R6And p It is synonymous.
Cyclic olefin resins involved in the present invention can also be commercially available product.The example of the commercially available product of cyclic olefin resins is included The Arton G (such as G7810) of JSR Corp., Arton F, Arton R (such as R4500, R4900 and R5000) With Arton RX.
Inherent viscosity (η) inh of cyclic olefin resins is preferably 0.2~5cm at 30 DEG C3/ g, more preferably 0.3~3cm3/ G, more preferably 0.4~1.5cm3/g。
The number-average molecular weight (Mn) of cyclic olefin resins is preferably 8000~100000, and more preferably 10000~80000, enter One step is preferably 12000~50000.The weight average molecular weight (Mw) of cyclic olefin resins is preferably 20000~300000, more preferably 30000~250000, more preferably 40000~200000.The number-average molecular weights of cyclic olefin resins, weight average molecular weight can be with It is measured by gel permeation chromatography (GPC) with polystyrene conversion.
If inherent viscosity (η) inh, number-average molecular weight and weight average molecular weight are in above range, cyclic olefin resins it is heat-resisting Property, water resistance, resistance to chemical reagents, mechanical property and good as the molding processibility of film.
The glass transition temperature (Tg) of cyclic olefin resins is usually more than 110 DEG C, preferably 110~350 DEG C, more preferably For 120~250 DEG C, more preferably 120~220 DEG C.If Tg is more than 110 DEG C, easily suppress under the high temperature conditions Deformation.On the other hand, if Tg is less than 350 DEG C, processing and forming becomes easy, also easily suppresses by hot institute during processing and forming The deterioration of the resin of cause.
The content of cyclic olefin resins does not include whole compositions of solvent relative in the material for constituting optical film, is preferably More than 70 mass %, more preferably more than 80 mass %.
1-2. particulates
Number average bead diameter when particulate involved in the present invention refers to be measured using transmission electron microscope is 400nm Following particle.In this case, the particle diameter of each particle is converted into phase as by the perspective plane in transmission electron microscope Defined with the diameter of the bowlder of area.In order to not produce the wavelength of unwanted scattering, the preferably particle diameter of particulate and visible ray Compared to very small, specifically, 1~200nm is preferred scope, more preferably 1~100nm scope, particularly preferably 5~ 60nm scope.The shape of particle is not limited to spherical or unsetting shape.
Can be inorganic particles or organic fine particles as particulate involved in the present invention.In addition it is also possible to be The inorganic particles of surface modification are carried out with organic compound.
As inorganic particles, for example, it is preferable to be the compound (silicon compound) comprising silicon, aluminum oxide, zirconium oxide, carbonic acid Calcium, talcum, clay, calcined kaolin, baked calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc., further Preferably silicon compound, aluminum oxide, particularly preferably using silica.They can enumerate spherical, tabular or without given shape (No shape shape) etc. shape particle.
As the particulate of silica, for example can be used AEROSIL R972, R972V, R972CF, R974, R812,50, 200th, 200V, 300, R202, OX50, TT600, R711, RY300, R106, R816, RA200HS, MOX170 (more than, Japan AEROSIL Co. Ltd. systems) etc. commercially available product.
As the particulate of aluminum oxide, for example can be used AEROSIL Alu C, Alu130 and Alu C805 (more than, Japan AEROSIL Co. Ltd. systems) etc. commercially available product.
In addition, as organic fine particles, for example, polystyrene resin, organic siliconresin, polyvinyl resin, epoxy can be enumerated What resin, polycarbonate resin, melmac etc., acrylic-styrene resin, melamine-silica etc. were combined Particulate, but it is not limited to them.
In addition, these inorganic particles and organic fine particles can be used alone, and two or more can also be used.In addition, using During organic fine particles, the few organic fine particles of the difference of the refractive index in single dispersing and the refractive index of resin are preferably used.
The content of particulate does not include whole compositions of solvent relative in the material for constituting optical film, preferably 0.01~ In the range of 5.0 mass %, more preferably in the range of 0.05~3.0 mass %.
1-3. surface conditioners
Surface conditioner refers to containing organosilicon material, fluorine system material, vinyl based material and acrylic acid series in the present invention At least one surface conditioner in material.
As organosilicon material, for example, it is preferable to using silicone based surfactants etc., as fluorine system material, for example, excellent Choosing is using fluorine system surfactant, fluoro- polysiloxane grafted compound or fluorine system compound etc., as vinyl based material, for example, Ethylenic copolymer, vinyl-polysiloxane grafted compound etc. is preferably used, as acrylic material, for example, it is preferable to use Acrylic acid-organosilicon graft compound, acrylic copolymer etc..
Here, organosilicon material refers to the oligomer or polymer as repeat unit with siloxane backbone.The silica Alkane repetitive structure can have as main chain, can also have as the side chain of grafting.
Fluorine system material refers to oligomer or polymer containing fluorine atom at least one repeat unit.The fluorine-containing repetition is tied Structure can have as main chain, can also have as the side chain of grafting.
Vinyl based material refers in repeat unit containing at least one kind of oligomer in vinyl, vinylidene, vinylene Or polymer.This, which contains vinyl repetitive structure, to have as main chain, can also have as the side chain of grafting.
Acrylic material refers to the oligomer or polymer in repeat unit with acryloyl group.This contains acryloyl group weight Complex structure can have as main chain, can also have as the side chain of grafting.
As silicone based surfactants, for example, organic silicon modified by polyether, acryl-modified silicone resin etc. can be enumerated, GL serial (for example, GL-01, GL-02R, GL-03, GL-04R etc.), the day letter chemistry of chemical company of above-mentioned common prosperity society can be enumerated Industrial group Silface series (for example, Silface SAG002, Silface SAG005, Silface SAG008, Silface SAG503A etc.) etc..
As fluorine system surfactant, for example, the Megafac RS series of Dainippon Ink Chemicals, Megafac can be enumerated F-444, Megafac F-556 etc..
Fluoro- polysiloxane grafted compound be instigate the polysiloxanes comprising siloxanes and/or organosiloxane simple substance and/or Compound of the organopolysiloxane at least with copolymer obtained from fluorine resin grafting.In addition, as commercially available product, can enumerate ZX-022H, ZX-007C, ZX-049, ZX-047-D of Fuji's chemical conversion industry Co. Ltd. system etc..
