CN101116017A - Optically-compensatory film, polarizing plate and liquid-crystal display device - Google Patents

Optically-compensatory film, polarizing plate and liquid-crystal display device Download PDF

Info

Publication number
CN101116017A
CN101116017A CNA2006800022803A CN200680002280A CN101116017A CN 101116017 A CN101116017 A CN 101116017A CN A2006800022803 A CNA2006800022803 A CN A2006800022803A CN 200680002280 A CN200680002280 A CN 200680002280A CN 101116017 A CN101116017 A CN 101116017A
Authority
CN
China
Prior art keywords
film
carbon atom
rth
cellulose acylate
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2006800022803A
Other languages
Chinese (zh)
Other versions
CN100573202C (en
Inventor
大轻郁子
大谷纯生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN101116017A publication Critical patent/CN101116017A/en
Application granted granted Critical
Publication of CN100573202C publication Critical patent/CN100573202C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B29K2001/08—Cellulose derivatives
    • B29K2001/12—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/40—Materials having a particular birefringence, retardation

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Mathematical Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

An optically-compensatory film comprising: a cyclic polyolefin film satisfying expression (I); and a cellulose acylate film satisfying expressions (II) and (III), or a liquid-crystal display device comprising at least one cyclic polyolefin film satisfying expression (I) and at least one cellulose acylate film satisfying expressions (II) and (III): (I) 35 = Re<SUB>(630) </SUB>= 350 and 70 = Rth<SUB>(630)</SUB> = 400, (II) 0 = Re<SUB>(630)</SUB> = 10 and | Rth<SUB>(630)</SUB>.

Description

Optical compensating film, polaroid and liquid crystal indicator
Technical field
The present invention relates to a kind of optical compensating film, polaroid and liquid crystal indicator.Specifically; the present invention relates to a kind of cyclic polyolefin optics twin shaft phase retardation film and the cellulose acylate film that is used for liquid crystal indicator; and the optical element that uses them, for example optical compensating film and polaroid etc. and use their liquid crystal indicator.
Background technology
Polaroid is normally made attached to the both sides of polarization film as protective film by the film that will be mainly formed by cellulose triacetate, and described polarization film is to be formed by arrangement and the iodine or the dichroic dye that are adsorbed on the polyvinyl alcohol (PVA).Cellulose triacetate has the characteristics of rigidity height, frame resistance (frame resistance) height and optical isotropy height (length of delay is low), and is widely used for above-mentioned polarizer protection film.Liquid crystal indicator is formed by polaroid and liquid crystal cell.Nowadays, TN-type TFT liquid crystal indicator is the main flow liquid crystal indicator, and it realizes high display visibility, as described in JP-A 8-50206 by insert optical compensating gage (phase retardation film) between polaroid and liquid crystal cell.
Cyclic polyolefin film is the center of paying close attention to as the high film of optical isotropy, but can improve its anisotropy, hydroscopicity or moisture-penetrability, and by using hot melt to become embrane method or solution film forming method can use it for the film that exploitation is used for polaroid and liquid crystal indicator by designing its molecular structure.Yet hot melt becomes embrane method to have the problem of the changes in optical properties of Width and length direction (retarding direction and optical axis direction).Usually the known solution film that becomes embrane method to provide to have better surface state.By with stenter at the Width oriented film, by between roller at the length direction oriented film, perhaps, can in solution film forming process, freely control optical anisotropy by their combination.Present (not having under the state of functional additive) much higher optical anisotropy when only using cellulose acylate film.
On the other hand, need liquid crystal indicator to have the viewing angle characteristic of raising recently more urgently.For the optical clear film, for example supporter of polarizer protective film and optical compensating film etc. is wished its optical isotropy more.With regard to optical isotropy, importantly length of delay is little, the described length of delay product representation of the thickness of birefringence and optical thin film.The display visibility in order to improve vergence direction and to observe particularly, the essential reduction postpones (Re) in thickness direction retardation (Rth) and the face.Particularly, when estimating the optical characteristics of optical clear film, the Re of direction detection is essential little in pellicular front, even and also must not change when measuring under different angles.
Usually can obtain the cellulose acylate film that Re reduces in the face, but it is little with the variation of angle to be difficult to form Re, promptly has the cellulose acylate film of little Rth.
As a solution, press for by further reduction optical anisotropy and improve cellulose acylate film the cohesive excellence of PVA.Particularly, the interior Re of demand side is almost nil and delay is little with the angle variation, promptly has the optical isotropy of almost nil Rth, optically transparent cellulose acylate film.
During the preparation cellulose acylate film, add usually and be called the compound of plastifier to improve filming performance.As plastifier, phosphotriester is disclosed, for example triphenyl phosphate and phosphoric acid xenyl diphenyl and phthalic acid ester class etc. (referring to, for example, Lecture of PlasticMaterials, the 17th volume, " Cellulose Resins ", The Nikkan Kogyo Shimbun Ltd. (1970), the 121st page).In known these plastifier some have the optically anisotropic effect that reduces cellulose acylate film.For example, the special fatty acid ester is disclosed (for example, JP-A2001-247717).Yet these conventional compound known are not thought the optically anisotropic effect with enough reduction cellulose acylate films.
Recently, wish that liquid crystal indicator has the demonstration tone level of improvement.In order to realize this point; the optical clear film; supporter of the protective film of polarizer and optical compensating film etc. for example; need in being the visible-range of 400-800nm, reduce wavelength Re and Rth; and need have little Re that depends on wavelength and Rth and change, the Re of promptly little wavelength dependency and Rth distribute.
Also wish liquid crystal indicator at display performance, for example aspects such as tone, contrast and view angle dependency are with respect to environmental factor, and for example the variation of humidity etc. does not change, and therefore provides high quality image.
Summary of the invention
First purpose of the present invention provides and a kind ofly changes the liquid crystal indicator that display characteristic has little variation with respect to environment temperature and humidity.Second purpose of the present invention provides a kind of cellulose acylate film, and it has little optical anisotropy (Re, Rth) (that is, being optical isotropy basically) and has the wavelength dependency distribution of low-level optical anisotropy (Re, Rth).The present invention's the 3rd purpose provides a kind of optical compensating film, polaroid and liquid crystal indicator that can present optically anisotropic cyclic polyolefin film and have the cellulose acylate film of low-level optical anisotropy (Re, Rth) (that is, being optical isotropy basically) that comprise.
The present invention's the 4th purpose is to show a kind of optical element, for example optical compensating film or polaroid etc. have excellent viewing angle characteristic, and described optical element is formed by the cellulose acylate film with the distribution of low-level optical anisotropy and low-level wavelength dependency; And provide a kind of liquid crystal indicator that uses described optical element.
Have the protective film of the cellulose acylate film of low-level optical anisotropy and the distribution of low-level wavelength dependency by use, can improve the optical characteristics of polaroid as polaroid.Using under the situation of this cellulose acylate film as the supporter of optical compensating film, can develop the optical property of optical compensating film itself.By this polaroid or optical compensating film are used for liquid crystal indicator, can improve contrast and tone.
As optical compensating layer, use to have the optically anisotropic cyclic polyolefin film that freely to control.Polarizer protection film as the supporter that is used as optical compensating layer; use has low-level optical anisotropy (Re, Rth) (promptly; basically be optical isotropy) and also have the cellulose acylate film that above-mentioned cellulose acylate film that the wavelength dependency of low-level optical anisotropy (Re, Rth) distributes replaces commercially available acquisition, example is Fujitac etc. as is generally known.Thus, separation function more clearly.
Particularly; having high-caliber optically anisotropic film is formed by cyclic polyolefin film; feasible variation with respect to environment temperature and humidity; its optical characteristics can not change; and the film of protection polarizer is formed by above-mentioned cellulose acylate film; it has the cohesive of sizable polyvinyl alcohol (PVA) to optically anisotropic inhibition level and high-caliber and polarizer; and with respect to the variation of environment temperature and humidity, the variation of display performance is littler than back nail film (plain tack film).Be used for liquid crystal indicator by this combination, can improve contrast and tone film.
In other words, realized above-mentioned purpose in the following manner.
(1) a kind of optical compensating film, it comprises:
Satisfy the cyclic polyolefin film of formula (I); With
Satisfy formula (II) and cellulose acylate film (III):
(I) 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400,
(II) 0≤Re (630)≤ 10 Hes | Rth (630)|≤25 and
(III) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Length of delay (unit: nm) in Re (λ) the representative face under wavelength X nm wherein; With
Thickness direction retardation value (the unit: nm) of Rth (λ) representative under wavelength X nm.
(2) a kind of liquid crystal indicator, it comprises:
At least two polarization films;
Between described at least two polarization films at least one satisfies the cyclic polyolefin film of formula (I); With
Between described at least two polarization films at least one satisfies formula (II) and cellulose acylate film (III):
(I) 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400,
(II) 0≤Re (630)≤ 10 Hes | Rth (630)|≤25 and
(III) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Length of delay (unit: nm) in Re (λ) the representative face under wavelength X nm wherein; With
Thickness direction retardation value (the unit: nm) of Rth (λ) representative under wavelength X nm.
(3) as top (1) described optical compensating film or as top (2) described liquid crystal indicator,
Wherein said cyclic polyolefin film comprises a kind of multipolymer, and described multipolymer contains the repetitive of at least one formula (A) representative and the repetitive of at least one formula (B) representative:
Formula (A)
Figure A20068000228000151
Formula (B)
Figure A20068000228000152
Wherein m represents the integer of 0-4;
R 1-R 4Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 1, X 2, Y 1And Y 2Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 1And Y 1Or X 2And Y 2Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
(4) as top (1) described optical compensating film or as top (2) described liquid crystal indicator,
Wherein said cyclic polyolefin film comprises a kind of polymkeric substance or a kind of multipolymer, at least two ring-type repetitives that the ring-type repetitive that described polymkeric substance contains formula (B) or (C) represents, described multipolymer contain formula (B) and (C) represent,
Formula (B)
Formula (C)
Figure A20068000228000162
Wherein m represents the integer of 0-4;
R 3-R 6Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 2, X 3, Y 2And Y 3Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 2And Y 3Or X 3And Y 3Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
(5) as top (3) or (4) described optical compensating film or as top (3) or (4) described liquid crystal indicator,
Wherein said cyclic polyolefin film is to obtain by the method that comprises the steps:
The organic solvent solution curtain coating that will contain the described polymkeric substance of 10 quality %-35 quality % or described multipolymer is to the endless metal supporter, and is and dry, to form dry film;
Peel off the film of described drying from described metal support, the film of peeling off with formation;
At least one direction in Width and length direction stretch described film of peeling off and
Further dry and roll.
(6) as any described optical compensating film in top (1) and (3)-(5) or as any described liquid crystal indicator in top (2)-(5),
Wherein said cellulose acylate film contains and at least a thickness direction retardation Rth is reduced to the compound that satisfies formula (IV) and scope (V),
(IV) (Rth (A)-Rth (0))/A≤-1.0 and
(V)0.01≤A≤30，
Wherein Rth (A) representative contains the Rth (nm) of film of compound of the reduction Rth of A%;
Rth (0) represents the Rth (nm) of the film of the compound that does not contain any reduction Rth (nm); With
When A representative is 100 when the quality as the polymkeric substance of the material of described film, the quality (%) of the compound of reduction Rth.
(7) as any described optical compensating film in top (1) and (3)-(6) or as any described liquid crystal indicator in top (2)-(6),
Wherein said cellulose acylate film comprises the cellulose acylate that the acyl substituted degree is 2.85-3.00.
(8) as any described optical compensating film in top (1) and (3)-(7) or as any described liquid crystal indicator in top (2)-(7),
Wherein said cellulose acylate film comprises at least a reduction | Rth (400)-Rth (700)| compound, with the solid content meter of described cellulose acylate, the content of described compound is 0.01-30 quality %.
(9) as any described optical compensating film in top (1) and (3)-(8) or as any described liquid crystal indicator in top (2)-(8),
The thickness of wherein said cellulose acylate film is 10-120 μ m.
(10) a kind of polaroid, it comprises:
Polarizer; With
Any described optical compensating film in (1) and (3)-(9) is as the protective film of described polarizer above at least one.
(11) as top (10) described polaroid,
Wherein on the surface of described polaroid, provide at least a in hard conating, anti-glare layer and the anti-reflecting layer.
(12) a kind of liquid crystal indicator, it comprise as top (1) and (3)-(9) arbitrarily a described optical compensating film and as top (10) or (11) described polaroid at least one.
(13) a kind of VA-type liquid crystal indicator or a kind of IPS-type liquid crystal indicator, it comprise as claim 1 and 3-9 arbitrarily optical compensating film and as in the polaroid of claim 10 or 11 at least one.
Description of drawings
Fig. 1 is the figure that shows the illustration structure of liquid crystal indicator of the present invention; With
Fig. 2 is the figure of illustration structure that shows the liquid crystal indicator of the present invention and Comparative Examples.
Embodiment
Describe the present invention below in detail.
1. at first, cyclic polyolefin film of the present invention is described.
Cyclic polyolefin film of the present invention satisfies following formula (I).
(I) 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400.
As for formula (I), preferred:
(I) 35≤Re (630)≤ 300 and 100≤Rth (630)≤ 350; With
More preferably:
(I) 35≤Re (630)≤ 250 and 100≤Rth (630)≤ 300.
Cyclic polyolefin film of the present invention can followingly form.
(cyclic polyolefin)
Example with thermoplastic polymer resin of cyclic polyolefin hydrocarbon structure comprises: (1) norborene based polyalcohol; (2) polymkeric substance of cycloolefin; (3) polymkeric substance of cyclic conjugated diene; (4) alicyclic vinyl cyclic hydrocarbon polymer; (1)-(4) hydride etc.Wherein, from the angle of optical characteristics, thermotolerance and physical strength etc., preferred norborene based polyalcohol and hydride and alicyclic vinyl cyclic hydrocarbon polymer and hydride thereof.
The preferred polymkeric substance of the present invention be contain at least a below general formula (A) representative repetitive and at least a below general formula (B) representative repetitive the multipolymer cyclic polyolefin or contain at least a below general formula (B) or (C) open loop (being total to) polymkeric substance or addition (being total to) polymkeric substance of the repetitive of representative.
Formula (A)
Formula (B)
Figure A20068000228000202
(C)
Figure A20068000228000203
In these formulas, m represents the integer of 0-4.R 1-R 6Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom.X 1-X 3And Y 1-Y 3Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 1And Y 1, X 2And Y 2Or X 3And Y 3Form (CO) 2O or (CO) 2NR 15R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom.Z representation hydrocarbyl or the alkyl that is replaced by halogen.W represents SiR 16 pD 3-p(R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16Represent the integer of 0-3 with p).N represents the integer of 0-10.
Described in pamphlet of JP-A1-240517,7-196736,60-26024 and 62-19801 and international publication number 04/070463 etc., encircle unsaturated compound then hydrogenation by addition polymerization or ring-opening metathesis polymerization more, make the hydride of norborene based polyalcohol.Be used for norborene based polyalcohol of the present invention, R 9-R 12Separately preferably hydrogen atom or-CH 3X 3, X 4, Y 3And Y 4Separately preferably hydrogen atom, Cl or-COOCH 3And suitably select other group.This norbornene resin can be from JSR Corporation with trade name Alton G or Arton F and commercially available with trade name Zeonor ZF14, Zeonor ZF16, Zeonex 250 or Zeonex 280 from Zeon Corporation.Can use these products.
The alicyclic vinyl cyclic hydrocarbon polymer is disclosed in JP-A 10-87752 and JP-A 2001-272534.The alicyclic vinyl cyclic hydrocarbon polymer can pass through polymerization, for example radical polymerization, coordinated anionic polymerization method or cationic polymerization etc. are used for ring compound and linear diolefin compound makes, described ring compound for example has the compound of the structure that the vinyl that therein ethylene base or alpha-alkyl replace links to each other with cycloalkenyl group that naphthenic base, cycloalkenyl group or the alkyl that monocyclic cycloalkyl, alkyl replace replaces, or the compound that forms by the vinyl of vinyl that is connected with aromatic hydrocarbon substituting group etc. or alpha-alkyl replacement etc.; For example ethene, propylene, butane, conjugated diolefine be (for example for described linear diolefin compound, butadiene, isoprene (isopulene)), non-conjugated diene (for example, ethylidene norbornene), vinyl cyanide, acrylic acid, methacrylic acid, maleic anhydride, acrylate, methacrylate, maleimide, vinyl acetate or vinyl chloride etc.This alicyclic vinyl cyclic hydrocarbon polymer is sold with trade name Apel by Mitsui Chemicals Inc., and the grade of glass temperature that can be different (Tg) obtains, for example APLg008T (Tg:70 ℃), APL6013T (Tg:125 ℃) and APL6015T (Tg:145 ℃) etc.
(adjuvant)
According to different purposes, in each preparation process, can in cyclic polyolefin solution of the present invention, add various adjuvants (for example, anti-degradation, UV resistant agent, delay (optical anisotropy) correctives, particulate, peel off promoter, infrared absorbent etc.).These adjuvants can be solid-state or oilies.In other words, fusing point or boiling point are had no particular limits.For example, can be 20 ℃ or lower ultraviolet absorption material with temperature with temperature be that 20 ℃ or higher ultraviolet absorption material mix.Similarly, different anti-degradations can be mixed.And, can use for example infrared ray absorbing dyestuff described in the JP-A2001-194522.Adjuvant can add in the random time of dope preparation process, and the step of adding adjuvant perhaps can be provided after the final step of dope preparation process.The addition of each material has no particular limits, as long as its function is provided.When cyclic polyolefin was formed by multilayer, the type of adjuvant or addition can be different in each layer.
(anti-degradation)
Can add known anti-degradation (antioxidant) to cyclic polyolefin film of the present invention, comprise for example phenol or quinhydrones (hydrokinenone) antioxidant, for example 2,6-two-tert-butyl group, 4-methylphenol, 4,4 '-thiobis-(the 6-tert-butyl group-3-methylphenol), 1,1 '-bis(4-hydroxyphenyl)cyclohexane, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,5-two-tertiary butylated hydroquinone or pentaerythrite base-four [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester etc.Preferably also add the phosphate antioxidant, three (4-methoxyls (methxy)-3 for example, the 5-diphenyl) phosphite ester, three (nonyl phenyl) phosphite ester, three (2,4-two-tert-butyl-phenyl) phosphite ester, two (2,6-two-tert-butyl group-4-aminomethyl phenyl) pentaerythritol diphosphites and two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites etc.With respect to the cyclic polyolefin of 100 mass parts, the addition of antioxidant is the 0.05-5.0 mass parts.
(ultraviolet light absorber)
With regard to cyclic polyolefin film of the present invention, preferably use ultraviolet light absorber to prevent deteriorations such as polaroid or liquid crystal.For gratifying liquid crystal display is provided, preferably use absorbing wavelength as 370nm or shorter ultraviolet ability and absorb the ultraviolet light absorber of a small amount of wavelength as 400nm or longer visible light with excellence.The instantiation that is preferred for ultraviolet light absorber of the present invention comprises hindered phenol compound, oxygen base benzophenone cpd, benzotriazole cpd, salicylate compound, benzophenone cpd, alpha-cyanoacrylate ester compounds and nickel complex salt compound etc.The example of hindered phenol based compound comprises 2, [3-(3 for 6-two-tert-butyl group-paracresol, pentaerythrite base-four, 5-two-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-two-tertiary butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4-6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene and three-(3,5-two-tertiary butyl-4-hydroxy benzyl)-chlorinated isocyanurates etc.The example of benzotriazole based compound comprise 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2, (4-(1 for the 2-di-2-ethylhexylphosphine oxide, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base (il)) phenol), (2, two (positive hot sulfenyl)-6-(the 4-hydroxyls-3 of 4-, 5-two-tert-butyl benzene amido)-1,3, the 5-triazine, triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-two-tertiary butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, 2 (2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-the 5-chlorobenzotriazole, (2 (2 '-hydroxyl-3 ', 5 '-two-tertiary pentyl phenyl)-the 5-chlorobenzotriazole, 2,6-two-tert-butyl group-paracresol and pentaerythrite base-four [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] etc.With respect to cellulose acylate, the addition of these adjuvants is 1 quality ppm-1.0 quality %, more preferably 10-1000 quality ppm preferably.(in this manual, quality % and mass parts equal weight % and weight portion respectively.)
(matting agent)
In the present invention, for the cyclic polyolefin film that prevents to make is damaged when the transportation or the rodability of the cyclic polyolefin film that prevents to form reduces, preferably add particulate.The instantiation of preferred matting agent comprises mineral compound, for example silicon-containing compound, silicon dioxide, titanium oxide, zinc paste, aluminium oxide, baryta, Zirconium oxide, strontium oxide, sb oxide, tin-oxide, tin-oxide/antimony, lime carbonate, talcum, clay, calcined kaolin, calcining calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc.More preferably siliceous mineral compound and Zirconium oxide.Especially preferably use silicon dioxide, this is because it can reduce the turbidity of film.As the silicon dioxide microparticle agent, for example, can use trade mark by name Aerozyl R972, R974, R812,200,300, the R202 of commercially available acquisition, the product (all by Nippon Aerozyl Co., Ltd. makes) of OX50, TT600 etc.As the Zirconium oxide fine granule, for example, can use the product (all by Nippon Aerozyl Co., Ltd. makes) of trade mark Aerozyl R976, the R811 by name of commercially available acquisition etc.
For mist degree is suppressed to low-level, the primary average particle size of these particulates is 0.001-20 μ m preferably, more preferably 0.001-10 μ m, even more preferably 0.002-1 μ m, preferred especially 0.005-0.5 μ m.The primary average particle size of particulate can be measured with transmission electron microscope.The particulate of buying is often assembled, and preferably will use after these microparticulate of buying by known method.These particulates are through disperseing to make preferably 0.2-1.5 μ m of secondary mean grain size, more preferably 0.3-1.0 μ m.With respect to the cyclic polyolefin of 100 mass parts, the addition of fine granule is the 0.01-0.3 mass parts preferably, more preferably 0.05-0.2 mass parts, most preferably 0.08-0.12 mass parts.