In addition, as fluorine system compound, OPTOOL DSX, the OPTOOL DAC of Daikin Industrial Co., Ltd can be enumerated Deng.
As acrylic copolymer, the BYK-350 of BYK Japan company systems, BYK-352 etc. can be enumerated.
As surface conditioner involved in the present invention, in addition to above-mentioned surface conditioner, following commercially available product can be used.Example Kao Corp's system can such as be enumerated：Emulgen 102KG、Emulgen 104P、Emulgen 105、Emulgen 106、 Emulgen 108、Emulgen 109P、Emulgen 120、Emulgen 123P、Emulgen 147、Emulgen 210P、 Emulgen 220、Emulgen 306P、Emulgen 320P、Emulgen 404、Emulgen 408、Emulgen 409PV、 Emulgen 420、Emulgen 430、Emulgen 705、Emulgen 707、Emulgen 709、Emulgen 1108、 Emulgen 1118S-70、Emulgen 1135S-70、Emulgen 2020G-HA、Emulgen 2025G、Emulgen LS- 106th, Emulgen LS-110, Emulgen LS114, Nishin Chemical Industry Co. Lt's system：Surfynol 104E、 Surfynol 104H、Surfynol 104A、Surfynol 104BC、Surfynol 104DPM、Surfynol 104PA、 Surfynol 104PG-50、Surfynol 104S、Surfynol 420、Surfynol 440、Surfynol 465、 Surfynol 485, Surfynol SE, Shin-Etsu Chemial Co., Ltd's system：FA-600、KC-89S、KR-500、KR-516、 X-40-9296、KR-513、X-22-161A、X-22-162C、X-22-163、X-22-163A、X-22-164、X-22-164A、X- 22-173BX、X-22-174ASX、X-22-176DX、X-22-343、X-22-2046、X-22-2445、X-22-3939A、X-22- 4039、X-22-4015、X-22-4272、X-22-4741、X-22-4952、X-22-6266、KF-50-100cs、KF-96L- 1cs、KF-101、KF-102、KF-105、KF-351、KF-352、KF-353、KF-354L、KF-355A、KF-393、KF-615A、 KF-618、KF-857、KF-859、KF-860、KF-862、KF-877、KF-889、KF-945、KF-1001、KF-1002、KF- 1005、KF-2012、KF-2201、X-22-2404、X-22-2426、X-22-3710、KF-6004、KF-6011、KF-6015、 KF-6123, KF-8001, KF-8010, KF-8012, X-22-9002 etc..
The content of surface conditioner does not include whole compositions of solvent relative in the material for constituting optical film, preferably exists In the range of 0.01~5.0 mass %, more preferably in the range of 0.05~3.0 mass %.Pass through the content of surface conditioner For more than 0.01 mass %, the effect of the present invention can be given full play to, can be by the mist degree of film by for below 5.0 mass % Suppress low and more reliably assign sliding.
The other additives of 1-4.
As described above, the optical film of the present invention can also further contain other additives.It is used as this additive, example Such as, ultra-violet absorber, antioxidant etc. can be enumerated.
(ultra-violet absorber)
The optical film of the present invention can also contain ultra-violet absorber as additive.
Ultra-violet absorber absorbs below 400nm ultraviolet, therefore can improve the durability of optical film.Ultraviolet is inhaled It is preferably less than 10% to receive transmissivity of the agent especially under wavelength 370nm, more preferably less than 5%, more preferably 2% Below.
As the concrete example of ultra-violet absorber, it is not particularly limited, for example, epoxide benzophenone series chemical combination can be enumerated Thing, BTA based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, three Piperazine based compound, nickel complex salt based compound, inorganic particle etc., particularly preferably BTA based compound and benzophenone series Compound etc..
As ultra-violet absorber, more specifically, for example, 5- chloro- 2- (3,5- di-sec-butyl -2- hydroxy benzenes can be used Base) -2H- BTAs, (2-2H- BTA -2- bases) -6- (straight chain and side chain dodecyl) -4- methylphenols, 2- hydroxyls Base -4- behzyloxybenzophenones, 2,4- behzyloxybenzophenones etc..They can also use commercially available product, for instance, it may be preferable to use (octyl group -3- [3- tertiary butyl-4-hydroxies -5- (the chloro- 2H- BTAs -2- of 5- of Tinuvin 109 of BASF Japan company systems Base) phenyl] propylene and 2- ethylhexyls -3- [3- tertiary butyl-4-hydroxies -5- (the chloro- 2H- BTAs -2- bases of 5-) phenyl] The mixture of propylene), Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, (2- (2H- BTA -2- bases) -6- (1- methyl isophthalic acids-the phenylethyl) -4- (1,1,3,3- tetramethyl butyls) of Tinuvin 928 Phenol) etc. Tinuvin classes.
In addition, the discoid compound such as compound with 1,3,5-triazines ring also serves as ultra-violet absorber and preferably made With.In addition, as ultra-violet absorber, polymeric UV absorber can also be preferably used, particularly preferably using polymer The ultra-violet absorber of type.
As triazine system ultra-violet absorber, the Tinuvin of the BASF JAPAN company systems as commercially available product can be used 400 (the reaction generations of 2- (double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazine -2- bases of 4,6-) -5- hydroxy phenyls and oxirane Thing), Tinuvin 460 (2,4- double [2- hydroxyl -4- butoxy phenyls] -6- (2,4- dibutoxies phenyl) -1,3-5- triazines), Tinuvin 405 (2- (2,4- dihydroxy phenyls) -4,6- pairs-(2,4- 3,5-dimethylphenyls) -1,3,5- triazines and (2- ethyl hexyls Base)-glycidic ester reaction product) etc..
, can also be in the alcohol such as methanol, ethanol, butanol, dichloromethane, acetic acid first as the adding method of ultra-violet absorber Dissolved in the organic solvents such as ester, acetone or dioxolanes or their mixed solvent after ultra-violet absorber, make an addition to optical film Manufacture in the resin solution (coating) that uses, or directly make an addition in coating.It is not dissolved in as inorganic particle organic The material of solvent uses dissolvers, puddle mixer in organic solvent and cellulose acetate, made an addition to after disperseing in coating.
As the content of ultra-violet absorber, for example, being preferably 0.5~10 mass % scope relative to optical film, enter One step is preferably 0.6~4 mass % scope.
(antioxidant)
The optical film of the present invention can also be used as other additives containing antioxidant (deterioration preventing agent).
As antioxidant, preferably use the compound of hindered phenol series, can for example enumerate 2,6- di-t-butyls-paracresol, Pentaerythrite base-four (3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester), triethylene glycol-bis- (3- (the 3- tert-butyl group -5- first Base -4- hydroxy phenyls) propylene), 1,6-HD-bis- (3- (3,5- di-tert-butyl-hydroxy phenyls) propylene), 2,4- Double (the 3- of double-(just pungent sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butyls amido) -1,3,5- triazines, 2,2- thiodiethylenes (3,5- di-tert-butyl-hydroxy phenyls) propylene), octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propylene, N, N '-hexamethylene bis (3,5- di-t-butyl -4- hydroxy-hydrocineamides), (3,5- of 1,3,5- trimethyls -2,4,6- three Di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5- di-tert-butyl-4-hydroxyl benzyls)-isocyanuric acid esters etc..
The content of antioxidant is for example preferably 1~10000 mass ppm scope relative to optical film, further preferably For 10~1000 mass ppm scope.
The physical property of 1-5. optical films
(surface roughness Ra)
The surface roughness Ra in the high face of surface roughness Ra is 3.0~50.0nm's in the two sides of the optical film of the present invention In the range of, preferably in the range of 4.0~40.0nm.If surface roughness Ra is more than 3.0nm, the sliding of optical film is carried Height, can suppress the surface irregularity in conveying, wrinkle.If surface roughness Ra is below 50nm, it can suppress by light Haze value, can be set to low value by the scattering of the light caused by the bumps on film surface.In addition, the surface roughness in the present invention Ra is JIS B0601：Arithmetic average roughness specified in 2001 (Ra).
In addition, the surface roughness Ra in the low face of surface roughness Ra is preferably 2.0 in the two sides of the optical film of the present invention In the range of~30.0nm, more preferably in the range of 2.0~20.0nm.By making surface roughness Ra value within the range, When making polarizer making the polarizer fit in the low face of surface roughness Ra of optical film, the high face with surface roughness Ra It is few compared to bumps, therefore it is difficult to generation gap in the bonding interface with the polarizer, the scattering of light can be suppressed, therefore can take Effectively suppress light leak when being loaded in liquid crystal display device.
Here, as described above, being contained in the film containing cyclic olefin resins together with surface conditioner by making particulate, it can make Particulate and surface conditioner are largely present in the one side (surface of Air Interface side during film) of film, the particulate and surface modulation Agent is also partly present in the another side (surface of supporter (for example, metal support described later) side during film) of film.
It is thought that because in the drying process of the membranoid substance in the manufacture of optical film, solvent is good solvent, therefore excellent First volatilize, but there is also some non-volatile good solvent compositions untill the terminal stage dried, therefore it is molten in the good solvent The above-mentioned association body of agent exists in the another side of film.Therefore, compared with the one side with film if particulate and surface conditioner Amount is few, but particulate and surface conditioner are formed with association body, therefore can obtain that particle diameter is big, scope described above surface is thick Rugosity Ra.
As the method by the surface roughness Ra control of above-mentioned another side within the above range, it can enumerate and suitably adjust micro- The method of stretching condition when the content of grain and surface conditioner, film are manufactured.
And then, the difference of the surface roughness Ra on optical film two sides is preferably more than 1.0nm.By making the surface on film two sides thick It is poor that rugosity Ra is present, and haze value can be kept as to transporting that is low and improving optical film.
In addition, surface roughness Ra can be measured with the surface roughness measurement device of light interference type, for example, it can be used Optical interference formula surface roughness meter RST/PLUS (WYKO company systems) is measured.
(optical characteristics)
The total light transmittance of optical film is preferably more than 90%, and more preferably more than 92%.In addition, being used as the upper of reality Limit, is 99% or so.Haze value is preferably less than 10%, and more preferably less than 2%.Total light transmittance and haze value can divide Not be measured according to JIS K7361 and JIS K7136.
(length of delay)
The use of the optical film of the present invention is not particularly limited, and can be used as polaroid protective film, can also Used as phase retardation film.As phase retardation film in use, various length of delays can be obtained according to its purposes.
For example, the present invention optical film be used as VA liquid crystal phase retardation film when, determine wavelength 590nm, 23 DEG C The length of delay Ro in direction preferably meets 10nm≤Ro≤100nm in the face determined in the environment of 55%RH, more preferably meets 20nm ≤Ro≤80nm.The length of delay Rt of thickness direction preferably meets 70nm≤Rt≤200nm, more preferably meet 90nm≤Rt≤ 150nm。
In addition, length of delay Ro and Rt are the values defined with following formula (i) and (ii).
Formula (i)：Ro=(nx-ny)×d
Formula (ii)：Rt={ (nx+ny)/2-nz}×d
(in formula (i) and (ii), nxRepresent the refractive index of the slow-axis direction in optics face, nyRepresent in optics face with The refractive index in the vertical direction of slow axis, nzThe refractive index of the thickness direction of optical film is represented, d represents the thickness (nm) of optical film.)
When the optical film of the present invention is used as into λ/4 film, surveyed in the environment of wavelength 590nm, 23 DEG C of 55%RH are determined The length of delay Ro in direction preferably meets 50nm≤Ro≤250nm in fixed face, more preferably meets 70nm≤Ro≤200nm.Thickness The length of delay Rt in direction preferably meets -200nm≤Rt≤200nm, more preferably satisfaction -120nm≤Rt≤120nm.
In addition, when the optical film of the present invention is used as into zero phase difference film, determining wavelength 590nm, 23 DEG C of 55%RH In the environment of in the face that determines the length of delay Ro in direction preferably meet 0nm≤Ro≤5nm, the length of delay Rt of thickness direction is preferably full Foot -5nm≤Rt≤5nm.
Automatic birefringence meter Axo Scan (Axo Scan Mueller Matrix for example can be used in above-mentioned length of delay Polarimeter：AcroMetrix company systems) obtained in the environment of 23 DEG C of 55%RH with wavelength 590nm.By using control The optical film of above-mentioned length of delay is made as, visual excellence during for image display devices such as contact panel, liquid crystal display devices, It is preferred from this respect.Length of delay can be by particulate, surface conditioner and other additives species or addition, optics Thickness or stretching condition of film etc. are adjusted.