Next, the organic solvent of dissolving cyclic polyolefin of the present invention is described.
(chloro solvent)
When the solution of preparation cyclic polyolefin of the present invention, preferably use the chloro organic solvent as primary solvent.In the present invention, the type of chloro organic solvent has no particular limits, as long as dissolving cyclic polyolefin and curtain coating form film and can achieve the goal thus.The chloro organic solvent is methylene chloride or chloroform preferably.Preferred especially methylene chloride.Can mix the organic solvent outside the chloro organic solvent, not have special problem.In this case, need to use the methylene chloride of at least 50 quality %.The non-chloro organic solvent that is used in combination with chloro organic solvent of the present invention is described below.Preferred non-chloro organic solvent is selected from ester with 3-12 carbon atom, ketone, ether, pure and mild hydrocarbon etc.Ester, ketone, ether and alcohol can have ring structure.Can use and have at least two esters, ketone and ether (that is ,-O-,-CO-or-compound of COO-) functional group is as solvent.This compound can have another functional group simultaneously, for example, and alcoholic extract hydroxyl group.Be to have under the situation of solvent of two or more functional groups, its carbon number can be in to the defined scope of the compound with any one functional group.Example with ester of 3-12 carbon atom comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate etc.Example with ketone of 3-12 carbon atom comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone etc.Example with ether of 3-12 carbon atom comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-two  alkane, 1, the 3-dioxolanes (1,3-dioxorane), tetrahydrofuran, anisole and phenetol etc.Example with organic solvent of two or more functional groups comprises acetic acid-2-ethoxy-ethyl ester, 2-methyl cellosolve and butoxy ethanol etc.
The alcohol that is used in combination with the chloro organic solvent can preferably have linear chain structure, branched structure or ring structure, and saturated aliphatic hydrocarbon preferably.The hydroxyl of alcohol can be primary, the second month in a season or uncle.The example of alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-methyl-2-butanols and cyclohexanol.As alcohol, also can use fluorine-based alcohol.For example, can use 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3,3-tetrafluoro-1-propyl alcohol etc.Hydrocarbon can have linear chain structure, branched structure or ring structure.Aromatic hydrocarbon or aliphatic hydrocrbon can use.Aliphatic hydrocrbon can be saturated or undersaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.
For the combination of the chloro organic solvent of preferred primary solvent of the present invention can be following combination for example, but be not limited thereto.
Methylene chloride/ethanol/butanols (80/8/5/2, mass parts)
Methylene chloride/butanols/cyclohexane (75/10/5/5/5, mass parts)
Methylene chloride/acetone/methyl ethyl ketone/ethanol/isopropyl alcohol (75/10/10/5/7, mass parts)
Methylene chloride/methyl acetate/butanols (80/10/10, mass parts)
Methylene chloride/1,3-dioxolanes/methanol/ethanol (70/20/5/5, mass parts)
Methylene chloride/two  alkane/acetone/methanol/ethanol (60/20/10/5/5, mass parts)
Methylene chloride/acetone/ethyl acetate/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts)
Methylene chloride/methyl acetoacetate/methanol/ethanol (65/20/10/5, mass parts)
Methylene chloride (100, mass parts)
Methylene chloride/ethanol (92/8, mass parts)
According to the composition that designs for solvent, the anti-fissility value marked change of the film that is still wetting to peeling off from metal support.By adding the non-solvent with polarity to the chloro organic solvent as primary solvent, anti-fissility significantly reduces.Provide the significant especially polar solvent that reduces the effect of anti-fissility to be, for example, have the alcohol of 1-4 carbon atom, single carbonic acid (monocarbonic acid), divalence or carbonic acid more at high price and their half ester etc. with 1-5 carbon atom.Wherein, most preferably pure, this is because they have excellent volatility.The chloro primary solvent is the polarity non-solvent of the chloro primary solvent of 70-98 mass parts than 2-30 mass parts with the preferred proportion of polarity non-solvent.More preferably ratio is the polarity non-solvent of the chloro primary solvent of 78-95 mass parts than 5-22 mass parts.Provide the preferred compositions of solvent of low-level anti-fissility as follows, but be not limited thereto.
Methylene chloride/ethanol/butanols (83/10/5/2, mass parts)
Methylene chloride/methyl acetate/ethanol (80/10/10, mass parts)
Methylene chloride/isopropyl alcohol (78/15/7, mass parts)
Methylene chloride (87/13, mass parts)
(non-chloro solvent)
Next, the non-chloro solvent that is preferred for preparing cyclic polyolefin solution of the present invention is described.In the present invention, non-chloro solvent has no particular limits, as long as dissolving cyclic polyolefin and curtain coating form film and achieve the goal thus.Be used for non-chloro solvent of the present invention and be preferably selected from chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon, ester, ketone and ether with 3-12 carbon atom.Ester, ketone and ether can have ring structure.Can use and have at least two esters, ketone and ether (that is ,-O-,-CO-or-compound of COO-) functional group is as primary solvent.This compound can also have another functional group, for example, and alcoholic extract hydroxyl group.Be to have under the situation of primary solvent of two or more functional groups, its carbon number can be in to the defined scope of the compound with any one functional group.Example with chain hydrocarbon of 3-12 carbon atom comprises hexane, octane, isooctane and decane etc.Example with cyclic hydrocarbon of 3-12 carbon atom comprises hexane and derivant thereof.Example with aromatic hydrocarbons of 3-12 carbon atom comprises benzene, toluene and dimethylbenzene etc.Example with ester of 3-12 carbon atom comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.Example with ketone of 3-12 carbon atom comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone.Example with ether of 3-12 carbon atom comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-two  alkane, 1,3-dioxolanes, tetrahydrofuran, anisole and phenetol.Example with organic solvent of two or more functional groups comprises acetic acid-2-ethoxy-ethyl ester, 2-methyl cellosolve and butoxy ethanol.
(dope preparation)
Next, about the preparation of cyclic polyolefin solution of the present invention (dope), the dissolving method of cyclic polyolefin has no particular limits.Availablely at room temperature dissolve by dissolution in low temperature method, high-temperature digestion method or their combination.About these methods, can use the technology identical with cellulose acylate film.Can be referring to Hatsumei Kyokai ' s DisclosureBulletin No.2001-1745 (March 15 calendar year 2001 publish, Hatsumei Kyokai), the 25th page and thereafter or the like, it describes the dissolving method of cellulose acylate in detail.When at high temperature dissolving, great majority carry out in the temperature of the boiling point that is not less than used organic solvent and adding to depress.
The viscosity of cyclic polyolefin solution of the present invention in 25 ℃ of preferred scopes at 1-500Pas, more preferably 5-200Pas.The described viscosity of following mensuration.With diameter 4cm/2 ° SteelCone measures this sample solution of 1mL by velocimeter (CSL 500) (by TA Instruments make) viscosity.Begin after the heated sample solution to measure, make that the liquid temperature is constant under mensuration beginning temperature.
Cyclic polyolefin solution has the characteristic that the high concentration dope is provided.Not relying on enrichment facility just can obtain highly to concentrate and high stability cyclic polyolefin solution.For easier dissolving, cyclic polyolefin can be dissolved to low concentration and use enrichment facility to concentrate then.Method for concentration has no particular limits.For example, can realize by the following method concentrating: low concentration solution is joined between the excircle rotate path of the cylinder and the rotatable wing, the described rotatable wing is installed in this cylinder and provides the temperature difference with solution simultaneously in the circumferencial direction rotation, make solvent evaporation obtain the method (for example, JP-A 4-259511) of highly concentrated solution; The low concentration solution that will be heated blows in the container from nozzle, so that entering into time durations between the solution bump container inner wall by nozzle from solution, remove solvent vapour and remove the method for highly concentrated solution that (for example, United States Patent (USP) 2 simultaneously from container from container bottom with solvent flashing, 541,012,2,858,229,4,414,341 and 4,504, the method described in 355); Deng.
Before the curtain coating, preferably use the suitable filtrator of wire netting or flannel etc. that solution is filtered to remove foreign matter, for example insoluble substance, dust or impurity etc.In order to filter the ring-type polyolefin solution, use absolute filtering accuracy to be 0.1-100 μ m, the filtrator of preferred 0.5-25 μ m.The thickness of filtrator is 0.1-10mm preferably, more preferably 0.2-2mm.In this case, filter pressure is 1.6MPa or littler, more preferably 1.3MPa or littler, even more preferably 1.0MPa or littler, preferred especially 0.6MPa or littler.As filtering material, can preferably use conventional known material, for example glass fibre, cellulose fibre, filter paper or fluororesin (for example, tetrafluoroethylene resin, etc.) etc.Also preferred pottery and the metal etc. of using.
Cyclic polyolefin solution can allow in the scope of described solution casting when film forming the time at once viscosity before the film forming.Typically, preparation viscosity is preferably at 5Pas-1000Pas, more preferably 15Pas-500Pas, even the more preferably solution in the scope of 30Pas-200Pas.The temperature of this moment has no particular limits, as long as its temperature when being solution casting, preferably-5 ℃ to 70 ℃, more preferably-5 ℃ to 35 ℃.
(film forming)
A kind of method of using the cyclic polyolefin film film forming is described.As the method and apparatus that forms cyclic polyolefin film of the present invention, use with the similar solution casting of the method and apparatus that is used to form cellulose acetate film to become embrane method and solution casting film-forming apparatus.At first will preserve in storage tank by the dope (cyclic polyolefin solution) that dissolver (groove) makes, and with the final step of dope froth breaking as preparation.Dope for example is pumped into the pressure-type die head through the pressure-type measurement gear from the dope conveying end, and described pump can shift the liquid of constant basis accurately by the revolution of control unit interval.From the pressure-type die head the mouth (slit) with the even curtain coating of dope on the metal support of the curtain coating section of cycle operation.Almost rotate once pick-up point in metal support, peel off down the dope film (also being referred to as " former ") that is still wetting from metal support.The gained former is clamped its two ends with clip, through the stenter transportation, and dry.Then, one of former drying device group of roller transportation.Thus, stop dry run.Former is rolled to have predetermined length around winder.The combination of one group of roller of stenter and described exsiccator changes with the purpose of film to be made.Solution casting at the function and protecting film that is used for electronic console becomes embrane method; except flow of solution flow casting molding equipment, also often use coating apparatus, so that on film, carry out surface treatment so that bottom, antistatic layer, anti-dizzy layer and protective film etc. to be provided.Below, briefly describe each step, but the present invention is not limited to following description.
In order to form cyclic polyolefin film, at first cyclic polyolefin (dope) curtain coating that makes is gone up with evaporating solvent to metal rotating cylinder or metal tape (belt) by the solvent cast method.Thus, form film.The concentration of pre-curtain coating dope preferably makes that through adjusting amount of polymers is 10-35 quality %.The surface of described rotating cylinder or band is preferred through being polished to mirror status.Preferably the dope curtain coating is 30 ℃ or lower rotating cylinder or is with to surface temperature.The surface temperature of metal support is especially preferably-10 ℃ to 20 ℃.
Cellulose acylate film formation technology described in JP-A 2000-301555,2000-301558,7-032391,3-193316,5-086212,62-037113,2-276607,55-014201,2-111511 and the 2-208650 can be used for the present invention.
(double-deck curtain coating)
Cyclic polyolefin solution can the individual layer curtain coating to as on the smooth zone or rotating cylinder of metal support, perhaps can become two-layer multiple cyclic polyolefin solution casting or multilayer.For the multiple cyclic polyolefin solution of curtain coating, contain a plurality of curtain coatings outlet curtain coatings that the solution of cyclic polyolefin can provide at certain intervals from the working direction in metal support, make these solution through curtain coating and laminated formation film.For example, can use the method described in JP-A 61-158414,1-122419 and the 11-198285.
Perhaps, can be by forming film from two curtain coating outlet curtain coating cyclic polyolefin solution.For example, can use the method described in JP-B 60-27562 and JP-A 61-94724,61-947245,61-104813,61-158413 and the 6-134933.Even or, also can use the polyolefin solution film casting method described in the JP-A 56-162617, wherein high concentration cyclic polyolefin flow of solution is enclosed in the low concentration cyclic polyolefin solution, and described height and low concentration cyclic polyolefin solution are extruded simultaneously.And, described in JP-A 61-94724 and 61-95725, preferred outside solution contain as big than in the inner face solution of the amount of the alkoxide component of poor solvent.Perhaps, can use two curtain coatings to go out the interruption-forming film.In this case, peel off the film that uses the outlet of first curtain coating on metal support, to form, and from the outlet of second curtain coating with second solution casting to film surface that the metallic support surface contacts on.This method for example is described in JP-B 44-20235.The cyclic polyolefin solution for the treatment of curtain coating can be mutually the same or different, has no particular limits.For a plurality of cyclic polyolefins with function are provided, can extrude from each curtain coating outlet corresponding to the cyclic polyolefin solution of each function.Can curtain coating cyclic polyolefin solution to form other functional layer (for example, bonding coat, dye layer, antistatic layer, anti-dizzy layer, UV-absorbing layer, polarization layer, etc.) simultaneously.
When using individual layer solution,, need extrude high concentration and high viscosity cyclic polyolefin solution for necessary film thickness is provided.In this case, the stability of the difference of cyclic polyolefin solution may cause solid matter to cause the generation of protruding defective or difference planarity.As a kind of method that addresses this is that, multiple cyclic polyolefin solution is exported curtain coating from curtain coating, can simultaneously high viscosity solution be expressed on the metal support thus.Improve planarity like this, thereby formed the film of surface state excellence.In addition, use thick cyclic polyolefin solution can reduce the speed of production that therefore dry load also can increase film.
When the multiple solution of while curtain coating, internal layer and outer field thickness have no particular limits.Yet outer field thickness is the 1-50% of whole film thickness preferably, more preferably 2-30%.Under the situation of three kinds of curtain coatings or multiple solution, the layer that definition contacts with metal support is outer field thickness with the gross thickness of the layer that contacts with air.When the multiple solution of while curtain coating, contain the above-mentioned adjuvant of variable concentrations by the while curtain coating, the cyclic polyolefin solution of for example anti-degradation, ultraviolet light absorber and matting agent etc. can form laminated structure ring shape polyolefin film.For example, can form the cyclic polyolefin film of structure with cortex/core layer/cortex.For example, can contain relatively large matting agent, perhaps only in cortex, contain matting agent at cortex.Anti-degradation and the ultraviolet light absorber content in core layer can be than in the cortex big, perhaps only in core layer, contain.In core layer and cortex, can contain dissimilar anti-degradation and ultraviolet light absorber.For example, in cortex, can contain volatile grade low anti-degradation and/or ultraviolet light absorber, and in core layer, can contain the plastifier of plasticity excellence or the ultraviolet light absorber of ultraviolet-absorbing excellence.The also preferred cortex that only contacts with metal support contains peels off promoter.Also preferred cortex makes the metal support cooling with gelling soln by the low temperature rotating-cylinder method than adding more alcohol in the core layer as poor solvent like this.Cortex can be different with Tg between the core layer.The Tg of preferred core layer is lower than the Tg of cortex.The viscosity that contains the solution of cyclic polyolefin during curtain coating may be different between cortex and core layer.The viscosity of preferred cortex is lower than the viscosity of core layer, also is acceptable but the viscosity of core layer is lower than the viscosity of cortex.
(curtain coating)
The method for optimizing of curtain coating solution comprises from pressing mold the dope that makes evenly is expressed into method on the metal support, adjusts the scraping the skill in using a kitchen knife in cookery and adopt the method etc. of reverse roll spreader of film thickness of the dope on the metal support of curtain coating with blade that described reverse roll spreader uses the roller of rotation in the opposite direction to adjust the thickness of dope film.The preferred method of using pressing mold.Pressing mold be the clothes hanger type or the T model etc.Can preferably use any type.Except said method, can also use the method for the known curtain coating cellulose triacetate solution film forming of various routines.Adjust various conditions etc. by the boiling point of considering solvent for use, provide basically and the identical effect of effect described in each document.As the metal support of the circular flow that is used to form cyclic polyolefin film of the present invention, use the surface through the bright finished rotating cylinder of chromium plating or surface through surface grinding and bright finished stainless band (also being referred to as " belt ").In order to form cyclic polyolefin film of the present invention, one or two or a plurality of pressing mold can be installed above metal support.Preferably, one or two pressing mold is installed.When two or more pressing mold is installed, between die head, the dope amount for the treatment of curtain coating can be separated in varing proportions, perhaps can with ratio separately dope be delivered to die head from a plurality of high precision constant pumps.The temperature of cyclic polyolefin solution for the treatment of curtain coating is preferably-10 ℃ to 55 ℃, more preferably 25 ℃-50 ℃.In this case, temperature in steps can be identical, perhaps can change, this depends on step.When temperature changes with step, only need before curtain coating solution, reach temperature required at once.
(drying)
The dope on metal support that forms cyclic polyolefin film is carried out dry common method comprise surface, promptly to the method for the surface of the former on metal support blowing hot-air metal support (rotating cylinder or band); Method to the back side blowing hot-air of rotating cylinder or band; With with the back side of temperature control liquid and band or rotating cylinder (with curtain coating dope on it surperficial relative) thus contact with liquid heat transfer method by heat transfer heated drums or band control surface temperature etc.Preferred back side liquid heat transfer method.The surface temperature of metal support can be the arbitrary temp that is equal to or less than the boiling point of the solvent that is used for dope before the curtain coating solution.Yet, in order to quicken drying or, preferably surface temperature to be adjusted to temperature than the low 1-10 degree of boiling point of the solvent that has minimum boiling point in the solvent for use in order to make the flowability of solution forfeiture on metal support.This is not used in without cooling or the dry situation that just can peel off the curtain coating dope.
(stretching)
Can adjust the delay of cyclic polyolefin film of the present invention by stretching.Technology at active (actively stetch) film that stretches of Width is also arranged, described in JP-A 62-115035,4-152125,4-284211,4-298310 and 11-48271.Use these technology, the cyclic polyolefin film that forms is stretched to postpone to increase in its face.
Oriented film under room temperature or heated condition.Preferably film is heated to glass temperature ± 50 ℃ of film, more preferably ± 45 ℃, even more preferably ± 40 ℃.Film can be only at length or Width through uniaxial tension, perhaps can be simultaneously or biaxial stretch-formed in succession at length and Width.With film stretching 0.5-200%, preferred 0.5-100%, preferred especially 0.5-50%.As for the birefringence of optical thin film, the refractive index of preferable width direction is greater than the refractive index of length direction.Therefore, preferred film is in the stretching of the Width stretching greater than length direction.Described stretching can be carried out in the centre of film forming procedure, perhaps carries out after film forms and rolls.In the former case, can when containing the solvent of residual quantity, stretch.This stretching can preferably be carried out when the residual quantity of solvent is 1-50%.
The thickness of (drying) cyclic polyolefin film finally of the present invention changes with application target, but typically in the scope of 5-500 μ m, preferably in the scope of 30-150 μ m.Particularly when being used for liquid crystal indicator, the preferred thickness of film is 40-110 μ m.
Can adjust the thickness of film by concentration, the gap size of die head mouth, the extrusion pressure of die head and the speed of metal support etc. of adjusting solid matter in the dope, thereby obtain required thickness.The width of the cyclic polyolefin film of Huo Deing 0.5-3m preferably as mentioned above, more preferably 0.6-2.5m, even more preferably 0.8-2.2m.Film rolled make the length 100-10 preferably of each volume, 000m, more preferably 500-7,000m, even more preferably 1,000-6,000m.When rolling film, preferably provide embossing at least one end.Embossing width is 3-50mm preferably, and more preferably 5-30mm, and embossed height is 0.5-500 μ m preferably, more preferably 1-200 μ m.Can provide embossing in one or both sides.The variation of the Re value of whole width preferably ± 5nm, more preferably ± 3nm.The variation of Rth value preferably ± 10nm, more preferably ± 5nm.The variation of the Re value of length direction and the variation of Rth value are preferably in the scope of the variation of the variation of the Re of Width value and Rth value.In order to keep the transparency of film, mist degree is 0.01-2% preferably.In order to reduce mist degree, the matting agent particulate that adds is fully disperseed perhaps only to use matting agent to reduce its addition at cortex to reduce the amount of flocculated particle.
Compare with the cellulose acylate film that is usually used in polaroid, the remarkable advantage of cyclic polyolefin film is that moisture-penetrability and equilibrium moisture content are low.The moisture-penetrabilitys that continue 24 hours at 60 ℃ and 95%RH are 1000g/m preferably 2Or littler, more preferably 400g/m 2Or it is lower.The equilibrium moisture content of under 25 ℃ and 80%RH, measuring preferably 2.0% or littler, more preferably 1.0% or littler.Work as adjuvant, for example ultraviolet light absorber or delay present agent etc., be volatile or can decompose and therefore when the quality of film or size change, the optical characteristics of film changes.In this case, the mass change of film preferably 5% or littler after 48 hours under 80 ℃ and 90%RH.Similarly, the variation of film dimensions preferably 5% or littler after 24 hours under 60 ℃ and 95%RH.Even quality or size slightly change, when the optics elasticity of film hour, changes in optical properties is less.Therefore, the optics elasticity of film preferably 30 * 10 -13Cm 2/ dyne or littler, more preferably 15 * 10 -13Cm 2/ dyne or littler.
(adhesion)
For cyclic polyolefin film of the present invention being adhered on polarization film, polarization film protective film or the phase retardation film etc. that form by PVA etc., below can using about the attachment technique described in the part of polaroid and following about the technology described in the surface-treated part.Can use the cohesive material adhering film.The type of material to be adhered to according to film (hydrophilic or hydrophobic) used proper method.