(thickness)
From the viewpoint of above-mentioned length of delay Ro and Rt meets above range and filming, the thickness of optical film is for example preferred For 3~200 μm, more preferably 5~100 μm, more preferably 7~40 μm.Especially optical film of the invention, which is assigned, slides Property, therefore conveyance tension can be relaxed, can also have good transporting even if filming.
2. the manufacture method of optical film
The optical film of the present invention is manufactured by using the solution-casting method of more than two kinds of solvent.That is, light of the invention Learning the manufacture method of film preferably has following process：At least make cyclic olefin resins, particulate and surface conditioner be dissolved in two kinds with On solvent and obtain the process (coating preparation process) of coating (resin solution)；After supporter upper coating, peel off and Obtain the process (cast stripping process) of membranoid substance；And the process (drying process) for drying membranoid substance.In addition, of the invention Optical film manufacture method preferably cast stripping process and drying process between have stretching membranoid substance process (stretching Process), preferably with the process (coiling process) for batching the optical film of gained after drying process.
2-1. coating preparation processes
Coating preparation process is illustrated.Denseer can reduce of resin concentration in coating is being poured into metal support Rear drying load and be preferred, if but resin concentration overrich, load increase during filtering and filtering accuracy is deteriorated.As Have the concentration of the two effects, more preferably preferably 10~45 mass %, 15~40 mass % concurrently.
The solvent contained in coating and can use two or more, from production efficiency aspect preferably by the good solvent of resin It is used in mixed way with poor solvent, it is more from the preferred good solvent of deliquescent aspect of resin.Good solvent and poor solvent The preferred scope of blending ratio is that good solvent is 70~98 mass %, and poor solvent is 2~30 mass %.Here, with regard to good solvent For poor solvent, the solvent of independent dissolving resin used is defined as good solvent, by swelling or insoluble when being used alone The solvent of solution is defined as poor solvent.
In addition, as the combination for preparing useful organic solvent to coating, if can dissolve simultaneously cyclic olefin resins, its Its additive is then not particularly limited.For example, as chlorine-based organic solvent, dichloromethane, chloroform can be enumerated, had as chlorine-free Machine solvent, can enumerate methyl acetate, ethyl acetate, pentyl acetate, acetone, tetrahydrofuran, DOX, Isosorbide-5-Nitrae-two Alkane, hexamethylene, cyclohexanone, toluene, paraxylene, Ethyl formate, 2,2,2 tfifluoroethyl alcohol, 2,2,3,3- hexafluoro -1- propyl alcohol, 1, The fluoro- 2- propyl alcohol of 3- bis-, 1,1,1,3,3,3- hexafluoro -2- methyl-2-propanols, 1,1,1,3,3,3- hexafluoro -2- propyl alcohol, 2,2,3,3, The fluoro- 1- propyl alcohol of 3- five, nitroethane, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol etc., preferably Use dichloromethane, toluene, tetrahydrofuran, ethanol, acetone.
Coating is preferably to make total 15~45 mass % cyclic olefin resins, particulate, surface conditioner and other additives It is dissolved in the coating of above-mentioned solvent.
As the during preparation above-mentioned coating, dissolving method of resin in a solvent, usual way can be used.Especially from From the viewpoint of the coloring for reducing to the burden of dissolver, preventing resin, the dissolving preferably under normal temperature, normal pressure.
Then, the solution for being dissolved with the resin is filtered using the appropriate filtering material such as filter paper.As filtering material, it is Removing insoluble matter etc., preferably filtering precision is smaller, if but filtering precision is too small, and exist and easily produce filter material The problem of blocking of material.Therefore preferably filtering precision be below 0.008mm filter material, more preferably 0.001~ The filter material of 0.008mm filter material, more preferably 0.003~0.006mm.
The material of filter material is not particularly limited, and can be used common filter material, the plastics such as polypropylene, teflon (registration mark) The metal filter material such as filter material, the stainless steel of system does not have coming off for fiber, is preferred.It is preferred that by filtering the resin of raw material Contained impurity, bright spot foreign matter is especially removed, reduce.
Bright spot foreign matter refers to 2 polarizers being set to Nicol crossed state and configured, and optical film is set therebetween Deng in the side irradiation light from a polarizer, from during the unilateral observation of another polarizer, the light from opposite side spills and seen Point (foreign matter), the quantity of a diameter of more than 0.01mm bright spot is preferably 200/cm2Below.More preferably 100/cm2With Under, more preferably 50/m2Hereinafter, particularly preferably in 0~10/cm2In the range of.Furthermore it is preferred that below 0.01mm Bright spot is also less.
The filtering of coating can be carried out with usual way, while more than the boiling point under the normal pressure of solvent and under elevated pressure The difference (be referred to as differential pressure) of filtering pressure at a temperature of the scope of solvent not boiling before and after the heating filtering of the method for filtering on one side shows Show small, be preferred.Preferable temperature is 45~120 DEG C, more preferably more preferably 45~70 DEG C, 45~55 DEG C.
Filtering pressure is preferably smaller.Specifically, filtering pressure is preferably below 1.6MPa, more preferably below 1.2MPa, further Preferably below 1.0MPa.
2-2. pours into a mould stripping process
The coating of gained is sprayed and is poured into metal support from cast die orifice, the casting film of gained is dried Membranoid substance is obtained with stripping.Cast width can for example be set to 1~4m.As metal support, can be used with stainless steel band or The drum that casting material finishes surface plating.The surface of metal support preferably carries out minute surface finishing.In addition, being cast with coating Supporter is not limited to any material such as metal system or resin-made.
The surface temperature of metal support be -50 DEG C~be less than solvent boiling point temperature, temperature is higher can to improve film The rate of drying of shape thing, therefore be preferred, if too high, membranoid substance foaming, or flatness deterioration.Therefore, metal support Surface temperature is preferably 0~40 DEG C, more preferably 5~30 DEG C.
Control the method for temperature of metal support to have no particular limits, the method for blowing warm air or cold wind can be enumerated, made The method of warm water and the rear-face contact of metal support.Can effectively it be conducted heat using warm water, therefore the temperature of metal support Time of the degree as steady temperature is short, is preferred.