(polaroid)
Polaroid is formed by polarizer and two transparent protective films that are installed in its both sides.As a protective film, can use cyclic polyolefin film of the present invention.As another protective film, can use typical cellulose acetate film.As polarizer, can use the dye type polarizer and polyalkenyl (polyen-based) polarizer of iodo polarizer, use dichroic dye.Usually use PVA-based film preparation iodo polarizer and dye type polarizer.When using cyclic polyolefin film of the present invention as polarizer protection film, the film that makes as described below is through surface treatment, and the film surface that will handle with bonding agent adheres to polarizer then.The example of operable bonding agent comprises polyvinyl alcohol-based adhesives, for example polyvinyl alcohol (PVA) and polyvinyl butyral etc.; Vinyl latex, for example butyl acrylate etc. and gelatin etc.Polaroid is made up of the protective film of polarizer and its both sides of protection.In addition, adhere to protective film, and barrier film is adhered to its opposite side in a side of polarizer.Protective film and barrier film are used for protection polaroid when transportation polaroid and product detection etc.In this case, adhere to the surface of protective film, and be used for the relative opposite side of side with the polaroid of waiting to adhere to liquid crystal board with the protection polaroid.Barrier film is used to cover with polaroid and the bonding bonding coat of liquid crystal board, and is used for a side of waiting to adhere to liquid crystal board of polaroid.
Preferred cyclic polyolefin film of the present invention links to each other with polarizer, like this slow axis of the axis of homology of polarizer and cyclic polyolefin film of the present invention coupling.The polaroid that evaluation makes with intersection Nicol state.Found that when the quadrature precision of the slow axis of cyclic polyolefin film of the present invention and the absorption axes of polarizer (with the axle of axis of homology quadrature) is 1 ° or when bigger, the polarization property of polaroid of Nicol state of intersecting is lower, causes light leak.When this polaroid and liquid crystal cell combination, can not obtain enough black level or contrast.Therefore, preferably 1 ° or littler of the skew between the direction of the direction of the principal refractive index of cyclic polyolefin film of the present invention and the axis of homology of polaroid, more preferably 0.5 ° or littler.
For monolithic transmittance TT, the rectilinear transmittance PT that measures polaroid and the transmittance CT that intersects, use UV3100PC (making) by Shimadzu Corporation.In the scope of 380nm-780nm, measure.For all monolithic transmittances, rectilinear transmittance and intersection transmittance, measure 10 times and obtain their mean value.Followingly carry out the polaroid serviceability test with two kinds of forms, that is, (1) only adopts polaroid and (2) to adopt polaroid and the combination by bonding agent glass sheet adhered thereto.With regard to the mensuration that only adopts polaroid, prepare two identical samples, wherein optical compensating film is placed and placed to two polarizers with quadrature between them.With regard to the mensuration that adopts polaroid and the glass sheet of adhesion on it, (about 5cm * 5cm), wherein polaroid adheres to and makes optical compensating film be positioned at a side of glass sheet on the glass sheet to prepare two identical samples.In order to measure the monolithic transmittance, each sample is set makes film point to light source.Two samples are measured, and guessed mean is the monolithic transmittance.The preferable range of polarization property is: with regard to monolithic transmittance TT, and 40.5≤TT≤45; With regard to rectilinear transmittance PT, 32≤PT≤39.5; And with regard to intersection transmittance CT, CT≤1.5.More preferably scope is: with regard to monolithic transmittance TT, and 41.0≤TT≤44.5; With regard to rectilinear transmittance PT, 34≤PT≤39.5; And with regard to intersection transmittance CT, CT≤1.3.In the polaroid serviceability test, variable quantity is preferably less.
(surface treatment of cyclic polyolefin film)
In the present invention, the surface of cyclic polyolefin film through surface treatment to improve the cohesive between polarizer and the protective film.As long as cohesive improves, can use the arbitrary surfaces disposal route.The surface treatment of preferred type comprises, for example, and glow discharge processing, ultraviolet treatment with irradiation, corona treatment and flame treatment.Glow discharge used herein is handled and be meant the so-called Low Temperature Plasma Treating of carrying out in low-pressure gas.For the present invention, the Cement Composite Treated by Plasma under the atmospheric pressure most preferably.At United States Patent (USP) 3,462,335,3,761299,4,072,769 and BrP 891469 in describe glow discharge in detail and handle.Also can use the method described in the JP-A59-556430, the atmosphere composition that wherein discharges only contains a kind of gas that polyester supporter discharge process is produced after the discharge beginning.Handle in order to carry out vacuum glow discharge, can use the method described in the JP-B 60-16614, wherein the surface temperature of film be 80 ℃ or higher and 180 ℃ or lower in discharge.
Vacuum tightness when glow discharge is handled is 0.5-3000Pa, more preferably 2-300Pa preferably.Voltage is 500-5000V preferably, more preferably 500-3000V.Used discharge frequency be from direct current to several kilo-mega cycles per seconds, more preferably 50Hz-20MHz, even more preferably 1kHz-1MHz.Discharge process intensity is 0.01kVAmin/m preferably 2-5kVAmin/m 2, more preferably 0.15kVAmin/m 2-1kVAmin/m 2
In the present invention, also preferably carry out the ultraviolet ray irradiation as surface treatment.The ultraviolet ray irradiation can for example be passed through, and the method described in JP-B 43-2603,43-2604 and the 45-3828 is carried out.Mercury lamp is the high-pressure sodium lamp that is formed by quartz ampoule, and the ultraviolet ray of wavelength in the scope of 180-380nm preferably is provided.Ultraviolet irradiation is as follows.As light source, if the capacity of supporter can make the surface temperature of protective film be increased to about 150 ℃ and no problem, can use so provides the high-pressure sodium lamp of main wavelength as the light of 365nm.When the needs sub zero treatment, it is the low pressure mercury lamp of the light of 254nm that main wavelength preferably is provided.Also can use few ozone type (ozone-less type) high-pressure sodium lamp and low pressure mercury lamp.Along with the amount of handling used light increases, polymer resinous thin film and the cohesive between the polarizer with the saturated alicyclic structure of thermoplasticity increase, but also have problem, are exactly that amount along with light increases, and film is painted and become fragile.Therefore, when using when the high-pressure sodium lamp of main wavelength as the light of 365nm is provided, the amount of the light of irradiation usefulness is 20-10 preferably, 000 (mJ/cm 2), more preferably 50-2,000 (mJ/cm 2).Be that the amount of the light of irradiation usefulness is 100-10 preferably, 000 (mJ/cm under the situation of low pressure mercury lamp of light of 254nm for main wavelength is provided 2), more preferably 300-1,500 (mJ/cm 2).
In the present invention, also preferably carry out Corona discharge Treatment as surface treatment.Corona discharge Treatment can for example be passed through, and the method described in JP-B 39-12838 and JP-A 47-19824,48-20867 and the 52-42114 is carried out.Operable Corona discharge Treatment equipment comprises solid-state corona treatment equipment, LEPEL type surface processing equipment and the VETAPHON type treatment facility etc. that Pillar Induction Company produces.Described processing can be carried out under atmospheric pressure in air.Discharge frequency during processing is 5-40kV preferably, more preferably 10-30kV.Waveform preferably exchanges the dextrorotation ripple.The transparent otch in gap (gaptransparent lance) between electrode and the dielectric roller is 0.1-10mm, more preferably 1.0-2.0mm.Discharge above the dielectric support body roller that in discharge band, provides, and pending amount is 0.3-0.4kVAmin/m 2, more preferably 0.34-0.38kVAmin/m 2
In the present invention, also preferably carry out flame treatment as surface treatment.Can use in rock gas, liquid propane gas and the town gas arbitrarily, but with Air mixing than being important.Reason is to think that by the effect that surface treatment provided of using flame be plasma generation by containing active oxygen.Key is the amount for activity of the plasma of the important performance of flame (temperature) and oxygen.This is by the ratio decision of gas/oxygen.When gas and oxygen did not have surplus or short ground to react each other, energy density was the highest and therefore plasma active high.Specifically, rock gas/Air mixing is than by volume preferably 1/6-1/10, more preferably 1/7-1/9.Liquid propane gas/Air mixing is than by volume preferably 1/14-1/22, more preferably 1/16-1/19.Town gas/Air mixing is than by volume preferably 1/2-1/8, more preferably 1/3-1/7.The amount of handling used flame is at 1-50kcal/m 2Scope in, more preferably 3-20kcal/m 2The top and the distance between the film of the internal flame of burner are 3-7cm, more preferably 4-6cm.The preferred nozzle shape of burner comprises band shape, the vesicular of Heat Wise Inc. (U.S.), the band shape of Aerogen Company Limited (Britain), the Kasuga Ew Co. of Flynn Burner Corp. (U.S.), Ltd. the zigzag vesicular of (Japan), with Koike SansoKogyo Co., the zigzag vesicular of Ltd. (Japan).The backing roll of supporting film to use with respect to flame is the hollow shape roller.Feasible is to come the cooled supports roller by chilled water, so that carry out described processing under 20-50 ℃ steady temperature.
The preferable range of surface treatment degree changes with the type of surface-treated type or cyclic polyolefin.After preferred surface was handled, the surface of surface-treated protective film and the contact angle of pure water were less than 50 °.Preferably 25 ° or bigger and of this contact angles less than 45 °.When the surface of protective film and the contact angle between the pure water were in above-mentioned scope, the bond strength between protective film and the polarization film was satisfactory.
(bonding agent)
In the present invention, the bonding agent that contains water-soluble polymers be used for the polarizer that will form by polyvinyl alcohol (PVA) and the protective film that forms by surface-treated fluoropolymer resin with thermoplasticity saturated fat ring structure bonded to each other.
The example that is preferred for the water-soluble polymers of bonding agent comprises single polymers or multipolymer, they have ethylenically unsaturated monomers as the unit, for example N-vinyl pyrrolidone, acrylic acid, methacrylic acid, maleic acid, senecioate-hydroxy methacrylate, methacrylic acid-beta-hydroxy ethyl ester, vinyl alcohol, methyl vinyl ether, vinyl acetate, acrylamide, Methacrylamide, diacetone acrylamide, vinyl imidazole; Polyoxyethylene; Polyoxypropylene etc.; Poly--2-methyl  azoles quinoline; Methylcellulose; Hydroxy ethyl cellulose; Hydroxy propyl cellulose; Gelatin etc.For the present invention, preferred PVA and gelatin.
The preferred characteristics of PVA preferred characteristics of PVA when PVA is used for above-mentioned polarizer was identical when PVA was used for bonding agent.In the present invention, the preferred crosslinking chemical that uses in addition.The example of the crosslinking chemical that preferably uses when PVA is used for bonding agent comprises boric acid, multivalence aldehyde, multifunctional isocyanuric acid ester compounds and multi-functional epoxy compound etc.For the present invention, special preferred boric acid.
As the gelatin that is used for bonding agent, can use the gelatin of so-called lime treatment, the gelatin of acid treatment, gelatin, gelatine derivative or the metagelatin etc. that enzyme was handled.In these kind gelatin, preferably use the gelatin of lime treatment and the gelatin of acid treatment.The example of the crosslinking chemical that can be preferably when gelatin is used for bonding agent uses with gelatin comprises active halogen compound (2; 4-two chloro-6-hydroxyls-1; 3; 5-triazine and sodium salt thereof etc.); active vinyl-compound ((1; 3-bi-vinyl sulfonyl-2-propyl alcohol; 1; 2-bi-vinyl sulfonyl acetamide) ethane; two (vinylsulfonyl methyl) ethers or the polyvinyl that has vinylsulfonyl at side chain) etc.); N-carbamyl pyridiniujm ((1-morpholinyl carbamyl-3-pyridine generation) methane sulfonates, etc.) and halogen acid amide salt (2-naphthalene sulfonic acids-1-(1-chloro-1-pyridine radicals methylene) pyrrolidine  etc.) etc.For the present invention, especially preferably use active halogen compound and active vinyl-compound.
With respect to water-soluble polymers in the bonding agent, the preferred addition of the crosslinking chemical that is used in combination with gelatin is 0.1 quality % or bigger and less than 40 quality %, more preferably 0.5 quality % or bigger and less than 30 quality %.Preferably, at least one surface coated of protective film or polarizer has bonding agent forming bonding coat, and protective film and polarizer are bonded to each other.Preferably, the surface treated of protective film is coated with bonding agent with the formation bonding coat, and this bonding coat and polarizer is surperficial bonding.The thickness of bonding coat after drying is 0.01-5 μ m preferably, preferred especially 0.05-3 μ m.
2. next, cellulose acylate film of the present invention is described.
[as the cotton of the raw material of cellulose acylate]
Cellulose as the raw material that is used for cellulose acylate of the present invention is cotton linters or wood pulp (hard wood pulp, soft wood pulp) etc.Can use the cellulose acylate that obtains by any raw cellulose.Can as required the plurality of raw materials cellulose be mixed.Can use for example Maruzawa﹠amp; Uda, Plastic Material Lecture (17) Cellulosic Resin, Nikkan KogyoShinbun (1970); With the raw cellulose described in the Hatsumei Kyokai ' s Disclosure Bulletin No.2001-1745 (7-8 page or leaf).Raw material to cellulose acylate film of the present invention has no particular limits.
[degree of substitution of cellulose acylate]
Next, the cellulose acylate of being made by above-mentioned cellulosic material of the present invention is described.Cellulose acylate of the present invention is by obtaining cellulosic acylated hydroxy.As substituting group, can use any acyl group with 2 (acetyl group)-22 carbon atoms.With regard to cellulose acylate of the present invention, the degree of substitution of cellulosic hydroxyl has no particular limits.The acetate of hydroxyl that can substituted cellulose and/or have 3-22 carbon atom fatty acid conjugation be determined as the basis, obtain degree of substitution by calculating.This assay method can carry out according to the ASTMD-817-91 method.
As mentioned above, with regard to cellulose acylate of the present invention, the degree of substitution of cellulosic hydroxyl has no particular limits.The degree of substitution of acyl substituted hydroxyl is 2.50-3.00 preferably, more preferably 2.75-3.00, even more preferably 2.85-3.00.
At the acetate of the hydroxyl of substituted cellulose and/or have in the fatty acid of 3-22 carbon atom, can use any acyl group with 2-22 carbon atom, have no particular limits, no matter it is aliphatic group or allyl.Can use the acyl group of single type or the potpourri of two or more acyl groups.They are for example cellulosic alkyl-carbonyl ester or alkenyl carbonyl ester, fragrant carbonyl ester or aromatic alkyl carbonyl ester, and can have substituting group.The example of their preferred acyl group comprises acetyl group, propiono, bytyry, heptanoyl group, caproyl, caprylyl, capryl, dodecane acyl group, tridecane acyl group, tetradecane acyl group, hexadecane acyl group, octadecanoyl, different-bytyry, uncle-bytyry, cyclohexane carbonyl, oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl etc.Wherein, preferred acetyl group, propiono, bytyry, dodecane acyl group, octadecanoyl, uncle-bytyry, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc.Preferred especially acetyl group, propiono and bytyry.
When the acyl substituent of the hydroxyl of substituted cellulose forms by two kinds in acetyl group, propiono and the bytyry basically, when being 2.50-3.00, can reduce total degree of substitution the optical anisotropy of cellulose acylate film.The acyl substituted degree is more preferably 2.60-3.00, even more preferably 2.65-3.00.
[degree of polymerization of cellulose acylate]
Measure according to viscosity average polymerization degree, the degree of polymerization that is preferred for cellulose acylate of the present invention is 180-700.With regard to cellulose acylate, the degree of polymerization is more preferably 180-550, even more preferably 180-400, preferred especially 180-350.When the degree of polymerization was too high, the viscosity of the rich liquor solution of cellulose acylate was too high and be difficult to form film by the described solution of curtain coating.Cross when low when the degree of polymerization, the intensity of the film of formation reduces.Can be as Uda etc., LimitingViscosity Method (Kazuo UDA and Hideo SAITO, the Journal of theSociety of Fiber Science and Technology, Japan, the 18th volume, No.1, the 105-120 page or leaf is measured average degree of polymerization described in 1962.This is described in detail in JP-A9-95538.
The molecular weight distribution that is preferred for cellulose acylate of the present invention is estimated by gel permeation chromatography.The preferred little and narrow molecular weight distribution of its polydispersity index (Mw/Mn) (Mw representation quality mean molecular weight and Mn represent number-average molecular weight).Concrete Mw/Mn value is 1.0-3.0 preferably, more preferably 1.0-2.0, most preferably 1.0-1.6.
When removing lower-molecular-weight component, mean molecular weight (degree of polymerization) increases but viscosity becomes and is lower than typical fibers plain acylate.Therefore, it is useful removing lower-molecular-weight component.By from the cellulose acylate that obtains by typical method, removing lower-molecular-weight component, can obtain to have the cellulose acylate of a small amount of lower-molecular-weight component.Can remove lower-molecular-weight component with suitable organic solvent washing cellulose acylate.In order to prepare the cellulose acylate with a small amount of lower-molecular-weight component, with respect to the cellulose of 100 mass parts, the amount that preferably will be used for the sulfuric acid catalyst of acetylization reaction is adjusted to the 0.5-25 mass parts.When the amount of sulfuric acid catalyst is in above-mentioned scope, can obtain to have the distribute cellulose acylate of (having uniform molecular weight distribution) of preferred molecular weight.The moisture of the cellulose acylate that makes according to the present invention is 2 quality % or littler preferably, more preferably 1 quality % or littler, preferred especially 0.7 quality % or littler.Usually, the moisture of the plain acylate of known fiber is 2.5-5 quality %.For moisture being reduced to above-mentioned level, must be with the cellulose acylate drying.Method has no particular limits, as long as obtain required moisture.Raw material synthetic method cotton and cellulose acylate of the present invention is described in detail in Hatsumei Kyokai ' s Disclosure Bulletin No.2001-1745 (publish March 15 calendar year 2001, Hatsumei Kyokai), 7-12 page or leaf.
With regard to cellulose acylate of the present invention, can use the cellulose acylate of single type or the potpourri of two or more cellulose acylates, as long as substituting group, degree of substitution, the degree of polymerization and molecular weight distribution etc. are respectively in above-mentioned scope.
[adjuvant of cellulose acylate]
Can be according to purposes; in each step, in cellulose acylate solution of the present invention, add various adjuvants (for example, reducing optically anisotropic compound, the agent of wavelength dependency profile adjustment, ultraviolet inhibitor, plastifier, anti-degradation, particulate, optical characteristics correctives etc.).These will be described below.Adjuvant can add in the random time of dope preparation process, and the step of adding adjuvant perhaps is provided after the final step of dope preparation process.
Preferred cellulose acylate film of the present invention contains at least a reduction optically anisotropic compound, particularly Rth=, and (the thickness direction retardation Rth of (nx+ny)/2-nz) * d representative is in satisfying following formula (IV) and scope (V).
(IV)(Rth(A)-Rth(0))/A≤-1.0
(V)0.01≤A≤30
As for top formula (I) and (II), preferred:
(IV) (Rth (A)-Rth (0))/A≤-2.0; With
(V) 0.05≤A≤25; With
More preferably:
(IV) (Rth (A)-Rth (0))/A≤-3.0; With
(V)0.1≤A≤20。
Wherein
Rth (A): the Rth (nm) of film of compound that contains the reduction Rth of A%;
Rth (0): the Rth (nm) of film that does not contain the compound of any reduction Rth (nm); With
A: the quality as the polymkeric substance of the material of film is the quality (%) of 100 o'clock described compounds.
[reducing the architectural characteristic of the optically anisotropic compound of cellulose acylate film]
The optically anisotropic compound that reduces cellulose acylate film is described.Use to suppress film inner cellulose acylate in face or the compound of thickness direction alignment,, make that Re is that zero-sum Rth is near zero so that fully reduce optical anisotropy.In order to realize this point, preferably reduce optically anisotropic compound and can fully be dissolved in the cellulose acylate and compound itself does not have club shaped structure or planar structure.Particularly, when compound had a plurality of plane functional groups such as aromatic group, preferred compound had functional group in the on-plane surface mode, not on same one side.
(Log P)
When production is used for cellulose acylate film of the present invention, preferred use as mentioned above in the face of retardation films inner cellulose acylate and the thickness direction orientation reduce the optically anisotropic compound of film thus.In this compounds, preferred octanol-water partition coefficient (log P value) is the compound of 0-7.Log P surpasses the compatibility difference of 7 compound and cellulose acylate and so film bleached and efflorescence.On the other hand, log P is less than 0 compound highly-hydrophilic and may reduce the water proofing property of cellulose acylate film.Log P is more preferably 1-6, even more preferably 1.5-5.
Octanol-water partition coefficient (log P) can be measured according to the flask infusion method (flask dipping method) of JIS Z7260-107 (2000).Replace practical measurement, can estimate octanol-water partition coefficient (log P) according to chemistry method or empirical method.With regard to computing method, preferred Crippen ' s fragmentation method (J.Chem.Inf.Comput.Sci., 27,21 (1987)); Viswanadhan ' s fragmentation method (J.Chem.Inf.Comput.Sa., 29,163 (1989)); Broto ' s fragmentation method (Eur.J.Med.Chem.-Chim.Theor., 19,71 (1984)).Wherein, more preferably Crippen ' s fragmentation method (J.Chem.Inf.Comput.Sci., 27,21 (1987)).When the log of compound P different and not simultaneously, preferably judge according to Crippen ' s fragmentation method whether described compound falls within the scope of the present invention with assay method or computing method.
[can reduce the physical property of optically anisotropic compound]
Compound with the optically anisotropic ability that reduces film can have or not have aromatic group.Preferably, the molecular weight with compound of the optically anisotropic ability that reduces film is 150-3000, more preferably 170-2000, even more preferably 200-1000.As long as molecular weight falls in this scope, compound can have the certain monomers structure or can have oligomer structure or the polymer architecture that a plurality of this monomeric units are bonded to each other.
Preferably, the compound with the optically anisotropic ability that reduces film is a liquid at 25 ℃, or fusing point is 25-250 ℃ solid, and more preferably it is a liquid at 25 ℃, or fusing point is 25-200 ℃ a solid.Preferably, the compound with the optically anisotropic ability that reduces film does not evaporate in dope curtain coating that forms cellulose acylate film and dry run.
The amount of adding the optically anisotropic compound of reduction in the film forming dope of the present invention to is the 0.01-30 quality % of cellulose acylate preferably, more preferably 1-25 quality %, even more preferably 5-20 quality %.
Here, the optically anisotropic compound of reduction that can one or more are dissimilar uses separately or is used in combination with any required ratio.
Reducing the time that optically anisotropic compound adds in the film forming dope can be the random time of dope preparation process, and can add described compound to dope in the final step of dope preparation.
As for reducing the content of optically anisotropic compound in cellulose acylate film of the present invention, the average content of compound from the surface of film at least to 10% the part that is no more than overall film thickness is the 80-99% of described compound at the average content of thin film center part.The amount of compound in film of the present invention can be determined by its amount and its amount at core in the film surface part of the IR absorption spectromtry described in the JP-A 8-57879.
Below, describe and be preferred for the instantiation that the present invention reduces the optically anisotropic compound of cellulose acylate film, but the present invention is not limited to these compounds.
The value of logP as herein described is based on Crippen ' s fragmentation method (J.Chem.Inf.Comput.Sci., 27,21 (1987)) acquisition.
Formula (1):
In the above in the general formula (1), R 1Represent alkyl or aryl, and R 2And R 3Represent hydrogen atom, alkyl or aryl independently of one another.Preferred especially R 1, R 2And R 3The total number of carbon atoms be 10 or bigger.As substituting group, preferred fluorine atom, alkyl, aryl, alkoxy, sulfuryl and sulfoamido; And special preferred alkyl, aryl, alkoxy, sulfuryl and sulfoamido.Alkyl can have straight chain, side chain or ring structure.。Alkyl preferably has 1-25 carbon atom, more preferably 6-25, even more preferably 6-20 (for example, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, heptyl, octyl group, dicyclo octyl group, nonyl, adamantyl, decyl, uncle's octyl group, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl and didecyl).Aryl preferably has 6-30 carbon atom, preferred especially 6-24 (for example, phenyl, xenyl, terphenyl, naphthyl, binaphthyl and triphenyl phenyl).The preferred embodiment that shows the compound of general formula (1) representative below, but the present invention is not limited to these preferred embodiment.
Figure A20068000228000481
Figure A20068000228000491
Formula (2):
Figure A20068000228000492
In the formula, R 31Represent alkyl or aryl, and R 32And R 33Represent hydrogen atom, alkyl or aryl independently of one another.Alkyl can have straight chain, side chain or ring structure.Alkyl preferably has 1-20 carbon atom, and more preferably 1-15, even more preferably 1-12.In the naphthenic base, preferred especially cyclohexyl.Aryl preferably has 6-36 carbon atom, more preferably 6-24.
Abovementioned alkyl or aryl can have substituting group.As substituting group, preferred halogen atom (for example, chlorine, bromine, fluorine, iodine etc.), alkyl, aryl, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, sulfuryl amino, hydroxyl, cyano group, amino and acyl amino; More preferably halogen atom, alkyl, aryl, alkoxy, aryloxy group, sulfuryl amino and acyl amino; Special preferred alkyl, aryl, sulfuryl amino and acyl amino.
The preferred embodiment that shows the compound of general formula (2) representative below, but the present invention is not limited to these preferred embodiment.
Figure A20068000228000511
Figure A20068000228000521
Figure A20068000228000531
Figure A20068000228000541
Figure A20068000228000551
Figure A20068000228000561
Figure A20068000228000571
[agent of wavelength dependency profile adjustment]
The compound (this paper back is referred to as " agent of wavelength dependency profile adjustment ") of the wavelength dependency distribution that reduces cellulose acylate film is described.For the wavelength dependency Rth that improves cellulose acylate film of the present invention distributes, preferably contain at least a reduction Δ Rth=|Rth (400)-Rth (700)| the compound that the wavelength dependency Rth of representative distributes, its in satisfying following formula (VI) and scope (VII),
(VI) (Δ Rth (B)-Δ Rth (0))/B≤-2.0 and
(VII)0.01≤B≤30。
As for following formula (VI) and (VII), preferred:
(VI) (Δ Rth (B)-Δ Rth (0))/B≤-3.0 and
(VII) 0.01≤B≤25; With
More preferably:
(VI) (Δ Rth (B)-Δ Rth (0))/B≤-4.0 and
(VII)0.01≤B≤20
Wherein,
Rth (400): the Rth under the 400nm (nm);
Rth (700): the Rth under the 700nm (nm);
Δ Rth (B): the Δ Rth (nm) of film of compound that contains the reduction Rth of B quality %;
Rth (0): the Rth (nm) of film that does not contain the compound of any reduction Rth; With
B: the quality as the polymkeric substance of membraneous material is the quality (%) of 100 o'clock described compounds.
The Re of cellulose acylate film and Rth value have the wavelength dependency distribution character usually, and wherein the Re in the longer wavelength scope and Rth value are greater than in the shorter wavelength scope.Therefore, need wavelength dependency be distributed smoothly by Re and the Rth that increases relative shorter wavelength side.By contrast, the compound of light that absorbs the ultraviolet ray range of 200-400nm has extinction in the longer wavelength scope greater than the wavelength dependency distribution character of the extinction in the shorter wavelength scope.Suppose under this compound isotropically is present in situation in the cellulose acylate film, the birefringence of compound itself, and wavelength dependency Re and Rth distribute is bigger in the shorter wavelength scope as the wavelength dependency of extinction distributes.
Therefore, the wavelength dependency Re and the Rth that use the compound of the light in the ultraviolet ray range be absorbed in 200-400nm can regulate cellulose acylate film distribute, and suppose that as mentioned above having big wavelength dependency in the shorter wavelength scope distributes.In order to realize this point, the compound that the adjusting wavelength dependency distributes is essential can be enough miscible with cellulose acylate equably.The UVA scope of this compound is 200-400nm preferably, more preferably 220-395nm, even more preferably 240-390nm.
In the liquid crystal indicator of the personal computer of nearest TV, notebook type and mobile display terminal, require optical element to have high transmittance, so that these display device can have high brightness with smaller power.In this, reduce cellulose acylate film when having in the ultraviolet region of 200-400nm to absorb and have | Re (400)-Re (700)| and | Rth (400)-Rth (700)| the compound of ability when joining in the film, have the film of described compound can have high spectral transmittance preferred the adding.Preferably, cellulose acylate film of the present invention has the spectral transmittance of 45%-95% under the wavelength of 380nm, and is to have 10% spectral transmittance at the most under the wavelength of 350nm at wavelength.
From the angle of its evaporation, as mentioned above, be preferred for wavelength dependency anisotropy distribution improver of the present invention, preferably have the molecular weight of 250-1000, more preferably 260-800, even more preferably 270-800, more preferably 300-800 once more.If molecular weight falls in this scope, described improver can have the certain monomers structure or can have oligomer structure or the polymer architecture that comprises a plurality of monomeric units that are connected with each other.
Optimal wavelength dependence anisotropy distribution improver does not evaporate in dope curtain coating that forms cellulose acylate film and dry run.
(addition of compound)
The amount that is preferred for above-mentioned wavelength dependency anisotropy distribution improver of the present invention is the 0.01-30 quality % of cellulose acylate preferably, more preferably 0.1-20 quality %, even more preferably 0.2-10 quality %.
(adding method of compound)
These wavelength dependency anisotropy distribution improvers that can one or more are dissimilar separately or combination be used for this paper.
Add as for it, can wavelength dependency anisotropy distribution improver be joined in the film forming dope in any stage of dope preparation or the final step for preparing at dope.
The instantiation that is preferred for wavelength dependency anisotropy distribution improver of the present invention has benzotriazole cpd, benzophenone (oxybenzophenone) compound, cyano-containing compound, oxidation of benzophenone compound, salicylate compound and nickel complex salt compound, yet the present invention is not limited to this.
The preferred embodiment that is used as the benzotriazole cpd of wavelength dependency anisotropy distribution improver of the present invention has those of following formula (101):
Q 1-Q 2-OH
Q wherein 1Represent nitrogenous aromatic heterocycle; And Q 2Represent aromatic rings.
Q 1It is nitrogenous aromatic heterocycle, the nitrogenous aromatic heterocycle of preferred 5-to 7-unit, more preferably 5-or 6-the unit nitrogenous aromatic heterocycle, comprise, for example, imidazoles, pyrazoles, triazole, tetrazolium, thiazole,  azoles, selenazoles, benzotriazole, benzothiazole, benzoxazol, benzo selenazoles, thiadiazoles,  diazole, aphthothiazoles, naphtho- azoles, azepine benzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, benzotriazole, the purine.More preferably, Q 1Be the nitrogenous aromatic heterocycle of 5-unit, specifically comprise imidazoles, pyrazoles, triazole, tetrazolium, thiazole,  azoles, benzotriazole, benzothiazole, benzoxazol, thiadiazoles,  diazole, preferred especially benzotriazole.
Q 1Nitrogenous aromatic heterocycle can have substituting group.With regard to this substituting group, can use following substituting group T.A plurality of substituting groups if any, can condensation form condensed ring.
Q 2Aromatic rings can be aromatic hydrocarbon ring or aromatic heterocycle.It can be monocycle or can form condensed ring with any other ring.
The aromatic hydrocarbon ring preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus) of 6-30 carbon atom, more preferably has 6-20 carbon atom, even the more preferably aromatic hydrocarbon ring of 6-12 carbon atom.Once more more preferably, it is a phenyl ring.
This aromatic heterocycle is the aromatic heterocycle of nitrogen atom or sulphur atom preferably.The example of heterocycle has thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles,  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, the purine.Aromatic heterocycle is pyridine, triazine or quinoline preferably.
Q 2Aromatic rings aromatic hydrocarbon ring preferably, more preferably naphthalene nucleus or phenyl ring, even more preferably phenyl ring.Q 2Can have substituting group.With regard to this substituting group, preferred following substituting group T.
Substituting group T comprises that for example, alkyl (preferably has 1-20 carbon atom; more preferably 1-12 carbon atom, even more preferably 1-8 carbon atom, for example; methyl; ethyl; isopropyl; the tert-butyl group; n-octyl; positive decyl; n-hexadecyl; cyclopropyl; cyclopentyl; cyclohexyl); thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, even more preferably 2-8 carbon atom; for example, vinyl; allyl; the 2-butenyl group; the 3-pentenyl); alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom; even more preferably 2-8 carbon atom; for example, propargyl; the 3-pentynyl); aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom; even more preferably 6-12 carbon atom; for example, phenyl; right-aminomethyl phenyl; naphthyl); replacement or unsubstituted amino (preferably have 0-20 carbon atom, more preferably 0-10 carbon atom; even more preferably 0-6 carbon atom; for example, amino; methylamino; dimethylamino; diethylamino; dibenzyl amino); alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom; even more preferably 1-8 carbon atom; for example, methoxyl; ethoxy; butoxy); aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, phenoxy group; the 2-naphthoxy); acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, acetyl group; benzoyl; formoxyl; valeryl); alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl; ethoxy carbonyl); aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-10 carbon atom; for example, phenyloxycarbonyl); acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetoxyl group; benzoyloxy); acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetyl-amino; benzoyl-amido); alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-12 carbon atom; for example, phenyloxycarbonyl amino); sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl amino; benzenesulfonyl amino); sulfamoyl (preferably has 0-20 carbon atom, more preferably 0-16 carbon atom; even more preferably 0-12 carbon atom; for example, sulfamoyl; the methyl sulfamoyl; the dimethylamino sulfonyl; the phenyl sulfamoyl base); carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, carbamyl; the methyl carbamyl; the diethyl amino formoxyl; the phenylamino formoxyl); alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methyl mercapto; ethylmercapto group); arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, thiophenyl); sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl; tosyl); sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methanesulfinyl; the phenylsulfinyl base); urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, urea groups; the methyl urea groups; the phenyl urea groups); the phosphinylidyne amido (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, diethyl phosphinylidyne amido; phenyl phosphinylidyne amido); hydroxyl; sulfydryl; halogen atom (for example, fluorine atom; the chlorine atom; bromine atoms; the iodine atom); cyano group; sulfo group; carboxyl; nitro; the hydroxamic acid base; sulfino; diazanyl; imino group; heterocyclic radical (preferably has 1-30 carbon atom; more preferably 1-12 carbon atom; wherein heteroatoms is a nitrogen-atoms; in oxygen atom or the sulphur atom arbitrarily, for example, imidazole radicals; pyridine radicals; quinolyl; furyl; piperidyl; morpholinyl; the benzoxazol base; benzimidazolyl; benzothiazolyl); silicyl (preferably has 3-40 carbon atom; more preferably 3-30 carbon atom; even more preferably 3-24 carbon atom, for example, trimethyl silyl; the triphenyl silicyl).These substituting groups can also be substituted.Two or more substituting groups, if any, can be identical or different.If possible, they can be connected with each other and form ring.
In the compound of formula (101), the compound of preferred following formula (101-A):
Formula (101-A)
Figure A20068000228000631
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Represent hydrogen atom or substituting group independently of one another.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Represent hydrogen atom or substituting group independently of one another.With regard to this substituting group, mention above-mentioned substituting group T.These substituting groups can have other substituting group arbitrarily.Substituting group can condensation form the condensed ring structure.
R 1And R 3Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or have the alkyl of 1-12 carbon atom; The alkyl (preferably having 4-12 carbon atom) that more preferably has 1-12 carbon atom once more.
R 2And R 4Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or have the alkyl of 1-12 carbon atom; More preferably hydrogen atom or methyl once more; Hydrogen atom most preferably.
R 5And R 8Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or have the alkyl of 1-12 carbon atom; More preferably hydrogen atom or methyl once more; Hydrogen atom most preferably.
R 6And R 7Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or halogen atom; More preferably hydrogen atom or chlorine atom once more.
In the compound of formula (101), more preferably those of following formula (101-B):
Formula (101-B)
Figure A20068000228000641
R wherein 1, R 3, R 6And R 7Have with formula (101-A) in identical implication, and their preferable range also with formula (101-A) in identical.
Provide the instantiation of the compound of formula (101) below, yet the present invention is not limited to this.
Figure A20068000228000651
Figure A20068000228000661
Figure A20068000228000671
In the above-mentioned benzotriazole cpd, preferred molecular weight is not less than those of 320.We, inventors of the present invention have confirmed that this compounds is being useful aspect the retentivity of the cellulose acylate film that is formed by them.
The preferred embodiment that is used as the benzophenone cpd of wavelength dependency anisotropy distribution improver of the present invention is the compound of following formula (102):
Formula (102)
Figure A20068000228000672
Q wherein 1And Q 2Represent aromatic rings independently of one another; X represents NR (wherein R represents hydrogen atom or substituting group), oxygen atom or sulphur atom.
Q 1And Q 2Aromatic rings can be aromatic hydrocarbon ring or aromatic heterocycle.It can be monocycle or can form condensed ring with any other ring.
Q 1And Q 2The aromatic hydrocarbon ring preferably have the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus) of 6-30 carbon atom, more preferably have 6-20 carbon atom, even a more preferably aromatic hydrocarbon ring of 6-12 carbon atom.Once more more preferably, it is a phenyl ring.
Q 1And Q 2Aromatic heterocycle preferably contain in oxygen atom, nitrogen-atoms or the sulphur atom any one aromatic heterocycle at least.The example of heterocycle has furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles,  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, the purine.Aromatic heterocycle is pyridine, triazine or quinoline preferably.
Q 1And Q 2Aromatic rings aromatic hydrocarbon ring preferably, more preferably have the aromatic hydrocarbon ring of 6-10 carbon atom, more preferably replace once more or unsubstituted phenyl ring.
Q 1And Q 2Can have substituting group, the preferably following substituting group T of this substituting group.Yet described substituting group does not comprise carboxylic acid, sulfonic acid and quaternary ammonium salt.If possible, the substituting group formation ring structure that can be connected with each other.
X represents NR (wherein R represents hydrogen atom or substituting group, and with regard to this substituting group, mentions following substituting group T), oxygen atom or sulphur atom.X is NR (wherein preferably acyl group or sulfonyl of R, described acyl group or sulfonyl can be substituted) or O, more preferably O preferably.
Substituting group T comprises that for example, alkyl (preferably has 1-20 carbon atom; more preferably 1-12 carbon atom, even more preferably 1-8 carbon atom, for example; methyl; ethyl; isopropyl; the tert-butyl group; n-octyl; positive decyl; n-hexadecyl; cyclopropyl; cyclopentyl; cyclohexyl); thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, even more preferably 2-8 carbon atom; for example, vinyl; allyl; the 2-butenyl group; the 3-pentenyl); alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom; even more preferably 2-8 carbon atom; for example, propargyl; the 3-pentynyl); aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom; even more preferably 6-12 carbon atom; for example, phenyl; right-aminomethyl phenyl; naphthyl); replacement or unsubstituted amino (preferably have 0-20 carbon atom, more preferably 0-10 carbon atom; even more preferably 0-6 carbon atom; for example, amino; methylamino; dimethylamino; diethylamino; dibenzyl amino); alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom; even more preferably 1-8 carbon atom; for example, methoxyl; ethoxy; butoxy); aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, phenoxy group; the 2-naphthoxy); acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, acetyl group; benzoyl; formoxyl; valeryl); alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl; ethoxy carbonyl); aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-10 carbon atom; for example, phenyloxycarbonyl); acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetoxyl group; benzoyloxy); acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetyl-amino; benzoyl-amido); alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-12 carbon atom; for example, phenyloxycarbonyl amino); sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl amino; benzenesulfonyl amino); sulfamoyl (preferably has 0-20 carbon atom, more preferably 0-16 carbon atom; even more preferably 0-12 carbon atom; for example, sulfamoyl; the methyl sulfamoyl; the dimethylamino sulfonyl; the phenyl sulfamoyl base); carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, carbamyl; the methyl carbamyl; the diethyl amino formoxyl; the phenylamino formoxyl); alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methyl mercapto; ethylmercapto group); arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, thiophenyl); sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl; tosyl); sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methanesulfinyl; the phenylsulfinyl base); urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, urea groups; the methyl urea groups; the phenyl urea groups); the phosphinylidyne amido (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, diethyl phosphinylidyne amido; phenyl phosphinylidyne amido); hydroxyl; sulfydryl; halogen atom (for example, fluorine atom; the chlorine atom; bromine atoms; the iodine atom); cyano group; sulfo group; carboxyl; nitro; the hydroxamic acid base; sulfino; diazanyl; imino group; heterocyclic radical (preferably has 1-30 carbon atom; more preferably 1-12 carbon atom; wherein heteroatoms is a nitrogen-atoms; in oxygen atom or the sulphur atom arbitrarily, for example, imidazole radicals; pyridine radicals; quinolyl; furyl; piperidyl; morpholinyl; the benzoxazol base; benzimidazolyl; benzothiazolyl); silicyl (preferably has 3-40 carbon atom; more preferably 3-30 carbon atom; even more preferably 3-24 carbon atom, for example, trimethyl silyl; the triphenyl silicyl).These substituting groups can also be substituted.Two or more substituting groups, if any, can be identical or different.If possible, they can be connected with each other and form ring.
In the compound of formula (102), those of preferred following formula (102-A):
Formula (102-A)
Figure A20068000228000701
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Represent hydrogen atom or substituting group independently of one another.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8And R 9Represent hydrogen atom or substituting group independently of one another.With regard to this substituting group, mention above-mentioned substituting group T.These substituting groups can have other substituting group arbitrarily.Substituting group can condensation form the condensed ring structure.
R 1, R 3, R 4, R 5, R 6, R 8And R 9Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or have the alkyl of 1-12 carbon atom; More preferably hydrogen atom or methyl once more; Hydrogen atom most preferably.
R 2Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, amino, alkoxy, aryloxy group or hydroxyl with 6-12 carbon atom with 1-12 carbon atom with 0-20 carbon atom with 1-20 carbon atom; Even more preferably has an alkoxy of 1-20 carbon atom; The alkoxy that more preferably has 1-12 carbon atom once more.
R 7Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, amino, alkoxy, aryloxy group or hydroxyl with 6-12 carbon atom with 1-12 carbon atom with 0-20 carbon atom with 1-20 carbon atom; Even more preferably hydrogen atom or have the alkoxy (preferably have 1-12 carbon atom, more preferably have 1-8 carbon atom, once more more preferably methyl) of 1-20 carbon atom; Special preferable methyl or hydrogen atom.
In the compound of formula (102), more preferably those of following formula (102-B):
Formula (102-B)
Figure A20068000228000711
R wherein 10Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted alkynyl or replacement or unsubstituted aryl.
R 10Be hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted alkynyl or replacement or unsubstituted aryl.With regard to substituting group, mention above-mentioned substituting group T.
R 10Preferably replace or unsubstituted alkyl, more preferably replace or unsubstituted alkyl with 5-20 carbon atom, even more preferably replace or unsubstituted alkyl with 5-12 carbon atom (for example, n-hexyl, 2-ethylhexyl, n-octyl, positive decyl, dodecyl, benzyl), more preferably replace once more or unsubstituted alkyl (for example, 2-ethylhexyl, n-octyl, positive decyl, dodecyl, benzyl) with 6-12 carbon atom.
The compound of formula (102) can make according to for example known method described in the JP-A11-12219.
Provide the instantiation of the compound of formula (102) below, yet the present invention is not limited to this.
Figure A20068000228000721
Figure A20068000228000731
Figure A20068000228000741
As the preferred embodiment of the compound of the cyano-containing of wavelength dependency anisotropy distribution improver of the present invention is those of following formula (103):
Formula (103)
Figure A20068000228000742
Q wherein 1And Q 2Represent aromatic rings independently of one another; X 1And X 2Represent hydrogen atom or substituting group independently of one another, and at least one is cyano group, carboxyl, sulfo group or aromatic heterocycle group in them.
Q 1And Q 2Aromatic rings can be aromatic hydrocarbon ring or aromatic heterocycle, and it can be monocycle or can form condensed ring with any other ring.
The aromatic hydrocarbon ring preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus) of 6-30 carbon atom, more preferably has 6-20 carbon atom, even more preferably has the aromatic hydrocarbon ring of 6-12 carbon atom.Once more more preferably, it is a phenyl ring.
Aromatic heterocycle preferably contains nitrogen-atoms or sulphur atom as heteroatomic ring.The example of heterocycle has thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles,  azoles quinoline,  azoles,  diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazol, benzothiazole, benzotriazole, the purine.Aromatic heterocycle is pyridine, triazine or quinoline preferably.