During using warm air, it is contemplated that the temperature drop of the tablet (ウ ェ Block) caused by the evaporation latent heat of solvent, use sometimes Warm air more than solvent boiling point, and prevent foaming while using the wind of the temperature higher than target temperature.
In order to obtain the membranoid substance with good flatness, the residual solvent of membranoid substance when being peeled off from metal support Amount is preferably 10~150 mass %, more preferably 20~40 mass % or 60~130 mass %, more preferably 20~30 Quality % or 70~120 mass %.
Here, the residual solvent amount of membranoid substance is defined by following formula.
Residual solvent amount (quality %)={ (M-N)/N } × 100
(in above-mentioned formula, M represents the quality of membranoid substance, and N represents the quality after the membranoid substance is heated 1 hour at 120 DEG C.)
2-3. drying processes
Drying process is below 1 mass % preferably by the membranoid substance drying peeled off from metal support to residual solvent amount, More preferably below 0.1 mass %, particularly preferably in the range of 0~0.01 mass %.Thus, it can obtain optical film.
It is general that membranoid substance (is alternately passed through by multiple rollers in configuration up and down using roller drying mode in film drying process And make its dry mode), while by stenter mode convey membranoid substance on one side make its drying in the way of.
Particularly preferably from be poured into peel off during change the temperature of above-mentioned metal support and the temperature of dry wind, it is high Effect it is dried.
In the present invention, it is believed that in coating, membranoid substance particulate and surface conditioner formation association body, the association body with it is good molten Agent compatibility is high, so that the association body is moved to air circle of film together with the good solvent volatilized from membranoid substance in drying process The surface of surface side, can obtain the optical film that particulate and surface conditioner are single-face side partially.
Thus, by manufacturing optical film with the solution-casting method for using more than two kinds of solvent, optical film can be assigned Sliding and improve transporting, just can make polarizer etc. in high yield without using diaphragm.
2-4. stretching process
In stretching process, membranoid substance obtained from stripping is stretched and carried out the adjustment of phase difference.
Stretching can be carried out at least in a direction.Draw direction can be the long side direction (MD directions) and film of membranoid substance The vertical broadside (TD directions) of the long side direction of shape thing and relative in the inclined direction of long side direction of membranoid substance Any one.Stretching can gradually be stretched or while stretch.
The stretching ratio of mutually perpendicular biaxially oriented it is preferred it is final respectively be in MD directions in the range of 1.0~2.0 times, In the range of TD directions is 1.05~2.0 times, more preferably in the range of MD directions is 1.0~1.5 times, it is in TD directions In the range of 1.05~2.0 times.It can for example enumerate and multiple rollers are applied with all speed differences, be drawn therebetween using all speed differences of roller in MD directions The method stretched；The two ends of membranoid substance are fixed with cloth gripper or needle plate, by cloth gripper or being spaced in direct of travel extension of needle plate in MD The method of direction stretching；Similarly it is extending transversely and TD directions stretch method；Or simultaneously in MD directions and the expansion of TD directions Method opened up and stretched in both direction etc..
These width in stretching process are kept or the stretching of broadside is preferably carried out by stenter, can be needle plates Stenter can also be clip stenter.
The film conveyance tension of stenter etc. also depends on temperature, preferably in the range of 120~200N/m, further preferably In the range of 140~200N/m, most preferably in the range of 140~160N/m.
When the glass transition temperature of optical film is set into Tg, temperature during stretching is preferably in (Tg-30)~(Tg+100) In the range of DEG C, more preferably in the range of (Tg-20)~(Tg+80) DEG C, further preferably at (Tg-5)~(Tg+20) DEG C In the range of.
The Tg of optical film can be controlled according to the ratio of the material category for constituting optical film and the material constituted.Optics The Tg during drying of film is preferably more than 110 DEG C, more preferably more than 120 DEG C, particularly preferably more than 150 DEG C.In addition, The Tg of optical film is preferably less than 190 DEG C, more preferably less than 170 DEG C.The Tg of optical film can be according to described in JIS K7121 Method etc. obtain.
, can if the temperature of optical film when stretching is set into more than Tg+10 DEG C, stretching ratio is set to more than 1.10 times To assign the roughness of appropriateness to the surface of optical film, therefore it is preferred.By assigning the roughness of appropriateness to optical film surface, Sliding is improved, and Surface Machining is improved, therefore is preferred.
2-5. coiling processes
In coiling process, the optical film of gained is batched with coiling machine.Method for coiling can use what is typically used Method, for example, the constant program tension control method of constant torque method, constant tension method, taper tension method, internal stress can be used Deng.
The optical film of the present invention is preferably strip, specifically, and preferred length is 100~7000m or so.This strip The optical film of shape usually can be carried in the form of the scroll for batching in the direction vertical relative to length direction as winding off spindle For.The width of optical film is preferably 1.3~4m, more preferably 1.4~2m.By the way that the length and width of optical film is set into the model Enclose the operational excellent of interior processing characteristics, optical film itself in the coating of functional layer etc..
Before batching, cut the end of optical film and be cut into the width as product, in order to prevent attaching in batching, wipe Two ends can also be implemented embossing processing (Embossing processing) by wound.As the method for embossing processing, it can enumerate by using in side The method that becket with relief pattern is heated to optical film, pressurizeed and be processed.The cloth gripper at optical film both ends Grip portion would generally deform and can not be used as product, therefore be removed, its cut off piece be reused as raw material.
《3. polarizer》
The polarizer of the present invention is characterised by possessing the polarizer and above-mentioned optical film.
The polarizer of the present invention can be made by general method.For example, it is preferable to which the optical film of the present invention is carried out into corona Processing, using fully saponified type polyvinyl alcohol water solution, the optical film through processing is attached at the dipping stretching in iodine solution and At least one side of the polarizer of making.In addition, the polarizer is preferably adhered to surface roughness in the two sides of the optical film of the present invention Face low Ra.
Can be attached in the another side of the polarizer above-mentioned optical film, as the KC8UX of commercially available product, KC4UX, KC4UY, KC8UY, KC6UA, KC4UA, KC4UE, KC4CZ, KC8UCR, KC4FR (Konica Minolta Co. Ltd. systems), Arton films (JSR Corp.'s system), Zeonor Film (Nippon Zeon Co. Ltd. systems) etc..
The polarizer is the element that passes through of light for the plane of polarization for only making certain orientation, it is now known that the representational polarizer be Polyethenol series polarizing coating.Polyethenol series polarizing coating, which has, to be made the polarizing coating of iodine staining on polyvinyl alcohol mesentery, makes dichroism The polarizing coating of dyeing.
Polyethenol series polarizing coating can carry out polyvinyl alcohol mesentery after uniaxial tension, be contaminated with iodine or dichroic dye The film (being preferably the film for further implementing durability processing with boron compound) of color or by polyvinyl alcohol mesentery After iodine or dichroic dye dyeing, the film for carrying out uniaxial tension (is preferably further to implement durability with boron compound The film of processing).The absorption axiss of the polarizer are generally parallel with maximum tension direction.
As the polarizer, for example, Japanese Unexamined Patent Publication 2003-248123 publications or Japanese Unexamined Patent Publication 2003-342322 can be used 1~4 mole of % of content of ethylene unit described in publication etc., the degree of polymerization 2000~4000, saponification degree 99.0~99.99 rub Your % ethylene modified polyvinyl alcohol.Wherein, the ethylene modified polyvinyl alcohol that hot water cut-out temperature is 66~73 DEG C is preferably used Film.
The thickness of the polarizer is preferably in the range of 5~30 μm, from the viewpoint grade of polarizer slimming is made, more preferably In the range of 5~20 μm.
《4. image display device》
The image display device of the present invention is characterised by possessing above-mentioned optical film.Thus, it is visual, no from that can play The aspect of excellent performance is preferred.As image display device, reflection-type, transmission-type, semi-transparent liquid crystal can be enumerated and shown The liquid crystal display device of the various type of drive such as showing device or TN types, STN types, OCB types, VA types, IPS types, ECB types, touch surface Panel display, organic EL display or plasma display system etc..
In addition, the optical film of the present invention can also be for example used in liquid crystal display device (by top side polarizer/liquid crystal list Member/following side polarizer is constituted) above the lower section of side polarizer use interior contact panel (the イ Application Na ー of contact panel component タ ッ チ パ ネ Le), the contact panel of capacitance-type etc..
Embodiment
Hereinafter, enumerate embodiment and specifically describe the present invention, but the present invention is not limited to them.It should illustrate, embodiment The expression of middle use " part " or " % ", then represents " mass parts " or " quality % " unless otherwise specified.
First, the various materials used in the present embodiment are illustrated.
(1) cyclic olefin resins
Arton G7810：ARTON-G7810 (JSR company systems), cyclic olefin resins are (by the monomer of formula (A-2) expression and its The copolymer (polymer of above-mentioned (5)) of its monomer, weight average molecular weight Mw=140000)
Arton R5000：ARTON-R5000 (JSR company systems), cyclic olefin resins (by formula (A-1) represent monomer with by The copolymer (polymer of above-mentioned (5)) of the monomer that formula (A-2) is represented and other monomers, weight average molecular weight Mw=50000)
Arton RX4500：ARTON-RX4500 (JSR company systems), cyclic olefin resins (by formula (A-1) represent monomer with The copolymer (polymer of above-mentioned (5)) of the monomer and other monomers that are represented by formula (A-2), weight average molecular weight Mw=63000)
Arton RH4900：ARTON-RH4900 (JSR company systems), cyclic olefin resins (by formula (A-1) represent monomer with The copolymer (polymer of above-mentioned (5)) of the monomer and other monomers that are represented by formula (A-2), weight average molecular weight Mw=57000)
(2) particulate
The particulate of (2-1) containing silicon compound
R812：The silicon dioxide microparticle (Japanese AEROSIL company systems) of surface modification is carried out with trimethyl silyl, is put down Equal primary particle size 7nm
R816：The silicon dioxide microparticle (Japanese AEROSIL company systems) of surface modification is carried out with acrylic, averagely once Particle diameter 12nm
R106：Silicon dioxide microparticle (the Japanese AEROSIL companies of surface modification are carried out with the silicyl of prestox ring four System), average primary particle diameter 7nm
R972V：The silicon dioxide microparticle (Japanese AEROSIL company systems) of surface modification is carried out with dimetylsilyl, Average primary particle diameter 12nm
200V：Silicon dioxide microparticle (Japanese AEROSIL company systems), average primary particle diameter 12nm
300V：Silicon dioxide microparticle (Japanese AEROSIL company systems), average primary particle diameter 7nm
RY300：Silicon dioxide microparticle (the Japanese AEROSIL companies of surface modification are carried out with the organic silicon ion of dimethyl System), average primary particle diameter 12nm
RA200HS：Silicon dioxide microparticle (the Japanese AEROSIL of surface modification is carried out with trimethyl silyl and amino Company system), average primary particle diameter 12nm
R711：Silicon dioxide microparticle (the Japanese AEROSIL companies of surface modification are carried out with methacryloxypropyl silane System), average primary particle diameter 12nm
MOX170：Silica/alumina particulate (Japanese AEROSIL company systems), average primary particle diameter 13nm
(2-2) other particulates
Alu130：Alumina particulate (Japanese AEROSIL company systems), average primary particle diameter 20nm
TiO2P90：Titanium dioxide fine particles (Japanese AEROSIL company systems), average primary particle diameter 20nm
Kraton RP6935：Styrene-ethylene-butylene-styrene block copolymer (Kraton Polymer Japan Co. Ltd. system), average primary particle diameter 18nm
(3) surface conditioner
(3-1) organosilicon material
GL-01：Acryl-modified silicone resin (chemical company of common prosperity society system), weight average molecular weight Mw=5200
GL-03：Acryl-modified silicone resin (chemical company of common prosperity society system), weight average molecular weight Mw=4100
GL-04R：Acryl-modified silicone resin (chemical company of common prosperity society system), weight average molecular weight Mw=4700
SAG005：Organic silicon modified by polyether (Xin chemical industry society system, Silface SAG005), weight average molecular weight Mw= 2800
SAG008：Organic silicon modified by polyether (Xin chemical industry society system, Silface SAG008), weight average molecular weight Mw= 7900
(3-2) fluorine system material
Lebron：TFE (Daikin company systems), weight average molecular weight Mw=2000
(3-3) vinyl based material
P-410EF：Polyvinyl (this chemical conversion of nanmu company system), weight average molecular weight Mw=4500
(3-4) acrylic material
LF-1984：Acrylate copolymer (this chemical conversion of nanmu company system), weight average molecular weight Mw=3000
230：Acrylate copolymer (this chemical conversion of nanmu company system), weight average molecular weight Mw=3500
《The making of optical film 101》
(preparations of silica dispersed dilute solutions)
After the ethanol of the AERO SIL R812 of 10 mass parts and 80 mass parts is mixed 30 minutes with dissolvers stirring, with Manton Gaulin (homogenizer) are disperseed, and prepare silica dispersions.Stir while in the silica of preparation The dichloromethane of 80 mass parts is put into dispersion liquid, after dissolvers stirring mixing 30 minutes, is filtered with particulate dispersed dilute solutions Device (AdvantechToyo Co., Ltd.：Polypropylene wind cartridge filter TCW-PPS-1N) carry out Filter and prepare silica dispersed dilute solutions.