Q 1And Q 2Aromatic rings preferably aromatic hydrocarbon ring, more preferably phenyl ring.
Q 1And Q 2Can have substituting group, mention following substituting group T for described substituting group.Substituting group T comprises that for example, alkyl (preferably has 1-20 carbon atom; more preferably 1-12 carbon atom, even more preferably 1-8 carbon atom, for example; methyl; ethyl; isopropyl; the tert-butyl group; n-octyl; positive decyl; n-hexadecyl; cyclopropyl; cyclopentyl; cyclohexyl); thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, even more preferably 2-8 carbon atom; for example, vinyl; allyl; the 2-butenyl group; the 3-pentenyl); alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom; even more preferably 2-8 carbon atom; for example, propargyl; the 3-pentynyl); aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom; even more preferably 6-12 carbon atom; for example, phenyl; right-aminomethyl phenyl; naphthyl); replacement or unsubstituted amino (preferably have 0-20 carbon atom, more preferably 0-10 carbon atom; even more preferably 0-6 carbon atom; for example, amino; methylamino; dimethylamino; diethylamino; dibenzyl amino); alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom; even more preferably 1-8 carbon atom; for example, methoxyl; ethoxy; butoxy); aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, phenoxy group; the 2-naphthoxy); acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, acetyl group; benzoyl; formoxyl; valeryl); alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl; ethoxy carbonyl); aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-10 carbon atom; for example, phenyloxycarbonyl); acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetoxyl group; benzoyloxy); acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-10 carbon atom; for example, acetyl-amino; benzoyl-amido); alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom; even more preferably 2-12 carbon atom; for example, methoxycarbonyl amino); aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom; even more preferably 7-12 carbon atom; for example, phenyloxycarbonyl amino); sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl amino; benzenesulfonyl amino); sulfamoyl (preferably has 0-20 carbon atom, more preferably 0-16 carbon atom; even more preferably 0-12 carbon atom; for example, sulfamoyl; the methyl sulfamoyl; the dimethylamino sulfonyl; the phenyl sulfamoyl base); carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, carbamyl; the methyl carbamyl; the diethyl amino formoxyl; the phenylamino formoxyl); alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methyl mercapto; ethylmercapto group); arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom; even more preferably 6-12 carbon atom; for example, thiophenyl); sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, mesyl; tosyl); sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, methanesulfinyl; the phenylsulfinyl base); urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, urea groups; the methyl urea groups; the phenyl urea groups); the phosphinylidyne amido (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom; even more preferably 1-12 carbon atom; for example, diethyl phosphinylidyne amido; phenyl phosphinylidyne amido); hydroxyl; sulfydryl; halogen atom (for example, fluorine atom; the chlorine atom; bromine atoms; the iodine atom); cyano group; sulfo group; carboxyl; nitro; the hydroxamic acid base; sulfino; diazanyl; imino group; heterocyclic radical (preferably has 1-30 carbon atom; more preferably 1-12 carbon atom; wherein heteroatoms is a nitrogen-atoms; in oxygen atom or the sulphur atom arbitrarily, for example, imidazole radicals; pyridine radicals; quinolyl; furyl; piperidyl; morpholinyl; the benzoxazol base; benzimidazolyl; benzothiazolyl); silicyl (preferably has 3-40 carbon atom; more preferably 3-30 carbon atom; even more preferably 3-24 carbon atom, for example, trimethyl silyl; the triphenyl silicyl).These substituting groups can also be substituted.Two or more substituting groups, if any, can be identical or different.If possible, they can be connected with each other and form ring.
X 1And X 2Each is hydrogen atom or substituting group naturally, and at least one is cyano group, carboxyl, sulfo group or aromatic heterocycle group in them.With regard to X 1And X 2Substituting group, mention above-mentioned substituting group T.X 1And X 2Substituting group can be replaced and X by any other substituting group 1And X 2Can condensation form ring structure.
X 1And X 2Preferably hydrogen atom, aryl, cyano group, nitro, carbonyl, sulfonyl or aromatic heterocycle; More preferably cyano group, carbonyl, sulfonyl or aromatic heterocycle; Even more preferably cyano group or carbonyl; More preferably cyano group or alkoxy carbonyl (C (=O) OR, wherein the R representative has the alkyl of 1-20 carbon atom, the aryl with 6-12 carbon atom or their combination) once more.
In the compound of formula (103), those of preferred following formula (103-A):
Formula (103-A)
Figure A20068000228000771
R wherein 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 10Represent hydrogen atom or substituting group independently of one another; X 1And X 2Have with formula (103) in identical implication, and their preferable range also with formula (103) in identical.
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9And R 10Represent hydrogen atom or substituting group independently of one another.With regard to this substituting group, mention above-mentioned substituting group T.These substituting groups can have other substituting group arbitrarily.Substituting group can condensation form the condensed ring structure.
R 1,, R 2, R 4, R 5, R 6, R 7, R 9And R 10Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, aryl, alkoxy, aryloxy group or halogen atom; Even more preferably hydrogen atom or have the alkyl of 1-12 carbon atom; More preferably hydrogen atom or methyl once more; Hydrogen atom most preferably.
R 3And R 8Preferably hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, hydroxyl or halogen atom; More preferably hydrogen atom, alkyl, amino, alkoxy, aryloxy group or hydroxyl with 6-12 carbon atom with 1-12 carbon atom with 0-20 carbon atom with 1-20 carbon atom; Even more preferably hydrogen atom or have the alkoxy of 1-12 carbon atom; The alkoxy that more preferably has 1-12 carbon atom once more; Preferred once more hydrogen atom.
In the compound of formula (103), more preferably those of following formula (103-B):
Formula (103-B)
Figure A20068000228000781
R wherein 3And R 8Have with formula (103-A) in identical implication, and their preferable range also with formula (103-A) in identical; X 3Represent hydrogen atom or substituting group.
X 3Represent hydrogen atom or substituting group.With regard to this substituting group, mention above-mentioned substituting group T.If possible, described substituting group can also replace with any other substituting group.X 3Preferably hydrogen atom, alkyl, aryl, cyano group, nitro, carbonyl, sulfonyl or aromatic heterocycle; More preferably cyano group, carbonyl, sulfonyl or aromatic heterocycle; Even more preferably cyano group or carbonyl; More preferably cyano group or alkoxy carbonyl (C (=O) OR, wherein R is the alkyl with 1-20 carbon atom, the aryl with 6-12 carbon atom or their combination) once more.
In the compound of formula (103), even more preferably those of following formula (103-C):
Formula (103-C)
Figure A20068000228000791
R wherein 3And R 8Have with formula (103-A) in identical implication, and their preferable range also with formula (103-A) in identical; R 21Representative has the alkyl of 1-20 carbon atom.
Work as R 3And R 8When all being hydrogen atom, R 21The alkyl that preferably has 2-12 carbon atom more preferably has the alkyl of 4-12 carbon atom, even more preferably has the alkyl of 6-12 carbon atom, once more more preferably n-octyl, uncle's octyl group, 2-ethylhexyl, positive decyl or dodecyl; 2-ethylhexyl most preferably.
Work as R 3And R 8When being not hydrogen atom, R 21Preferably have the alkyl of 20 carbon atoms at the most, the molecular weight of the compound of same up-to-date style (103-C) can be at least 300.
The compound that is used for formula of the present invention (103) can be according to Journal of AmericanChemical Society, the 63rd volume, and the method described in the 3452nd page (1941) makes.
Provide the instantiation of the compound of formula (103) below, yet the present invention is not limited to this.
Figure A20068000228000801
Figure A20068000228000811
Figure A20068000228000821
[duller particle]
Cellulose acylate film of the present invention preferably contains the particle as matting agent.Particle used herein comprises silicon dioxide, titania, aluminium oxide, Zirconium oxide, lime carbonate, talcum, clay, calcined kaolin, calcining calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate.The particle that particle is preferably siliceous, this is owing to the mist degree that contains their film can be low.Preferred especially silicon dioxide.The silica dioxide granule that is used for this paper preferably has the primary average particle size of 20nm at the most and the apparent specific gravity of 70g/l at least.The particle that more preferably has the little primary average particle size of 5-16nm, this is owing to the mist degree of the film that contains them is lower.Apparent specific gravity is more preferably 90-200g/l, even more preferably 100-200g/l.Particle with big apparent specific gravity can provide the dispersion with higher concentration, and since contain the mist degree of their film may be lower and owing to can reduce deposition of solid in the film, be preferred therefore.
Particle forms the secondary granule that mean grain size is 0.1-3.0 μ m usually, and in film, they exist with the aggregation of primary granule, therefore forms size at film surface and is the protrusion of 0.1-3.0 μ m.Preferably, the secondary mean grain size is 0.2 μ m-1.5 μ m, more preferably 0.4 μ m-1.2 μ m, most preferably 0.6 μ m-1.1 μ m.Elementary and the secondary particle diameter of following mensuration: with the particle in the sem observation film, and with the external diameter of a circle of particle as particle diameter.At 200 particles of diverse location random observation, and their data are average, obtain their mean grain size.
With regard to silica dioxide granule, can use commercially available prod Aerosil R972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600 (all deriving from Nippon Aerosil) here.Also for example Aerosil R976 and R811 (deriving from Nippon Aerosil) are commercially available for the Zirconium oxide particle, and can be used for this paper.
Wherein, Aerosil 200V and Aerosil R972V are that primary average particle size is that 20nm and apparent specific gravity are the silica dioxide granule of 70g/l at least at the most, and especially preferably they are used for this paper, this is because they can reduce the friction factor of optical thin film effectively, and does not increase its mist degree.
In the present invention, in order to obtain to contain the cellulose acylate film of particle, can use some to prepare the method for particle dispersion with young waiter in a wineshop or an inn's level mean grain size.For example, a kind of method comprises by stirring and mixed solvent and particle and prepares particle dispersion in advance, joins in the cellulose acylate solution that makes separately on a small quantity dispersions obtained then, it is mixed with main cellulose acylate dope afterwards again.Because the favorable dispersibility of silica dioxide granule and because the dispersion of the silica dioxide granule that makes reassociates therefore preferred this method hardly.In addition, this paper can also use the method that comprises the steps: the plain ester of small amount of fibers is joined in the solvent, stir they dissolvings, and in the on-line mixing device particle dispersion of gained is fully mixed with dope.The invention is not restricted to these methods.When silica dioxide granule being mixed and be distributed in the solvent, the silica concentration in dispersions obtained is 5-30 quality %, more preferably 10-25 quality %, most preferably 15-20 quality % preferably.With respect to the amount of wherein particle, the dispersion with higher concentration can have less mist degree, and owing to can reduce the muddy of film with it and can reduce deposition of solid in the film, is preferred therefore.At last, the amount of matting agent 0.01-1.0g/m preferably in the cellulose acylate dope 2, more preferably 0.03-0.3g/m 2, 0.08-0.16g/m most preferably 2
Solvent can be a lower alcohol, particular methanol, ethanol, propyl alcohol, isopropyl alcohol or butanols.Except these lower alcohols, the solvent that can be used for this paper has no particular limits, yet, the solvent of using always when being preferably formed cellulose ester film.
[plastifier, anti-degradation, release agent]
Except optically anisotropic compound of above-mentioned reduction and wavelength dependency anisotropy dispersion improving agent; cellulose acylate film of the present invention can contain in its preparation process and add wherein each kind of adjuvant (for example, plastifier, ultraviolet inhibitor, anti-degradation, release agent, infrared absorbent) according to the purposes of film.Adjuvant can be solid or oily.In other words, fusing point and the boiling point to them has no particular limits.For example, ultraviolet absorption material can be at 20 ℃ or lower and mix under 20 ℃ or higher temperature; And this can be used for mixed plasticizer equally.For example, this is described in JP-A2001-151901.And, for example, the infrared ray absorbing dyestuff has been described in JP-A2001-194522.The interpolation time of adjuvant can be the random time in the dope preparation process.Depend on the circumstances, adjuvant can add in the final step of dope preparation process.The addition of each adjuvant has no particular limits, as long as adjuvant can present its function.When cellulose acylate film had sandwich construction, the type that joins every layer adjuvant can be different with amount.For example, in JP-A2001-151902, described this point, and this technology is known in this area.Its details is described in Hatsumei Kyokai ' s Disclosure Bulletin No.2001-1745 (publish March 15 calendar year 2001, Hatsumei Kyokai), the 16-12 page or leaf, and preferably wherein said material is used for the present invention.
[mixing ratio of compound]
In cellulose acylate film of the present invention, with respect to the quality of cellulose acylate, molecular weight is the total amount 5-45% preferably of 3000 compound at the most, more preferably 10-40%, even more preferably 15-30%.As mentioned above, described compound comprises the optically anisotropic compound of reduction, wavelength dependency anisotropy dispersion improving agent, ultraviolet inhibitor, plastifier, anti-degradation, particulate, release agent and infrared absorbent.Preferably, they have at the most 3000, and more preferably at the most 2000, even more preferably 1000 molecular weight at the most.If the total amount of these compounds is less than 5%; the problem that may exist is: the performance of the plain acylate of individual fibers may be too remarkable in the film; and for example, the optical property of film and physical strength are easy to fluctuate with the variation of environment temperature and humidity, therefore may have problems.Yet; if the total amount of compound is greater than 45%; compound will be above the limit of their compatibilities in cellulose acylate film so, and because excessive compound can be deposited on film surface and film can bleach (oozing out from film) thus, therefore also may have problems.
[organic solvent in the cellulose acylate solution]
In the present invention, cellulose acylate film wherein is dissolved in cellulose acylate and makes solution (dope) in the organic solvent also with this dope formation film preferably according to the preparation of solvent cast method.The organic solvent that is preferably used as primary solvent of the present invention is selected from ester, ketone and ether with 3-12 carbon atom and the halogenated hydrocarbons with 1-7 carbon atom.The ester, ketone and the ether that are used for this paper can have ring structure.Have any two or more ester, ketone and ether functional group (that is, and-O-,-CO-and-COO-) compound also can be used for this paper as primary solvent, for example, they can have arbitrarily for example alcoholic extract hydroxyl group of other functional group.The carbon number that constitutes the primary solvent with two or more functional groups can fall in any one the scope of compound with these functional groups.
With regard to cellulose acylate film of the present invention; can use the chloro halogenated hydrocarbons as primary solvent, perhaps also can use non-chlorine solvent among the Hatsumei Kyokai ' s Disclosure Bulletin2001-1745 (pp.12-16) as primary solvent.In any case to cellulose acylate film of the present invention, primary solvent is not restrictive.
In addition, disclose the solvent and the method that is dissolved in wherein of cellulose acylate solution and film below in the patent documentation, and they are to be used for preferred implementation of the present invention.For example, they are described in JP-A 2000-95876,12-95877,10-324774,8-152514,10-330538,9-95538,9-95557,10-235664,12-63534,11-21379,10-182853,10-278056,10-279702,10-323853,10-237186,11-60807,11-152342,11-292988,11-60752,11-60752.These patent documentations not only disclose the preferred solvent of cellulose acylate of the present invention, and disclose their physical property of solution and the material that can coexist with them, and they also are to be used for preferred implementation of the present invention.
[preparation method of cellulose acylate film]
[dissolving step]
Preparing cellulose acylate solution of the present invention (dope) is having no particular limits aspect its dissolving method.It can at room temperature prepare or can hot-cold lysis or the mode of high-temperature digestion or prepare in their mode of combination.Hatsumei Kyokai ' s Disclosure Bulletin2001-1745 (publish by March 15 calendar year 2001; Hatsumei Kyokai); describe in detail in the 22-25 page or leaf and a kind ofly comprise that preparation is used for the step of cellulose acylate solution of the present invention and, and preferably use it for the present invention next with the method for the step of this solution concentration and filtration.
(transparency of rich liquor solution)
Preferably, the dope transparency of cellulose acylate solution of the present invention is at least 85%, more preferably at least 88%, even more preferably at least 90%.We, inventors of the present invention have confirmed that various adjuvants fully are dissolved in the cellulose acylate rich liquor solution of the present invention.A kind of concrete grammar of measuring the dope transparency is described.Rich liquor solution is put into size be 1cm 2Glass cuvette in and with spectrophotometer (UV-3150 derives from Shimadzu) measure its absorbance at 550nm.To only there be solvent to measure, and calculate the transparency of cellulose acylate solution by the solution absorbance and the ratio of blank absorbency as blank.
[curtain coating, drying and roll step]
Next, a kind of method of using cellulose acylate formulations prepared from solutions film of the present invention is described.As the method and apparatus that forms cellulose acylate solution of the present invention, use the solution casting that is usually used in preparing cellulose acetate film to become embrane method and solution casting film-forming apparatus.At first will preserve in storage tank by the dope (cyclic polyolefin solution) that dissolver (groove) makes, and with the final step of dope froth breaking as preparation.Dope for example is pumped into the pressure-type die head through the pressure-type measurement gear from the dope conveying end, and described pump can shift the liquid of constant basis accurately by the control rotating speed.From the pressure-type die head the mouth (slit) with the even curtain coating of dope on the metal support of the curtain coating section of cycle operation.Almost rotate once pick-up point in metal support, peel off down the dope film (also being referred to as " former ") of leather hard from metal support.The gained former is clamped its two ends with clip keep its width simultaneously, through the stenter transportation, and dry.Then, one group of roller mechanical transport of gained film drying device.Thus, stop dry run.Former is rolled to have predetermined length around winder.The combination of one group of roller of stenter and described exsiccator changes with purpose.Solution casting in the main application that is used for cellulose acylate film of the present invention becomes embrane method; described main application is promptly as the function and protecting film of the light intensifying material of the optical element of electronic console and silver halide photograph; except the solution casting film-forming apparatus, also often use coating apparatus, so that on film, carry out surface treatment so that bottom, antistatic layer, anti-dizzy layer and protective film etc. to be provided.(publish March 15 calendar year 2001 at Hatsumei Kyokai ' s DisclosureBulletin No.2001-1745 for they, Hatsumei Kyokai), in curtain coating classification (comprising parallel curtain coating), metal support, drying with the aspect such as peel off and have a detailed description, and can be preferred for the present invention in the 25-30 page or leaf.
The thickness of cellulose acylate film is 10-120 μ m preferably, more preferably 20-100 μ m, even more preferably 30-90 μ m.
[variation of the optical property of film after high humility is handled]
[evaluation of the physical property of cellulose acylate film]
Variation as for the optical property of the cellulose acylate film of the present invention that causes because of environmental change; the variable quantity of handling 240 hours the Re of film and Rth under 60 ℃ and 90%RH is 15nm or littler preferably; more preferably 12nm or littler, even more preferably 10nm or littler.
[variation of the optical property of film after pyroprocessing]
At 80 ℃ of variable quantities of handling 240 hours the Re of film and Rth 15nm or littler preferably, more preferably 12nm or littler, even more preferably 10nm or littler.
[burst size of compound after the thermal treatment film]
Be preferred for cellulose acylate film of the present invention reduction Rth compound and reduce the compound of Δ Rth, from 80 ℃ of amounts of handling to discharge 240 hours the film preferably 30% or littler, more preferably 25% or littler, even more preferably 20% or littler.
The amount that following acquisition discharges from film.To be dissolved in the solvent respectively at 80 ℃ of film and untreated films of handling 240 hours, and measure compound by high performance liquid chromatography.Use following expression to calculate burst size, the amount that wherein remains in the compound in the film is the peak area of compound.
Burst size (%)={ (remaining in the amount of the compound in the untreated film)-(remaining in the amount of the compound in the film of handling) }/(remaining in the amount of the compound in the untreated film) * 100.
[the glass temperature Tg of film]
The glass temperature Tg of cellulose acylate film of the present invention drops on 80-165 ℃.From the stable on heating angle of film, Tg preferably drops on 100-160 ℃, more preferably at 110-150 ℃.Following mensuration glass temperature Tg: 10mg cellulose acylate film sample of the present invention is heated to 200 ℃ with the firing rate of 5 ℃/min from room temperature; and with differential scanning calorimeter (DSC 2910; derive from T.A.Instrument) heat of working sample, and calculate the glass temperature Tg of film thus.
[mist degree of film]
Preferably, the mist degree of cellulose acylate film of the present invention drops on 0.01-2.0%, more preferably at 0.05-1.5%, even more preferably 0.1-1.0%.When film was used as optical thin film, film clarity was an importance.Can following mensuration mist degree: under 25 ℃ and 60%RH, measuring size according to JIS K-6714A method be the cellulose acylate film sample of the present invention of 40mm * 80mm with muddy meter (HGM-2DP derives from Suga Test Instruments).
[the humidity dependence of the Re of film and Rth]
Preferably, the humidity dependent change of delay Re and thickness direction retardation Rth is as far as possible little in the face of cellulose acylate film of the present invention.Specifically, the Rth's under the Rth under 25 ℃ and the 10%RH and 25 ℃ and the 80%RH is poor, Δ Rth (=Rth10%RH-Rth80%RH) drop on 0-50nm, more preferably at 0-40nm, even more preferably at 0-35nm.
[the equivalent moisture of film]
The equivalent moisture of cellulose acylate film of the present invention is described.When using described film as the protective film of polaroid; in order not damage for example cohesive of polyvinyl alcohol (PVA) of film and water-soluble polymers, it is at the equivalent moisture of 25 ℃ and 80%RH preferably 0-4%, more preferably 0.1-3.5%; even more preferably 1-3%, irrelevant with film thickness.If the equivalent moisture is higher than 4%, because the humidity dependence delay of described film may be too big when film being used as the supporter of optical compensating film, not preferred therefore so.
Following mensuration moisture: in conjunction with sample drying device (CA-03, VA-05 derive from Mitsubishi Chemical), analyzing size according to the Karl-Fisher method is the cellulose acylate film sample of the present invention of 7mm * 35mm with the moisture content analyzer.With the amount (g) of water in the sample of measuring thus weight (g) divided by sample.