(preparation of coating)
Above composition is put into closed container, heat, stir while be completely dissolved it, uses to pacify and accumulates filter paper plant formula The peace product filter paper No.24 of commercial firm is filtered, and prepares coating.
Then, equably it is poured on stainless steel band supporter using Strip casting film forming apparatus.In stainless steel band supporter On make solvent be evaporated to residual solvent amount untill 80 mass %, to peel off from stainless steel band supporter.The tablet of gained is protected The further evaporation solvent at 35 DEG C is held, 1.15m width is cut into, it is dried under 160 DEG C of drying temperature.Thereafter, one While after it is conveyed in 130 DEG C of drying device with multiple rollers while drying 15 minutes, 1.0m width is cut into, to film two ends Implement the annular knurl processing of width 10mm, 5 μm of height, batch as core, obtain optical film 101.The thickness of optical film 101 is 20 μ M, rolls up a length of 5000m.In addition, the stretching in the MD directions calculated by the rotating speed of stainless steel band supporter and the speed of service of stenter Multiplying power is 1.01 times.
《The making of optical film 102~109》
In the making of above-mentioned optical film 101, surface conditioner is changed to as described in Table 1, in addition, similarly to make Make optical film 102~109.
《The making of optical film 110~116》
In the making of above-mentioned optical film 102, turned into such as with the content of the particulate of the film finally given and surface conditioner Mode described in table 1 changes the addition of particulate and surface conditioner, in addition, similarly makes optical film 110~116.
《The making of optical film 117~128》
In the making of above-mentioned optical film 102, particulate is changed to as described in Table 2, in addition, similarly to make optics Film 117~128.
《The making of optical film 129~131》
In the making of above-mentioned optical film 102, cyclic olefin resins are changed to as described in Table 2, in addition, similarly to make Make optical film 129~131.
《The making (comparative example) of optical film 132》
In the making of above-mentioned optical film 102, using the particulate of film and the content of surface conditioner that finally give as such as table 2 Described mode changes the addition of particulate and surface conditioner, in addition, similarly makes optical film 132.
《The making (comparative example) of optical film 133》
In the making of above-mentioned optical film 101, when preparing coating without surface conditioner, in addition, similarly Make optical film 133.
《The making (comparative example) of optical film 134》
In the making of above-mentioned optical film 101, when preparing coating without particulate and surface conditioner, in addition, Similarly make optical film 134.
《The making (comparative example) of optical film 135》
So that diaphragm is peeled off into what is removed from the Zeonor Film ZF14 of commercially available Nippon Zeon company systems Film is optical film 135.
《The physical property measurement of optical film 101~135 and evaluation》
The following physical property measurement of the progress of optical film 101~135 to making and evaluation.Measurement result and evaluation result are shown In Tables 1 and 2.
(measure of surface roughness Ra)
By the value of the arithmetic surface roughness Ra on the two sides of each optical film of making according to JIS B0601 at 23 DEG C 55% It is measured under conditions of RH with optical interference formula surface roughness meter RST/PLUS (WYKO company systems).
Now,, will using the face contacted when making optical film with Air Interface as A faces in the two sides of each optical film The face contacted when making optical film with stainless steel band supporter is as B faces.
(evaluation of haze value)
Each optical film of making is cut into 3.0cm × 3.0cm size and test film is made.By the test film according to JIS K7136 determines mist degree under conditions of 23 DEG C of 55%RH with haze meter NDH-2000 (electricity Se Industrial Co., Ltd of Japan system) Value, is evaluated based on following benchmark.
○：Haze value is less than 2.0.
△：Haze value is 2.0 less than 5.0.
×：Haze value is more than 5.0.
【Table 1】
【Table 2】
《The making 201 of image display device》
(making of the polarizer)
Long side direction by the polyvinyl alcohol film of 120 μm of thickness in film carries out uniaxial tension (110 DEG C of temperature, stretching ratio 5 Times).It is impregnated in the aqueous solution being made up of iodine 0.075g, KI 5g, water 100g 60 seconds, next, being impregnated in by iodine Change in 68 DEG C of the aqueous solution that potassium 6g, boric acid 7.5g, water 100g are constituted.Washed, dried and obtained 20 μm of thickness The polarizer.The absorption axiss of the polarizer are parallel with its long side direction.
(making of the 1st polarizer (visible side polarizer))
Next, according to following processes 1~4, the optical film for above-mentioned making of being fitted in the one side of the polarizer of above-mentioned making 102, make polarizer in the KC4UA (polarizer protective film) of another side laminating Konica Minolta company systems.
Process 1：Corona discharge is carried out to the B faces of the optical film 102 of making, implements sided corona treatment.In addition, by Konica After Minolta company systems KC4UA (polarizer protective film) impregnates 90 seconds in 60 DEG C of 2 moles/L sodium hydroxide solution, enter Water-filling wash and dry and by the saponified of the side fitted with the polarizer.
Process 2：The polarizer is impregnated 1~2 second in the mass % of solid constituent 2 polyvinyl alcohol bonding agent groove.Next, Gently wipe away and be attached to after the excessive bonding agent of the polarizer, be configured at the optical film 102 that sided corona treatment is implemented in process 1 B faces on.
Process 3：The polarizer protective film that saponification process has been carried out by optical film 102 and the polarizer and in process 1 exists 20~30N/cm of pressure2, transporting velocity be about lower laminating in 2m/ minutes, obtain layered product.
Process 4：The layered product obtained in process 3 is dried drying in 2 minutes in 80 DEG C of drying machine, had 1st polarizer of the stepped construction of KC4UA (the polarizer protective film)/polarizer/optical film 102.
(making of the 2nd polarizer (backlight side polarizer))
Made in the same manner as making with the 1st polarizer with 102/ polarizer of optical film/KC4UA's (polarizer protective film) 2nd polarizer of stepped construction.
(making of image display device)
The Xperia Z2 D6502 (Sony Co. Ltd. systems) for preparing IPS modes use liquid crystal display device as portable.From The device peels off 2 polarizers, and the 1st polarizer of above-mentioned making is attached in the face of the visible side of liquid crystal cells via bonding agent, The 2nd polarizer of above-mentioned making is attached in the face of backlight side and makes image display device 1.
The attaching of 1st polarizer is carried out in the way of KC4UA turns into visible side.In addition, the attaching of the 2nd polarizer be with The mode that KC4UA turns into backlight side is carried out.
《The making of image display device 202~216》
Optical film 102 is changed as described in table 3 in the making of above-mentioned liquid crystal display device 201, in addition, Similarly make image display device 202~216.
《The making of image display device 217》
The optical film for the state being stripped in the making of above-mentioned liquid crystal display device 201 using diaphragm before removing 135 (being expressed as in table 3 " 135 (having PF) ") replace optical film 102, in addition, similarly make image display device 217.
《The evaluation of image display device 201~217》
Following evaluate is carried out to the image display device 201~217 of making.Evaluation result is shown in table 3.
(evaluation of surface irregularity during conveying)
Make above-mentioned 1 polarizer when, visually to confirm optical film in the conveying before just being fitted with the polarizer, according to Lower benchmark is evaluated.
○：Surface irregularity can not be observed completely.
△：Confirm surface irregularity at film end.
×：Integrally confirm surface irregularity in film.
(corrugated evaluation during conveying)
When making above-mentioned 1 polarizer, visually to confirm optical film in the conveying before just being fitted with the polarizer, according to Following benchmark is evaluated.
○：Corrugation can not be observed completely.
△：Confirm to wrinkle at film end.
×：Integrally confirm corrugation in film.
(evaluation of defect transfer)
The defect transfer to diaphragm cause is evaluated in the following manner.
That is, the 1st polarizer of above-mentioned making is cut into 1m2Size and test film is made, by the test film towards light source In the state of, with the number for the bright spot for visually determining point-like, evaluated according to following benchmark.The bright spot of the point-like of measure is made For the defect transferred from diaphragm.
○：The number of defect is less than 1/m2
×：The number of defect is 1/m2More than
(evaluation of light leak)
In the environment of 23 DEG C, 55%RH, by the backlight continuity point of the image display device 201~217 of above-mentioned making After lamp 1 week, (60 ° right for contrast of the measure in the direction of 60 ° of the normal direction inclination of the display picture from the image display device Than degree).Specifically, determine respectively when the image display device is shown in vain using the EZ-Contrast160D of ELDIM company systems 60 ° of directions brightness and the brightness in 60 ° of directions when making its black display, obtain their ratio (60 ° of contrasts=at 60 ° The brightness of brightness during the white display in direction/in the black display in 60 ° of directions).When will come from positive contrast as 100, Based on following 60 ° of contrasts of benchmark evaluation.
○：60 ° of contrasts are 90 less than 100.
△：60 ° of contrasts are 80 less than 90.
×：60 ° of contrasts are less than 80.
【Table 3】
In image display device 201~208,212,213, the A faces of optical film and the surface roughness Ra in B faces used is Appropriate scope, and with good sliding, therefore surface irregularity and corrugation will not be produced.In addition, making the 1st He Diaphragm is not used during 2 polarizer, therefore will not also produce defect transfer.
In addition, the Ra values in the B faces of optical film are very small compared with A faces, optical film is fully be bonded with the polarizer, therefore will not Produce light leak.
In image display device 209, the A faces of optical film used and the surface roughness Ra in B faces are very high, therefore sliding Dynamic property is good, will not produce surface irregularity and corrugation, but B faces surface roughness Ra not in preferred scope, therefore in light The bonding interface for learning film and the polarizer produces gap, produces light bias.
In image display device 210,211, the surface roughness Ra in the B faces of optical film used is insufficient, therefore Generation minor surface is uneven in optical film conveying and wrinkles, but the not up to level of actual damage.In addition, leakage unconfirmed Light.
In image display device 214, the A faces and B faces of optical film used are sufficient surface roughness Ra, therefore sliding Dynamic property is high, will not produce surface irregularity and corrugation, but produces gap in the bonding interface of optical film and the polarizer, produces bright Aobvious light leak.
In image display device 215,216, the A faces of the optical film used and the surface roughness Ra in B faces are insufficient, because This produces obvious surface irregularity and corrugation in optical film conveying.Therefore, it is impossible to carry out image display device 215,216 Light leak evaluation.
In addition, using the optical film for being fitted with diaphragm in image display device 217, it is thus identified that obvious transfer lacks Fall into.Therefore, it can observe the light leak from the defect.

Claims (7)

1. a kind of optical film, it is characterised in that containing cyclic olefin resins, particulate and surface conditioner,
The surface conditioner contains in organosilicon material, fluorine system material, vinyl based material and acrylic material at least One kind,
The surface roughness Ra in the high face of surface roughness Ra is in the range of 3.0~50.0nm in film two sides.
2. optical film as claimed in claim 1, it is characterised in that
The surface roughness Ra in the low face of surface roughness Ra is in the range of 2.0~20.0nm in film two sides,
The difference of the surface roughness Ra on film two sides is more than 1.0nm.
3. optical film as claimed in claim 1 or 2, it is characterised in that the particulate contains silicon compound.
4. a kind of manufacture method of optical film, it is characterised in that be the optical film any one of manufacturing claims 1~3 Optical film manufacture method,
Manufactured by using the solution-casting method of more than two kinds of solvent.
5. a kind of polarizer, it is characterised in that possess：
The polarizer and
Optical film according to any one of claims 1 to 3.
6. polarizer as claimed in claim 5, it is characterised in that the polarizer is adhered to table in the two sides of the optical film Face low surface roughness Ra.
7. a kind of image display device, it is characterised in that possess optical film according to any one of claims 1 to 3.
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