[moisture-penetrability of film]
Preferably, be used for the moisture-penetrability of the cellulose acylate film of optical compensating gage of the present invention, being 60 ℃ in temperature is to measure and convert to the Standard Thin film thickness of 80 μ m under the 95%RH according to JIS Z0288 method with humidity, is 400-2000g/m 224h, more preferably 500-1800g/m 224h, even more preferably 600-1600g/m 224h.If it surpasses 2000g/m 224h, dependent Re of the humidity of film and Rth absolute value may be apparently higher than 0.5nm/%RH so.In addition, when laminated optical anisotropic layer is with the preparation optical compensating film on the plain acylate film of this fibrid of the present invention, because therefore described dependent Re of humidity and Rth absolute value may also be not beneficial apparently higher than 0.5nm/%RH also.When being installed in this class optical compensating gage or polaroid in the liquid crystal indicator, it can cause that variable color and visual angle reduce.On the other hand, if the moisture-penetrability of cellulose acylate film less than 400g/m 224h, the drying that its can interference adhesive when the both sides that this film adheres to polarization film make polaroid so, perhaps promptly, film can cause the bonding failure of polaroid.
When the thickness of cellulose acylate film was big, its moisture-penetrability may be less; And when described thickness hour, moisture-penetrability may be bigger.Therefore, must measure the moisture-penetrability of each sample, convert the Standard Thin film thickness of 80 μ m to different-thickness.According to its film thickness, the moisture-penetrability of following mensuration film: moisture-penetrability=(moisture-penetrability of mensuration) * (the film thickness μ m/80 μ m of mensuration) that converts the Standard Thin film thickness conversion of 80 μ m to.Assay method as for moisture-penetrability, mention Physical Properties of Polymer II (Polymer ExperimentalLecture 4, Kyoritsu Publishing), pp.285-297, the method described in " Determination of VaporPermeation (mass method, temperature method, vapor method, absorption method) ".In brief, be that the cellulose acylate film sample of 70mm φ was all nursed one's health 24 hours at 25 ℃ and 90%RH with at 60 ℃ and 95%RH with size.Use perviousness analyzer (KK-709007 derives from Toyo Seiki), according to the moisture (g/m of JIS Z-0208 method analytical unit area sample 2), and the moisture-penetrability of following calculation sample: the weight of the sample of conditioning of the weight of the sample of moisture-penetrability=nursed one's health-not.
[change in size of film]
The dimensional stability of cellulose acylate film of the present invention is preferably as follows: 60 ℃ and 90%RH storage 24 hours (high humility storage) afterwards film change in size and 90 ℃ and 5%RH preserve 24 hours (high-temperature storage) afterwards the change in size of film all be at the most 0.5%.More preferably, change in size is at the most 0.3%, even more preferably at the most 0.15%.
A concrete assay method is described.Two samples that prepare cellulose acylate film of the present invention, size is 30mm * 120mm, and nurses one's health 24 hours with 60%RH at 25 ℃.Use automatic pin gauge (deriving from Shinto Kagaku), form the hole of 6mm φ in each sample both sides with the interval of 100mm.Distance between the initial Kong Yukong is L0.A sample was handled 24 hours with 90%RH at 60 ℃, measured the distance (L1) between the Kong Yukong then; And another sample handled 24 hours at 90 ℃ and 5%RH, and measure distance (L2) between the Kong Yukong.The minimum measuring limit of each mensuration is 1/1000mm.Following definite change in size: the change in size of 60 ℃ and 90%RH (high humility storage)=| L0-L1|/L0} * 100.The change in size of 90 ℃ and 5%RH (high-temperature storage)=| L0-L2|/L0} * 100.
[elastic modulus of film]
(elastic modulus)
Preferably, the elastic modulus of cellulose acylate film of the present invention is 200-500kgf/mm 2, more preferably 240-470kgf/mm 2, even more preferably 270-440kgf/mm 2A kind of concrete assay method is as follows: use general tension measuring device, Toyo Boldwin ' s STMT50BP, film sample draw speed with 10%/min under the environment of 23 ℃ and 70%RH is stretched, and the stress when measuring it and producing 0.5% extensibility.It is the elastic modulus of sample.
[the optics elasticity coefficient of film]
(optics elasticity coefficient)
Preferably, the optics elasticity coefficient of cellulose acylate film of the present invention is at the most 50 * 10 -13Cm 2/ dyne, more preferably at the most 30 * 10 -13Cm 2/ dyne, even more preferably at the most 20 * 10 -13Cm 2/ dyne.A kind of concrete assay method is as follows: to size is that the cellulose acylate film sample of the present invention of 12mm * 120mm applies drawing stress at its major axes orientation; use the delay of ellipsometer (Nippon Bunko ' s M150) working sample thus, and change the optics elasticity coefficient of acquisition sample by sample with respect to the delay of the stress that is applied thereto.
[stretching before and the interior variation that postpones of face afterwards the mensuration of slow axis]
The sample of preparation 100 * 100mm, and in machine transporting direction (MD direction) or perpendicular horizontal (TD direction).Using fixing uniaxial tension equipment is to stretch under 140 ℃ the condition in temperature.Using automatic birefringence meter KOBRA 21ADH to measure each sample postpones before stretching and in the face afterwards.The alignment angle that obtains when measuring based on above-mentioned delay is determined slow axis.Preferably the Re variation that causes because of stretching is little.Specifically, preferred | Re (n)-Re (0) |/n≤1.0, more preferably | and Re (n)-Re (0) |/n≤0.3 or littler, wherein Re (n) postpones (nm) in the face during with film stretching n (%), and Re (0) postpones (nm) in the face of the film that do not stretch.
[direction] with slow axis
Polarizer has absorption axes at machine transporting direction (MD direction).Therefore, when being used for the polarizer protective film, cellulose acylate film of the present invention preferably has near the MD direction or near the slow axis the TD direction.By making slow axis parallel or vertically can reduce light leak and tonal variation with respect to polarizer." ... near " be meant slow axis and MD or TD direction in 0-10 ° scope, preferred 0-5 °.
[having just intrinsic birefringent cellulose acylate film]
When the direction of cellulose acylate film of the present invention slow axis in pellicular front is stretched, increase in its face and postpone Re, and when in the direction stretching vertical, reduce in its face and postpone Re with the direction of slow axis in the pellicular front.This illustrates that intrinsic birefringence is positive.In order to offset the Re that produces in the film, be effective at the direction oriented film vertical with slow-axis direction.When film when the MD direction has slow axis, this is by for example using stenter to realize at the direction oriented film vertical with machine transporting direction (MD direction) (that is, at TD direction oriented film).Therefore, can reduce delay Re in the face.By contrast, for example, when film when the TD direction has slow axis, the tensile force of the mechanical transport roller by increasing the MD direction comes oriented film to reduce to postpone Re in the face.
[having negative intrinsic birefringent cellulose acylate film]
In some cases, postpone Re when slow-axis direction stretches, and postpone Re when when the direction vertical with slow-axis direction stretches, increasing in its face when cellulose acylate film of the present invention is reduced in its face.This illustrates that intrinsic birefringence bears.In order to offset the Re that produces in the film, be effective at the slow-axis direction oriented film.When film when the MD direction has slow axis, this be by, for example, the tensile force that increases the machine transport roller at machine transporting direction (MD direction) comes oriented film to realize.Therefore, can reduce delay Re in the face.By contrast, for example, when film when having slow axis, face in postpones Re by using stenter can reduce at TD direction oriented film in the direction vertical with the MD direction (that is, in the TD direction).
[evaluation method of cellulose acylate film of the present invention]
Carry out the evaluation of cellulose acylate film of the present invention by following mensuration.
(postponing Re, thickness direction retardation Rth in the face)
Under 25 ℃ and 60%RH, adjust the humidity 2 hours of the sample of 30mm * 40mm.By making wavelength is the normal direction incident of the light of λ nm from film, measures Re (λ) with automatic birefringence instrument KOBRA 21ADH (being made by Oji Keisoku Kiki Kabushiki Kaisha).The length of delay that Rth (λ) is based on the Re (λ) that measures above and following mensuration calculates with 1.48 interim mean refractive index and film thickness.Length of delay is following mensuration: making wavelength is the incident of λ nm light, and each sample of while tilts to 50 ° with 10 ° spacing, and the interior slow axis of use face is as sloping shaft and suppose that the normal direction of film is 0 °.
(wavelength dependency Re and Rth Determination of distribution)
Adjust the humidity 2 hours of the sample of 30mm * 40mm at 25 ℃ and 60%RH.Use ellipsometer M-150 (being made by Nihon Bunko Kabushiki Kaisha), making wavelength is the normal direction incident of the light of 780nm-380nm at film, obtains the Re under each wavelength like this.Thus, measuring wavelength dependency Re distributes.Wavelength dependency Rth distribute to be based on the length of delay of three following direction detections and to calculate with 1.48 interim mean refractive index and film thickness.Length of delay is: in the R of direction detection in the above, use face slow axis as sloping shaft make wavelength for the light of 780-380nm from the normal direction of the relative film length of delay that+40 ° direction incident measures that tilts, with slow axis in the use face as sloping shaft make wavelength for the light of 780-380nm from the normal direction of the relative film length of delay that-40 ° direction incident measures that tilts.
(molecular orientation axis)
With the conditioning 2 hours under 25 ℃ and 60%RH of the sample of 70mm * 100mm.Use automatic birefringence instrument (Oji Keisoku Kiki ' s KOBRA 21ADH), calculate molecular orientation axis by the delay that the incident angle that changes vertical incidence light is measured.
(axis shift)
Use automatic birefringence instrument (Oji Keisoku Kiki ' s KOBRA 21ADH), measure the axis shift angle.Measure rule 20 points at interval of whole width at the sample Width, and the absolute value that will measure thus is average.The scope at slow axis angle (axis shift) is as follows: rule 20 points at interval of measuring whole width at the sample Width, and obtain to have the mean value of 4 points of 4 larger axis displacement of the lines absolute values, poor with the mean value of 4 points with 4 less axis shift absolute values.
(transmittance)
Use transparency meter (AKA photoelectric tube tintmeter derives from Kotaki Seisakusho) at 25 ℃ and 60%RH, measure visible light (615nm) transmittance of the sample of 20mm * 70mm.
(spectral characteristic)
Use spectrophotometer (U-3210 derives from Hitachi) at 25 ℃ and 60%RH, measure the transmittance of sample in the wavelength coverage of 300-450nm of 13mm * 40mm.Obtain the inclination width with (72% wavelength)-(5% wavelength).Limiting wave length is represented by (inclination width/2)+(5% wavelength).Absorption edge is represented with the wavelength of transmittance 0.4%.Obtain the transmittance of sample at 380nm and 350nm.
[surface property of film]
(surface configuration)
The surface property of cellulose acylate film of the present invention is described.Preferably, the arithmetic average roughness of the surfaceness of film (Ra) according to JIS B0601-1994 method, is 0.1 μ m at the most, and its maximum height (Ry) is 0.5 μ m at the most.More preferably, arithmetic average roughness (Ra) is 0.05 μ m at the most, and maximum height (Ry) is 0.2 μ m at the most.With atomic force microscope (AFM) can the analysed film surface concavo-convex issue.
(changing in the face of the delay of cellulose acylate film)
Cellulose acylate film of the present invention preferably satisfies expression.
| Re (MAX)-Re (MIN)|≤3 Hes | Rth (MAX)-Rth (MIN)|≤5
In this expression formula, Re (MAX)And Rth (MAX)The maximum delay value of 1m * 1m film that each cuts naturally at random, Re (MIN)And Rth (MIN)Each is the minimum delay value of this film naturally.
[adjuvant of film keeps performance]
Require cellulose acylate film of the present invention fully to keep making an addition to wherein each kind of compound.Specifically, storage is in the time of 48 hours under 80 ℃ and 90%RH when cellulose acylate film, and the mass change of film is 0-5% preferably, more preferably 0-3%, even more preferably 0-2%.
The adjuvant of＜film keeps the evaluation method of performance 〉
Sample is cut into the size of 10cm * 10cm, and 23 ℃ and 55%RH storage 24 hours, and measure its quality.Then, with it 80 ± 5 ℃ and 90 ± 10%RH storage 48 hours.After the processing, preserved 1 day with 55%RH at 23 ℃, once more the quality of working sample then on the wipe samples surface again gently.The adjuvant of following calculation sample keeps performance:
Adjuvant keeps performance (quality %)
={ (quality after the quality-storage before the storage)/(quality before the storage) } * 100.
[mechanical property of film]
(curling)
The crimp values of the Width of cellulose acylate film of the present invention preferably-10/m is to+10/m.As described below with the surface treatment of cellulose acylate film process, perhaps friction is coated with optical anisotropic layer then, or coating or laminated oriented layer or optical anisotropic layer.With regard to these processing, when film is long film, film is processed.If outside the scope, film can be difficult to processing and can cut off or break long cellulose acylate film so on the crimp values of its Width drops on.In addition, if so, the edge of film contacts strongly with transport roller with central part branch and produces dust, and the result can the many impurity of deposition on film.In this case, the frequency of spot defects and coating streak can surpass acceptable level.In addition, in the time of in crimp values is controlled at described scope, the trouble of the color spot that coating produces through regular meeting during optical anisotropic layer reduces, and is useful therefore, in addition, and can be when laminated polarization film with preventing that film from catching bubble.
Crimp values is measured according to the described method of the American National Standard Institute (ANSI/ASCPH1.29-1985).
(tear strength)
Preferably, measure according to the method for testing (Elmendorf tears method of testing) of tearing of JISK7128-2:1998, thickness of the present invention is that the cellulose acylate film of 20-80 μ m has the tear strength of 2g at least, more preferably 5-25g, even more preferably 6-25g.Same preferred, thickness is that the tear strength of the film of 60 μ m is 8g, more preferably 8-15g at least.Specifically, size is nursed one's health under 25 ℃ and 65%RH for the sample strip of 50mm * 64mm, with the tear strength analyzer test of underload, measures its tear strength then.
[the solvent residue in the film]
Preferred cellulose acylate film of the present invention remaining quantity of solvent in film is available as 0.01-1.5 quality %, and is more preferably dry under the condition of 0.01-1.0 quality %.Remaining quantity of solvent controls at the most 1.5% in the transparent supporting body that the present invention is used, can reduce film thus and curl.More preferably, it is at the most 1.0%.Its main cause may be owing to reduce according to remaining quantity of solvent in the film of above-mentioned solvent cast method formation, therefore can reduce the free volume of film.
[the moisture expantion coefficient of film]
Preferably, the moisture expantion coefficient of cellulose acylate film of the present invention is at the most 30 * 10 -5/ %RH, more preferably at the most 15 * 10 -5/ %RH, even more preferably at the most 10 * 10 -5/ %RH.The moisture expantion coefficient of film is preferably less, but in general, it can be at least 1.0 * 10 -5/ %RH.The moisture expantion coefficient is meant the variation of sample length when the relative humidity around the sample changes under the constant temperature.When as above controlling the moisture expantion coefficient and when using cellulose acylate film of the present invention as the supporter of optical compensating film; frame-like transmittance (frame-like transmittance) rises; perhaps promptly, can when the optical compensation function that keeps optical compensating film is constant, prevent the light leak that strain causes.
[surface treatment]
Under certain situation,, can improve the cohesive between cellulose acylate film and each functional layer (for example, bottom or internal layer) by cellulose acylate film is carried out surface treatment.For example, can use glow discharge processing, ultraviolet treatment with irradiation, corona treatment, flame treatment, acid or alkali treatment.Here, the glow discharge processing can be 10 -3The Low Temperature Plasma Treating of carrying out in the low-pressure gas of-20 Torr or can be the Cement Composite Treated by Plasma of under atmospheric pressure carrying out.The two all is preferred.Plasma exciatiaon gas is meant under these conditions and comprises that through the gas of plasma exciatiaon for example, argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, flons (fluorochlorohydrocarbon) be tetrafluoromethane or their potpourri for example.They are described in detail in Hatsumei Kyokai ' s Disclosure Bulletin No.2001-1745 (i2001 published Hatsumei Kyokai March 15), the 30-32 page or leaf, and can be preferred for the present invention.
[contact angle of the film surface of alkali soap processing]
For the transparent protective film that uses cellulose acylate film of the present invention as polaroid, effective means of surface-treated is the alkali soap processing.In this case, preferably 55 ° or littler of the contact angles of film surface after the alkali soap processing, more preferably 50 ° or littler, even more preferably 45 ° or littler.Contact angle can be estimated with typical evaluation method, wherein after the alkali soap processing is that the water droplet of 3mm drops on the film surface with diameter, and obtains the angle between film surface and the water droplet.Can use contact angle as water wettability and hydrophobic measuring.
(photostability)
The sunproof index of cellulose acylate film of the present invention is as follows.Aberration Δ E with 240 hours film of super xenon rayed *Ab preferably 20 or littler, and more preferably 18 or littler, even more preferably 15 or littler.Use the following mensuration aberration of UV3100 (making) by Shimadzu Corporation.The humidity 2 hours of conditioning film under 25 ℃ and 60%RH, before the xenon rayed, the color of measuring film is to obtain initial value (L0 then *, a0 *, b0 *).Afterwards, use super xenon Weather meter SX-75 (by Suga Test Instruments Co., Ltd. make), with xenon light at 150W/m 2, 60 ℃ and 50%RH condition under to film irradiation 240 hours.After the schedule time, film is taken out from thermostatic bath, and adjust humidity 2 hours with 60%RH at 25 ℃.Then, measure the color of film once more to obtain postradiation value (L1 *, a1 *, b1 *).Obtain aberration Δ E by these values *Ab=((L0 *-L1 *) ^2+ (a0 *-a1 *) ^2+ (b0 *-b1 *) ^2) ^0.5.
[functional layer]
The application of cellulose acylate film of the present invention comprises optical application and photographic material.The optical application of film is particularly preferred for liquid crystal indicator, the device that more preferably comprises following element: between two electrode base boards, be loaded with liquid crystal liquid crystal cell, be placed on two polarizers of liquid crystal cell both sides, and at least one is placed on the optical compensating gage between liquid crystal cell and the polarizer.With regard to liquid crystal indicator, preferred TN, IPS, FLC, AFLC, OCB, STN, ECB, VA and HAN.
When cellulose acylate film of the present invention is used for these optical application, can add various functional layers to it.These layers for example have antistatic layer, curing resin layer (transparent hard conating), anti-reflecting layer, easy bonding coat, anti-glare layer, optical compensating layer, oriented layer, liquid crystal layer.These functional layers and their material that can be used for cellulose acylate film of the present invention comprise surfactant, lubricant, matting agent, antistatic layer and hard conating; and they are described in detail in Hatsumei Kyokai ' s Disclosure Bulletin 2001-1745, and (publish March 15 calendar year 2001; Hatsumei Kyokai); the 32-45 page or leaf, and also be preferred for the present invention.
[purposes (polaroid)]
The purposes of cellulose acylate film of the present invention is described.
Optical thin film of the present invention especially can be used as polarizer protection film.When cellulose acylate film of the present invention was used as polarizer protection film, polaroid can be used by the conventional method preparation, has no particular limits.According to a kind of method,, and use the aqueous solution of fully saponified polyvinyl alcohol (PVA) that it is adhered to the polarizer both sides with the alkali treatment of gained cellulose acylate film.Polarizer makes by polyvinyl alcohol film is soaked in iodine solution and stretches.Replace alkali treatment, can use the adhesion process described in JP-A 6-94915 and the 6-118232.
The example that is used for the bonding agent of the surface treated of bonding protective film and polarizer comprises polyvinyl alcohol-based adhesives (for example polyvinyl alcohol (PVA) and polyvinyl butyral etc.); With vinyl base latex (for example butyl acrylate etc.) etc.
Polaroid is made up of the protective film of polarizer and its both sides of protection.In addition, protective film adheres to polarizer one side, and barrier film is adhered to its opposite side.When being used for polaroid transportation and product detection etc., protective film and barrier film protect polaroid.In this case, adhere to the surface of protective film, and be used for waiting to adhere to the relative opposite side of side of liquid crystal board with polaroid with the protection polaroid.Barrier film is used to cover with polaroid and the bonding bonding coat of liquid crystal board, and is used for a side of waiting to adhere to liquid crystal board of polaroid.
Liquid crystal indicator typically comprises the substrate that contains liquid crystal between two polaroids.Use the polarizer protection film of optical thin film of the present invention that excellent display visibility is provided, and no matter where film is positioned at.The polarizer protection film that particularly is positioned on the display surface of liquid crystal indicator provides transparent hard conating, anti-glare layer or anti-reflecting layer etc.Therefore, polarizer protection film is particularly preferred for this position.
[purposes (optical compensating film)]
Cellulose acylate film of the present invention can be used for various uses, and effective especially when being used as the optical compensating film of liquid crystal indicator.Optical compensating film is meant a kind of optical element that is usually used in the liquid crystal indicator and is used for compensating phase retardation.Optical compensating film has and identical implications such as phase retarder or optical compensating gage.Optical compensating film has birefringence, and the look that is used to remove the display board of liquid crystal indicator becomes or improve the viewing angle characteristic of liquid crystal indicator.Cellulose acylate film of the present invention has by 0≤Re (630)≤ 10nm and | Rth (630)| the low-level optical anisotropy the shown in≤25nm and by | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)| the low-level wavelength dependency shown in≤35 distributes.Therefore, film does not have any superfluous anisotropy.When cellulose acylate film of the present invention with have birefringent optical anisotropic layer when being used in combination, only can present the optical property of optical anisotropic layer.
Therefore, when cellulose acylate film of the present invention was used as the optical compensating film of liquid crystal indicator, the Re of the optical anisotropic layer that is used in combination with it and Rth be Re preferably (630)=0-350nm and | Rth (630)|=0-400nm.Can use and have the interior Re of this scope and any optical anisotropic layer of Rth.Can use any optical anisotropic layer with optical compensating film desirable characteristics, and no matter the optical property or the drive system of the liquid crystal cell of the liquid crystal indicator of use cellulose acylate film of the present invention.Used optical anisotropic layer can or have birefringent thin polymer film by the composition that contains liquid-crystal compounds and form.
The optical anisotropic layer that is used in combination with optical compensating film of the present invention is formed by cyclic polyolefin film, and described cyclic polyolefin film is for having birefringence and satisfying 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400, more preferably 35≤Re (630)≤ 300 and 100≤Rth (630)≤ 350, even more preferably 35≤Re (630)≤ 250 and 100≤Rth (630)≤ 300 thin polymer film.
As above-mentioned liquid-crystal compounds, preferred discotic liquid-crystal compounds or rod shaped liquid crystal compound.
(disc liquid-crystal compounds)
In various documents (C.Destrade etc., MoI.Cryst.Liq.Cryst., the 111st page (1981) of the 71st volume; Quarterly Journal of Outline of Chemistry, Chemical Societyof Japan, No.22, Chemistry of Liquid Crystal, part 2 the 10th chapter (1994); B.Kohne etc., Angew.Chem.Soc.Chem.Comm., the 1794th page (1985); J.Zhang etc., J.Am.Chem.Soc, the 116th volume the 2655th page (1994)) in the example that can be used for disc liquid-crystal compounds of the present invention has been described.
Preferably, discotic liquid-crystalline molecules fixedly is aligned in the optical anisotropic layer of the present invention, most preferably fixing wherein by polyreaction.The polyreaction of discotic liquid-crystalline molecules has been described in JP-A8-27284.For by the fixing discotic liquid-crystalline molecules of polyreaction, polymerizable groups must link to each other as the substituting group on it with the disc-shaped core core of each discotic liquid-crystalline molecules.Yet if this polymerizable groups directly links to each other with the disc-shaped core core, these molecules almost can not keep their orientation during polyreaction so.Therefore, between disc-shaped core core and polymerizable groups, introduce linking group to be connected thereon.This discotic liquid-crystalline molecules with polymerizable groups is disclosed in JP-A 2001-4387.
(rod shaped liquid crystal compound)
Can be used for rod shaped liquid crystal examples for compounds of the present invention the phenyl pyrimidine class of azomethine class, azoxy based compound, cyanobiphenyl class, cyano-phenyl ester class, benzoates, phenyl-cyclohexane-carboxylic acid ester class, cyano-phenyl cyclohexanes, cyano group replacement, phenyl pyrimidine, phenyl two  alkane, diphenyl acetylene class and the thiazolinyl cyclohexyl benzonitrile class that alkoxy replaces are arranged.Not only this low molecular weight liquid crystal compound can be used for this paper, and the high molecule liquid crystal compound also can be used for this paper.
In optical anisotropic layer, preferred rod shaped liquid crystal molecule is fixed with aligned condition, and most preferably they are fixed by polyreaction.Can be used for polymerizable rod shaped liquid crystal examples for compounds of the present invention and be described in Macromol.Chem., the 190th volume, the 2255th page (1989); AdvancedMaterials, the 5th volume, the 107th page (1993); United States Patent (USP) 4683327,5622648,5770107; The pamphlet of international publication number 95/22586,95/24455,97/00600,98/23580,98/52905; JP-A1-272551,6-16616,7-110469,11-80081,2001-328973.
(by the film formed optical anisotropic layer of polymer thin)
As mentioned above, optical anisotropic layer can be formed by thin polymer film.Thin polymer film forms by presenting optically anisotropic polymkeric substance.The example of this polymkeric substance comprises that polyolefin (for example, tygon, polypropylene, norborene based polyalcohol), polycarbonate, polyarylate, polysulfones, polyvinyl alcohol (PVA), polymethacrylate, polyacrylate, and cellulose esters (for example, cellulose triacetate, cellulose diacetate ester).Can use the multipolymer or the potpourri of these polymkeric substance.
In optical compensating film of the present invention, optical anisotropic layer is by satisfied 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400 cyclic polyolefin film forms.
The optical anisotropy of thin polymer film preferably produces by stretching.Preferably uniaxial tension or biaxial stretch-formed stretches.Specifically, preferably utilize the difference of the peripheral speed between two or more rollers to realize the machine direction uniaxial tension; Perhaps clamp the both sides of thin polymer film and stretch at Width that it realizes that stenter stretches; Combination biaxial stretch-formed that perhaps comprises these stretchings.If necessary, can use two or more thin polymer films so that the whole optical property of these two or more films can satisfy above-mentioned condition.Preferably, thin polymer film gets according to the solvent cast legal system so that reduce the birefringence inhomogeneity of film as much as possible.Preferably, the thickness of thin polymer film drops in the scope of 20-500 μ m, most preferably in the scope of 40-100 μ m.
(structure of general liquid crystal indicator)
With regard to the thin polymer film that forms optical anisotropic layer, can use at least a polymeric material that is selected from polyamide, polyimide, polyester, polyetherketone, polyamidoimide-polyester-imide and PAEK.It is dissolved in the solvent, then gained solution is coated on the substrate, thereby and solvent evaporation fallen to form film on film.Preferably this method is used for this paper.In this case, thereby also preferably make film have optically anisotropic method thin polymer film and substrate stretching, and the film of processing thus can be used as optical anisotropic layer.Cellulose acylate film of the present invention is preferably used as the supporter in these embodiments.Another method for optimizing is as follows: form thin polymer film on different substrate, and it is peeled from substrate, then it is adhered on the cellulose acylate film of the present invention, obtain having the optical anisotropic layer of laminate structures.In the method, can make the thin polymer film thinning, and its thickness preferably 50 μ m, more preferably 1-20 μ m at the most.
(structure of general liquid crystal indicator)
When using cellulose acylate film of the present invention as optical compensating film, the axis of homology of its polarizer element can be in arbitrarily angled with respect to the slow axis of the optical compensating film of cellulose acylate film.Liquid crystal indicator comprises the liquid crystal cell that is loaded with liquid crystal between two electrode base boards, is placed on two polarizers of this elements on either side, and at least one is placed on the optical compensating film between liquid crystal cell and the polarizer.
The liquid crystal layer of liquid crystal cell is normally adding liquid crystal formation in the formed space of the dividing plate of placing between them between two substrates, and liquid crystal is closed in wherein.On substrate, form transparent electrode layer as the transparent membrane that contains conductive materials.Liquid crystal cell can also have gas barrier layer, hard conating or internal coating (being used to be adhered to transparent electrode layer).Usually these layers are formed on the substrate.The substrate of liquid crystal cell has the thickness of 50 μ m-2mm usually.
(type of liquid crystal indicator)
Cellulose acylate film of the present invention can be used for the liquid crystal cell of various display modes.Mentioned for example TN (twisted nematic), IPS (face internal conversion), FLC (ferroelectrics liquid crystal), AFLC (anti-ferroelectrics liquid crystal), OCB (optical compensation curved), STN (STN Super TN), VA (vertical alignment), ECB (ECB electrically controlled birefringence) and HAN (mixing alignment) pattern of various display modes to row.Other display mode of any above-mentioned display mode through aliging and separating has also been proposed.Cellulose acylate film of the present invention is effective in the liquid crystal indicator of any display mode.And, in transmission-type, reflection-type and transflective liquid crystal display device arbitrarily, also be effective.
(TN-type liquid crystal indicator)
Cellulose acylate film of the present invention can be used as the supporter of the optical compensating gage of the TN-type liquid crystal indicator with TN-type liquid crystal cell.TN-type liquid crystal cell and TN-type liquid crystal indicator are known.The optical compensating gage that is used for TN-type liquid crystal indicator is described in JP-A 3-9325,6-148429,8-50206 and 9-26572.In addition, it also be described in Mori etc. article (Jpn.J.Appl.Phys., Vol.36 (1997), p.143; Jpn.J.Appl.Phys., the 36th (1997) volume, the 1068th page) in.
(STN-type liquid crystal indicator)
Cellulose acylate film of the present invention can be used as the supporter of the optical compensating gage of the STN-type liquid crystal indicator with STN-type liquid crystal cell.Usually in STN-type liquid crystal indicator, the rod shaped liquid crystal molecule in the liquid crystal cell is at the scope intort of 90-360 degree, and the refraction ansiotropy of rod shaped liquid crystal molecule (Δ n) and element gap (d) long-pending (Δ nd) are in the scope of 300-1500nm.The optical compensating gage that is used for STN-type liquid crystal indicator has been described among the JP-A2000-105316.
(VA-type liquid crystal indicator)
Cellulose acylate film of the present invention is preferably used as the supporter of the optical compensating gage of the VA-type liquid crystal indicator with VA-type liquid crystal cell especially.The Re length of delay 0-150nm preferably that is used for the optical compensating gage of VA-type liquid crystal indicator, and its Rth length of delay 70-400nm preferably.The Re length of delay is more preferably 20-70nm.Two optical anisotropy thin polymer films are being used under the situation of VA-type liquid crystal indicator, and the Rth length of delay of these two films is 70-250nm preferably.An optical anisotropy thin polymer film is being used under the situation of VA-type liquid crystal indicator, and the Rth length of delay of film is 150-400nm preferably.VA-type liquid crystal indicator of the present invention can have the system that the orientation described in the JP-A 10-123576 is for example separated.
(IPS-type liquid crystal indicator and ECB-type liquid crystal indicator)
Cellulose acylate film of the present invention is preferably used as the IPS-type liquid crystal indicator with IPS-type liquid crystal cell especially or has the supporter or the polarizer protection film of optical compensating gage of the ECB-type liquid crystal indicator of ECB-type liquid crystal cell.In these patterns, liquid crystal material aligns abreast with pellicular front is approaching under black display, and this black display provides by liquid crystal molecule is alignd abreast with substrate surface.In these embodiments, use the polaroid of cellulose acylate film of the present invention to help improving tone, enlarge the visual angle, and improve contrast.In these embodiments, the protective film (that is component side protective film) that provides between at least one polaroid that preferred cellulose acylate film of the present invention provides as liquid crystal cell and this liquid crystal cell both sides.More preferably, between polarizer protection film and liquid crystal cell, provide optical anisotropic layer and the length of delay of the optical anisotropic layer that provides thus is adjusted to the twice of value of the Δ nd of the delay that is equal to or less than liquid crystal layer.
(OCB-type liquid crystal indicator and HAN-type liquid crystal indicator)
Cellulose acylate film of the present invention also is preferably used as the OCB-type liquid crystal indicator with OCB-type liquid crystal cell or has the supporter of optical compensating gage of the HAN-type liquid crystal indicator of HAN-type liquid crystal cell.Preferably, at the optical compensating gage that is used for OCB-type liquid crystal indicator or HAN-type liquid crystal indicator, the absolute value of delay is not present in the interior direction of face and the normal direction of optical compensating gage for minimum direction.The optical property that is used for the optical compensating gage of OCB-type liquid crystal indicator or HAN-type liquid crystal indicator is to be determined by the optical property of the optical property of optical anisotropic layer, supporter and the relation of the position between optical anisotropic layer and the supporter.The optical compensating gage that is used for OCB-type liquid crystal indicator or HAN-type liquid crystal indicator is described in JP-A 9-197397 and also is described in the article (Jpn.J.Appl.Phys. the 8th (1999) volume, the 2837th page) of Mori etc.
(reflection-type liquid-crystal display device)
Cellulose acylate film of the present invention also is preferably used as the optical compensating gage of TN-type, STN-type, HAN-type or GH (guest-master)-type reflection-type liquid-crystal display device.These patterns are known.TN-type reflection-type liquid-crystal display device is described in the pamphlet and Jap.P. 3022477 of JP-A 10-123478, international publication number 98/48320.The optical compensating gage that is used for reflection-type liquid-crystal display device is described in the pamphlet of international publication number 00/65384.
(liquid crystal indicator of other type)
Cellulose acylate film of the present invention also is preferably used as the supporter of the optical compensating gage of ASM (rotational symmetry alignment the micro element)-type liquid crystal indicator with ASM-type liquid crystal cell.ASM-type liquid crystal cell is characterised in that the thickness by the whole resin dividing plate holding element of adjustable positions.Other performance of ASM-type liquid crystal cell is identical with TN-type liquid crystal cell.ASM-type liquid crystal cell and ASM-type liquid crystal indicator are described in the article (Kume etc., SID 98 Digest 1089 (1998)) of Kume etc.
(hard-coated film, anti-dazzle film, anti-reflection film)
Cellulose acylate film of the present invention is preferred for hard-coated film, anti-dazzle film and anti-reflection film.In order to improve for example visibility of LCD, PDP, CRT, EL of flat-panel monitor, any or all layers in hard conating, anti-glare layer and the anti-reflecting layer can be fixed to one or two face of cellulose acylate film of the present invention.The preferred implementation of these anti-dazzle films and anti-reflection film is described in Hatsumei Kyokai ' s Disclosure Bulletin2001-1745 and publishes on March calendar year 2001 15; Hatsumei Kyokai); in the 54-57 page or leaf, and cellulose acylate film of the present invention can be preferred in these.
(photographic negative supporter)
Can be used for the supporter that cellulose acylate film of the present invention can be used for photographic silver halide material, in some patent documentations, described their various materials and prescription and their preparation method, and they can be used for the present invention.As for these technology, JP-A 2000-105445 has described the colour negative film in detail, and cellulose acylate film of the present invention is preferred for these.Also preferred, film of the present invention can be used for the supporter of colour reversal photographic silver halide material, and their various materials and prescription and their preparation method who is described among the JP-A 11-282119 can be used for the present invention.
(transparency carrier)
Because cellulose acylate film of the present invention has near zero optical anisotropy and has good transparency; it can replace the glass substrate of liquid crystal cell in the liquid crystal indicator; perhaps promptly, it can be used as the transparent supporting body that drives liquid crystal in the described device of sealing.
Because the transparency carrier that is used for encapsulated liquid crystals has the good gas-barrier properties energy, therefore if necessary, can choose wantonly gas barrier layer is fixed on the surface of cellulose acylate film of the present invention.The form and the material of gas barrier layer have no particular limits.For example, can at least one face of cellulose acylate film of the present invention, deposit SiO 2, perhaps can on film of the present invention, form the ethenylidene based polyalcohol with higher relatively gas barrier properties or the polymer coating of vinyl alcohol based polyalcohol.Can suitably select these technology to be used for the present invention.
When film of the present invention is used as the transparency carrier of encapsulated liquid crystals, transparency electrode can be fixed thereon to drive liquid crystal by it is applied voltage.Transparency electrode is had no particular limits.For example, go up to form transparency electrode thereon on available at least one surface that metallic film or metal-oxide film are laminated in cellulose acylate film of the present invention.At first, consider transparency, electric conductivity and the mechanical property of film, the preferable alloy sull; And more preferably mainly comprise tin-oxide and contain the indium oxide film of 2-15% zinc paste.These technology for example are described in detail in JP-A 2001-125079 and 2000-22760.
Embodiment
Below, describe embodiments of the present invention, and the invention is not restricted to these embodiments.
[film forming embodiment 1] (formation of cyclic polyolefin film F-1)
Synthesizing of＜cyclic polyolefin polymer P-1 〉
The pure toluene of 100 mass parts and the norborene methyl carbonate of 100 mass parts are put into reactive tank.Next, three (pentafluorophenyl group) boron (with respect to the quality of monomer) that is dissolved in ethyl hexanoate-Ni (with respect to the quality of monomer), 0.225mol% in the toluene of 25mmol% and the aluminium triethyl (with respect to the quality of monomer) that is dissolved in the toluene of 0.25mol% are put into reactive tank.When at room temperature stirring with these substance reactions 18 hours.After the reaction, reaction mixture is put into excess ethyl alcohol produce the multipolymer sediment.With this sediment purifying and with gained multipolymer (P-1) 65 ℃ of dryings 24 hours in a vacuum.
Following composition is put into mixing channel and these components of stirring and dissolving, is that the filter paper of 34 μ m and sintered metal filter that average pore size is 10 μ m filter through average pore size then.
Cyclic polyolefin solution D-1
Cyclic polyolefin P-1 dichloromethane methanol 150 mass parts, 380 mass parts, 70 mass parts
Next, the following composition that will contain the cyclic polyolefin solution D-1 that forms by said method is put into decollator with preparation liquid matting agent spreading agent M-1.
Liquid matting agent spreading agent M-1
Mean grain size is silica dioxide granule (Aerosil R972 is made by Nihon Aerosil Kabushiki Kaisha) the dichloromethane methanol cyclic polyolefin solution D-1 of 16nm 2 mass parts, 73 mass parts, 10 mass parts, 10 mass parts
With the liquid matting agent spreading agent M-1 of the cyclic polyolefin solution D-1 of 100 mass parts and 1.35 mass parts to be mixed with the dope that film forming is used.
With the described dope of belt curtain coating device curtain coating.The residual solvent amount when being about 25 quality % from being with stripping film, film is stretched with stenter with 10% draw ratio and with 130 ℃-140 ℃ heated-air drying, keeps film simultaneously at Width, make film not shrink.After stenter transportation, again film is transported through roller, and once more 120 ℃ of-140 ℃ of dryings and roll.The thickness of gained cyclic polyolefin film (F-1) is 80 μ m, and mist degree is 0.5, and delay Re is 63nm, and delay Rth is 200nm.
[film forming embodiment 2] (formation of cyclic polyolefin film F-2)
Following composition is put into pressure-resistant seal groove and stirring, be heated to 80 ℃ to dissolve these components with hot water then.After the cooling, be that the filter paper of 34 μ m and sintered metal filter that average pore size is 10 μ m filter through average pore size with the gained material.
Cyclic polyolefin solution D-2
topAS (by Polyplastics Co., Ltd. sells) hexane 150 mass parts, 600 mass parts
Next, the following composition that will contain the cyclic polyolefin solution D-2 that forms by said method is put into decollator with preparation liquid matting agent spreading agent M-2.
Liquid matting agent spreading agent M-2
Mean grain size is silica dioxide granule (Aerosil R972 is made by Nihon Aerosil Kabushiki Kaisha) the hexane cyclic polyolefin solution D-2 of 16nm 2 mass parts, 80 mass parts, 10 mass parts
The cyclic polyolefin solution D-2 of 100 mass parts and the liquid matting agent spreading agent M-2 of 1.1 mass parts are mixed the dope of using with the preparation film forming.
With the described dope of belt curtain coating device curtain coating.The residual solvent amount when being about 18 quality % from being with stripping film, film is stretched with stenter with 50% draw ratio and with hot blast (130 ℃-140 ℃) drying, keeps film simultaneously at Width, make film not shrink.After stenter transportation, again film is transported through roller, and once more 120 ℃ of-140 ℃ of dryings and roll.The thickness of gained cyclic polyolefin film (F-2) is 80 μ m, and mist degree is 0.4, and delay Re is 60nm, and delay Rth is 180nm.
[film forming embodiment 3] (formation of cyclic polyolefin film F-3)
Following composition is put into mixing channel and these components of stirring and dissolving.The gained material is that the filter paper of 34 μ m and sintered metal filter that average pore size is 10 μ m filter through average pore size then.
Cyclic polyolefin solution D-3
ARTON (making) hexane by ISR Corporation 150 mass parts, 600 mass parts
Next, the following composition that will contain the cyclic polyolefin solution D-3 that forms by said method is put into decollator with preparation liquid matting agent spreading agent M-3.
Liquid matting agent spreading agent M-3
Mean grain size is silica dioxide granule (Aerosil R972 is made by Nihon Aerosil Kabushiki Kaisha) the hexane cyclic polyolefin solution D-3 of 16nm 2 mass parts, 80 mass parts, 10 mass parts
The cyclic polyolefin solution D-3 of 100 mass parts and the liquid matting agent spreading agent M-3 of 1.1 mass parts are mixed the dope of using with the preparation film forming.
With the described dope of belt curtain coating device curtain coating.The residual solvent amount when being about 22 quality % from being with stripping film, film is stretched with stenter with 2% draw ratio and with hot blast (130 ℃-140 ℃) drying, keeps film simultaneously at Width, make film not shrink.After stenter transportation, again film is transported through roller, and once more 120 ℃ of-140 ℃ of dryings and roll.The thickness of gained cyclic polyolefin film (F-3) is 80 μ m, and mist degree is 0.2, and postponing Re is 60 nm, and delay Rth is 190nm.
[film forming embodiment 4] (formation of cellulose acylate film 001-003,101-104)
(preparation of cellulose acetate ester solution)
Following composition is put into mixing channel also to be stirred to dissolve these components.Thus, preparation cellulose acetate ester solution D.
(composition of cellulose acetate ester solution D)
The acetify degree is 2.86 cellulose acetate ester 100.0 mass parts
Methylene chloride (first solvent) 402.0 mass parts
Methyl alcohol (second solvent) 60.0 mass parts
(preparation of matting agent solution)
With the mean grain size of 20 mass parts is that the silica dioxide granule (AEROSILR972 is made by Nihon Aerosil Kabushiki Kaisha) of 16nm and the methyl alcohol of 80 mass parts stir and abundant the mixing 30 minutes, forms liquid silica dioxide granule dispersion.This liquid dispersion put into decollator with following composition and stirred 30 minutes or longer to dissolve these components.Thus, make matting agent solution.
(composition of matting agent solution)
Mean grain size is silica dioxide granule 10.0 mass parts of 16nm
Methylene chloride (first solvent) 76.3 mass parts
Methyl alcohol (second solvent) 3.4 mass parts
Cellulose acetate ester solution D 10.3 mass parts
(preparation of additive solution)
Following composition is put into mixing channel and stirring, and heating is so that with these components dissolved simultaneously.Thus, make additive solution.
(composition of additive solution)
Reduce optically anisotropic compd A-19 49.3 mass parts
Wavelength dependency profile adjustment agent UV-102 7.6 mass parts
Methylene chloride (first solvent) 58.4 mass parts
Methyl alcohol (second solvent) 8.7 mass parts
Cellulose acetate ester solution D 12.8 mass parts
(formation of cellulose acetate film sample 101)
The additive solution of the matting agent solution of the cellulose acetate ester solution D of 94.6 mass parts, 1.3 mass parts and 4.1 mass parts filtered respectively then mix, and with belt curtain coating device curtain coating.In the above in the composition, reducing optically anisotropic compd A-19 is 12% with respect to the mass ratio of cellulose acetate ester, and wavelength dependency profile adjustment agent UV-102 is 1.8% with respect to the mass ratio of cellulose acetate ester.In the residual solvent amount is film to be peeled off and 140 ℃ of dryings 40 minutes, to form cellulose acetate film from being with in about 30% o'clock.The residual solvent amount of gained cellulose acetate film is 0.2%, and the thickness of film is 80 μ m.(formation of cellulose acetate film sample 001-003,102-104)
To form cellulose acetate film sample 001-003 and 102-104 with top identical mode, just type and the quantitative change with the wavelength dependency profile adjustment agent in optically anisotropic compound of the reduction in the additive solution and the additive solution is shown in the table 1.Table 1 has also shown the solution composition of sample 101.
Table 1
The cellulose acetate film sample Methylene chloride (mass parts) Methyl alcohol (mass parts) The cellulose acylate degree of substitution Film thickness (μ m) The optical anisotropy depressant Wavelength dependency disperses correctives Total amount of compound (% is with respect to cellulose acylate)
Compound Amount (mass parts) Compound Amount (mass parts)
Comparative Examples 001 58.4 8.7 2.86 80 Do not have - Do not have - 0
Comparative Examples 002 58.4 8.7 2.86 80 Do not have - UV-3 7.6 1.8
Comparative Examples 003 58.4 8.7 2.86 80 BDP 49.3 UV-3 7.6 13.6
The present invention 101 58.4 8.7 2.92 80 A-19 49.3 UV-102 7.6 13.6
The present invention 102 80 20 2.92 80 A-19 50 UV-102 8 17.4
The present invention 103 80 20 2.92 80 A-19 58 UV-102 8 19.9
The present invention 104 80 20 2.92 80 A-19 58 UV-102 8 19.9
Measure these samples relative humidity be 10% and relative humidity be the thickness direction retardation between 80% difference Δ Rth (=Rth10%RH-Rth80%RH).The comparative sample 001 that does not contain the optical anisotropy depressant and 002 and phosphoric acid xenyl diphenyl (BDP) replace in the comparative sample 003 of optical anisotropy depressant as plastifier, Δ Rth is not reduced to 30 nm or littler, and optically anisotropic humidity dependence height.
By contrast, in the sample 101 that contains the optical anisotropy depressant, confirm Δ Rth in the scope of 0-30 and optically anisotropic humidity dependence reduce.Also measure these samples at 25 ℃ of equilibrium moisture contents with 80%RH.Confirmation is in all samples except that comparative sample 001, and equilibrium moisture content is 4% or littler, and makes cellulose acylate film hydrophobic by adding optical anisotropy depressant or the agent of wavelength dependency profile adjustment.Measure these samples 60 ℃ and lasting 24 hours moisture-penetrability (converting the value of 80 μ m to) of 95%RH.Confirmation is in all samples except that comparative sample 001, and moisture-penetrability is 400g/m 224hr or bigger and 2000g/m 224hr or littler, and compare with 003 with comparative sample 002, the moisture-penetrability that contains the sample 101-103 of optical anisotropy depressant and the agent of wavelength dependency profile adjustment improves.
The evaluation result to cellulose acylate film sample 101-104 and comparative sample 001-003 that obtains is shown in table 2.
Table 2
The cellulose acetate film sample ΔRth Moisture Moisture-penetrability Re(630) (nm) Rth(630) (nm) |Re(400) - Re(700)| (nm) |Rth(400)- Rth(700)| (nm)
(Rth10％RH- Rth80％) 80％RH Convert the value of 80 μ m to
Comparative Examples 001 52.4 4.4 2250 3.3 27.8 13 39.8
Comparative Examples 002 49.4 3.4 1410 2.5 26.4 7.8 22.3
Comparative Examples 003 36.8 2.9 1317 3.0 30.4 10.8 21.4
The present invention 101 25.1 3.3 1060 0.2 3.1 1.3 7.4
The present invention 102 10.3 2.8 950 0.4 -4.1 1.0 12.4.
The present invention 103 8.5 2.2 905 0.3 -6.1 0.8 11.5
The present invention 104 8.2 2.2 910 0.2 -3.5 0.5 5.1
Compare with the comparative sample 003 that contains for the phosphoric acid xenyl diphenyl (BDP) of conventional plastifier with 002 with the comparative sample 001 that does not contain this compound, contain the Re of the sample 101-104 that reduces optically anisotropic compound (630)And Rth (630)All fully reductions and almost optical isotropy.Compare with Comparative Examples, contain the sample of regulating the compound that wavelength dependency distributes | Re (400)-Re (700)| and | Rth (400)-Rth (700)| all enough low, and wavelength dependency distributes almost near zero.
[embodiment 1]
Fig. 1 and 2 has shown the illustration structure that adopts liquid crystal indicator of the present invention.Film A represents the cellulose acetate film of commercially available acquisition, film B represents the cellulose acetate film of the sample 101-104 that forms among the film forming embodiment 4, PVA represents polarization film described below, and film C represents the cyclic polyolefin film that forms among the film forming embodiment 1-3.
In the present embodiment, use VA-type liquid crystal indicator, but be to use the purposes of the polaroid of film of the present invention and optical compensating film and their structure not to be subjected to the restriction of the mode of operation of liquid crystal indicator.
(preparation of polaroid)
With the cellulose acetate film sample 101 of acquisition among the film forming embodiment 4 and the cellulose acetate film (TF80UL of commercially available acquisition, 80 μ m) in the 1.5N sodium hydrate aqueous solution, soaked 2 minutes in 55 ℃, washing in washing is bathed at room temperature, and with 0.1N sulfuric acid in 30 ℃ of neutralizations.The gained material is washing in washing is bathed at room temperature once more, uses 100 ℃ of air dryings then.Thus, with the surperficial saponification of cellulose acylate film.
Next, be that the web-like polyvinyl alcohol film of 80 μ m is continuously elongated and dry with coefficient 5 in iodine aqueous solution with thickness, obtain polarization film.The cellulose acylate film sample 101 and the TF80UL that provide alkali soapization to cross, and they are adhered on the two sides of the polarization film of placing between them as bonding agent with 3% polyvinyl alcohol water solution (PVA-117H, by Kuraray Co., Ltd. makes).Thus, obtain a kind of polaroid, a surface of described polaroid is protected with cellulose acylate film 10, and another surface is protected with TF80UL.Adhere to and make cellulose acylate film sample 101 parallel with the axis of homology of polarization film with TF80UL slow axis separately.
Stick with glue agent the cyclic polyolefin film F-1 that film forming embodiment 1 obtains is adhered on the polaroid of cellulose acetate film sample 101 sides, make that the slow axis of cyclic polyolefin film F-1 is parallel with the axis of homology of polarization film.Thus, make the upside polaroid.
Next, the acetate films (TF80UL, 80 μ m) of commercially available acquisition is used for the both sides of polarization film, prepares polaroid as the downside polaroid in substantially the same mode.
(preparation of VA-type liquid crystal cell and VA-type liquid crystal indicator)
Be prepared as follows liquid crystal cell.(" MLC6608 " is by Merck﹠amp will to have the liquid crystal material of negative dielectric anisotropic; Co. make) drip and be expelled to that the element gap is between the substrate of 3.6 μ m between substrate, and with base plate seals between substrate, to form liquid crystal layer.The delay of liquid crystal layer (that is the long-pending Δ nd of thickness d of liquid crystal layer (μ m) and refraction ansiotropy Δ n) is adjusted to 300nm.The liquid crystal layer vertical alignment.At the upside (observer's side) of the liquid crystal cell of this vertical alignment, stick with glue agent and adhere to the upside polaroid that makes above, make cyclic polyolefin film F-1 in the face of liquid crystal cell.At the downside (backlight side) of liquid crystal cell, stick with glue agent and adhere to the downside polaroid that makes above.These polaroids are placed to intersect the Nicol state, make the vertical operation of the axis of homology of upside polaroid and the axis of homology level run (structure 101 of Fig. 1) of downside polaroid.
The liquid crystal indicator that observation makes found that and realized being neutral black display at frontal and view directions.Use sensing equipment (EZ-Contrast 160D, make by EDLIM S.A.) measure the visual angle (contrast be 10 or scope bigger and that black display is nonreversible) in eight stages from black display (L1) to white demonstration (L8), found that at the visual angle of left and right directions and above-below direction it all is gratifying 80 ° or bigger.
Make this liquid crystal board change (10%RH, 80%RH) through ambient humidity.Even after 1 week, equating of mensuration, all almost descended with 60%RH in the color harmony visual angle of black display.Think that liquid crystal display visibility does not significantly reduce after ambient humidity changes.
When using cyclic polyolefin film F-2 or F-3 to replace cyclic polyolefin film F-1, obtain substantially the same result.When using cellulose acetate film sample 102-104 to replace cellulose acetate film sample 101, being reduced in 102 of the liquid crystal display visibility that the ambient humidity variation causes is more medium and small than 101, more medium and small in 103 than 102, and more medium and small in 104 than 103, still be that F-3 is like this no matter use F-1, F-2.This hint when Rth with the variation of humidity more hour, it is more little that ambient humidity changes the reduction of display visibility of the liquid crystal board that causes.
[Comparative Examples 1]
Obtain the structure 001 of Fig. 2 in the mode identical, only be to use the cellulose acetate film (TF80UL, 80 μ m) of commercially available acquisition to replace cellulose acetate film sample 101 to be used for the upside polaroid with embodiment 1.
Adopt the liquid crystal indicator of gained, slightly blue at frontal and view directions black display.At the visual angle of left and right directions and above-below direction all is satisfactory with 80 ° or bigger.
Make this liquid crystal board change (10%RH, 80%RH) through ambient humidity.After 1 week, the tone of black display is for more blue; Think that promptly liquid crystal display visibility reduces after ambient humidity changes.
Can see from embodiment 1 and Comparative Examples 1, even when changes in optical properties circlet shape polyolefin film F-1 that the variation of environment for use humidity causes and cellulose acetate film sample 101, display visibility changes the back reduction through ambient humidity, may be subjected to the ambient humidity variable effect and have non-zero that to differ the film (for example cellulose acetate film of commercially available acquisition) of (Re, Rth) also like this even comprise another between two polarization films.
[embodiment 2]
Obtain the structure 201 of Fig. 1 in the mode substantially the same with embodiment 1, just the upside polaroid is positioned at lower end (backlight side) and the downside polaroid is positioned at upper end (observer's side).
Observation post gets liquid crystal indicator, found that to have realized being neutral black display at frontal and view directions.Use sensing equipment to measure visual angle (contrast be 10 or scope bigger and that black display is nonreversible), found that at the visual angle of left and right directions and above-below direction it all is gratifying 80 ° or bigger.
Make this liquid crystal board change (10%RH, 80%RH) through ambient humidity.Even after 1 week, the identical of mensuration all almost descended with 60%RH in the color harmony visual angle of black display.Think that the reduction of the liquid crystal display visibility that the ambient humidity variation causes is not remarkable.
[Comparative Examples 2]
Obtain the structure 002 of Fig. 2 in the mode identical, only be to use the cellulose acetate film (TF80UL, 80 μ m) of commercially available acquisition to replace cellulose acetate film sample 101 to be used for the downside polaroid with embodiment 2.
Adopt the liquid crystal indicator of gained, slightly blue at frontal and view directions black display.All be gratifying 80 ° or bigger at the visual angle of left and right directions and above-below direction.
Make this liquid crystal board change (10%RH, 80%RH) through ambient humidity.After 1 week, the tone of black display is more blue; Think that promptly liquid crystal display visibility reduces after ambient humidity changes.
From embodiment 1 and 2 and Comparative Examples 1 and 2 can see, even environment for use humidity changes changes in optical properties circlet shape polyolefin film F-1 and the cellulose acetate film sample 101 that causes, display visibility reduces after ambient humidity changes, even between two polaroids, above or below liquid crystal cell, comprise that another may be subjected to the ambient humidity variable effect and have non-zero that to differ the film (for example cellulose acetate film of commercially available acquisition) of (Re, Rth) also like this.
[embodiment 3]
Obtain structure 102-108 and the 202-208 of Fig. 1 and the tone of observation visual angle and black display respectively with the method substantially the same with embodiment 1 and 2.Obtain and embodiment 1 and 2 substantially the same results.Provide good display visibility, even and think that liquid crystal display visibility does not significantly reduce yet after ambient humidity changes.
[embodiment 4]
Also obtain structure 109-113 and the 209-213 of Fig. 1 and 2 respectively, and observe the visual angle of liquid crystal indicator of each acquisition and the tone of black display with the method substantially the same with embodiment 1-3.Obtain the result substantially the same with embodiment 1-3.Provide good display visibility, and the ambient humidity reduction that changes the liquid crystal display visibility cause is less than among the embodiment 1-3, and is quite little.
Think that this result is owing to following reason causes.Environment for use humidity changes changes in optical properties circlet shape polyolefin film F-1 and the cellulose acetate film sample 101 that causes, and between two polaroids, above or below liquid crystal cell, do not comprise to be subjected to the ambient humidity variable effect and to have the film (for example cellulose acetate film of commercially available acquisition) that non-zero differs (Re, Rth).Therefore, liquid crystal display visibility does not reduce because of ambient humidity changes almost.
[embodiment 5]
Also obtain structure 114-118 and the 214-218 of Fig. 2 in the mode substantially the same with embodiment 1-4.Yet, in embodiment 5, with regard to the downside polaroid of the upside polaroid of structure 114-118 and structure 214-218, following that polarization film and cyclic polyolefin film C is adhering to each other.Each cyclic polyolefin film F-1, F-2 and F-3 handle with glow discharge and (apply the HF voltage of 3000Hz and 4200V between upper/lower electrode; Handled for 20 seconds), and adhere to polyvinyl alcohol-based adhesives.The gained polaroid is in 70 ℃ of dryings 10 minutes or longer.
Observe the visual angle of each gained liquid crystal indicator and the tone of black display.Obtain the result substantially the same with embodiment 4.Good display visibility is provided.The variation that the ambient humidity variation causes is substantially the same with embodiment's 4.
In the present embodiment, can reduce the quantity of the film that is used for liquid crystal indicator, and this can reduce production costs.In addition, also can reduce the thickness of liquid crystal indicator.
Industrial applicibility
The cellulose acylate film and the cyclic polyolefin film that have the wavelength dependency distribution of low-level optical anisotropy and low-level Re and Rth by use; can provide and have excellent viewing angle characteristic and the less optical element of relative ambient humidity variation display visibility minimizing; such as optical compensating film and polarizer etc., and use their liquid crystal indicator.
The application require foreign priority benefit each and each foreign patent application full content all by reference mode add this paper, as whole descriptions.

Claims (21)

1. optical compensating film, it comprises:
Satisfy the cyclic polyolefin film of formula (I); With
Satisfy formula (II) and cellulose acylate film (III):
(I) 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400,
(II) 0≤Re (630)≤ 10 Hes | Rth (630)|≤25 and
(III) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Length of delay (unit: nm) in Re (λ) the representative face under wavelength X nm wherein; And the thickness direction retardation value (unit: nm) of Rth (λ) representative under wavelength X nm.
2. liquid crystal indicator, it comprises:
At least two polarization films;
Between described at least two polarization films at least one satisfies the cyclic polyolefin film of formula (I); With
Between described at least two polarization films at least one satisfies formula (II) and cellulose acylate film (III):
(I) 35≤Re (630)≤ 350 and 70≤Rth (630)≤ 400,
(II) 0≤Re (630)≤ 10 Hes | Rth (630)|≤25 and
(III) | Re (400)-Re (700)|≤10 Hes | Rth (400)-Rth (700)|≤35,
Length of delay (unit: nm) in Re (λ) the representative face under wavelength X nm wherein; And the thickness direction retardation value (unit: nm) of Rth (λ) representative under wavelength X nm.
3. optical compensating film as claimed in claim 1,
Wherein said cyclic polyolefin film comprises a kind of multipolymer, and described multipolymer contains the repetitive of at least one formula (A) representative and the repetitive of at least one formula (B) representative:
Formula (A)
Figure A2006800022800003C1
Formula (B)
Figure A2006800022800003C2
Wherein m represents the integer of 0-4;
R 1-R 4Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 1, X 2, Y 1And Y 2Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 1And Y 1Or X 2And Y 2Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
4. optical compensating film as claimed in claim 1,
Wherein said cyclic polyolefin film comprises a kind of polymkeric substance or a kind of multipolymer, at least two ring-type repetitives that the ring-type repetitive that described polymkeric substance contains formula (B) or (C) represents, described multipolymer contain formula (B) and (C) represent,
Formula (B)
Figure A2006800022800004C1
Formula (C)
Figure A2006800022800004C2
Wherein m represents the integer of 0-4;
R 3-R 6Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 2, X 3, Y 2And Y 3Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 2And Y 3Or X 3And Y 3Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
5. as the optical compensating film of claim 3 or 4,
Wherein said cyclic polyolefin film is to obtain by the method that comprises the steps:
The organic solvent solution curtain coating that will contain the described polymkeric substance of 10 quality %-35 quality % or described multipolymer is to the endless metal supporter, and is and dry, to form dry film;
Peel off the film of described drying from described metal support, the film of peeling off with formation;
At least one direction in Width and length direction stretch described film of peeling off and
Further dry and roll.
6. as claim 1 and 3-5 optical compensating film arbitrarily,
Wherein said cellulose acylate film contains and at least a thickness direction retardation Rth is reduced to the compound that satisfies formula (IV) and scope (V),
(IV) (Rth (A)-Rth (0))/A≤-1.0 and
(V)0.01≤A≤30，
Wherein Rth (A) representative contains the Rth (nm) of film of compound of the reduction Rth of A%;
Rth (0) represents the Rth (nm) of the film of the compound that does not contain any reduction Rth (nm); With
When A representative is 100 when the quality as the polymkeric substance of the material of described film, the quality (%) of the compound of reduction Rth.
7. as claim 1 and 3-6 optical compensating film arbitrarily,
Wherein said cellulose acylate film comprises the cellulose acylate that the acyl substituted degree is 2.85-3.00.
8. as claim 1 and 3-7 optical compensating film arbitrarily,
Wherein said cellulose acylate film comprises at least a reduction | Rth (400)-Rth (700)| compound, with the solid content meter of described cellulose acylate, the content of described compound is 0.01-30 quality %.
9. as claim 1 and 3-8 optical compensating film arbitrarily,
The thickness of wherein said cellulose acylate film is 10-120 μ m.
10. polaroid, it comprises:
Polarizer; With
At least one as claim 1 and 3-9 optical compensating film arbitrarily as described in the protective film of polarizer.
11. as the polaroid of claim 10,
Wherein on the surface of described polaroid, provide at least a in hard conating, anti-glare layer and the anti-reflecting layer.
12. a liquid crystal indicator, it comprise as claim 1 and 3-9 arbitrarily optical compensating film and as in the polaroid of claim 10 or 11 at least one.
13. a VA-type liquid crystal indicator, it comprise as claim 1 and 3-9 arbitrarily optical compensating film and as in the polaroid of claim 10 or 11 at least one.
14. an IPS-type liquid crystal indicator, it comprise as claim 1 and 3-9 arbitrarily optical compensating film and as in the polaroid of claim 10 or 11 at least one.
15. liquid crystal indicator as claimed in claim 2,
Wherein said cyclic polyolefin film comprises a kind of multipolymer, and described multipolymer contains the repetitive of at least one formula (A) representative and the repetitive of at least one formula (B) representative:
Formula (A)
Figure A2006800022800007C1
Formula (B)
Figure A2006800022800007C2
Wherein m represents the integer of 0-4;
R 1-R 4Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 1, X 2, Y 1And Y 2Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 1And Y 1Or X 2And Y 2Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
16. liquid crystal indicator as claimed in claim 2,
Wherein said cyclic polyolefin film comprises a kind of polymkeric substance or a kind of multipolymer, at least two ring-type repetitives that the ring-type repetitive that described polymkeric substance contains formula (B) or (C) represents, described multipolymer contain formula (B) and (C) represent,
Formula (B)
Figure A2006800022800008C1
Formula (C)
Figure A2006800022800009C1
Wherein m represents the integer of 0-4;
R 3-R 6Represent hydrogen atom independently of one another or have the alkyl of 1-10 carbon atom;
X 2, X 3, Y 2And Y 3Represent hydrogen atom independently of one another, have 1-10 carbon atom alkyl, halogen atom, have 1-10 carbon atom and the alkyl that is replaced by halogen atom ,-(CH 2) nCOOR 11,-(CH 2) nOOCR 12,-(CH 2) nNCO ,-(CH 2) nNO 2,-(CH 2) nCN ,-(CH 2) nCONR 13R 14,-(CH 2) nNR 13R 14,-(CH 2) nOCOZ ,-(CH 2) nOZ ,-(CH 2) nW or by X 2And Y 3Or X 3And Y 3Form (CO) 2O or (CO) 2NR 15
R 11, R 12, R 13, R 14And R 15Representative independently of one another has the alkyl of 1-20 carbon atom;
Z representation hydrocarbyl or the alkyl that is replaced by halogen;
W represents SiR 16 pD 3-p, prerequisite is R 16Representative has the alkyl of 1-10 carbon atom; D represent halogen atom ,-OCOR 16Or-OR 16P represents the integer of 0-3; With
N represents the integer of 0-10.
17. as the liquid crystal indicator of claim 15 or 16,
Wherein said cyclic polyolefin film is to obtain by the method that comprises the steps:
The organic solvent solution curtain coating that will contain the described polymkeric substance of 10 quality %-35 quality % or described multipolymer is to the endless metal supporter, and is and dry, to form dry film;
Peel off the film of described drying from described metal support, the film of peeling off with formation;
At least one direction in Width and length direction stretch described film of peeling off and
Further dry and roll.
18. as the liquid crystal indicator of claim 2 and any item of 15-17,
Wherein said cellulose acylate film contains and at least a thickness direction retardation Rth is reduced to the compound that satisfies formula (IV) and scope (V),
(IV) (Rth (A)-Rth (0))/A≤-1.0 and
(V)0.01≤A≤30，
Wherein Rth (A) representative contains the Rth (nm) of film of compound of the reduction Rth of A%;
Rth (0) represents the Rth (nm) of the film of the compound that does not contain any reduction Rth (nm); With
When A representative is 100 when the quality as the polymkeric substance of the material of described film, the quality (%) of the compound of reduction Rth.
19. as the liquid crystal indicator of claim 2 and any item of 15-18,
Wherein said cellulose acylate film comprises the cellulose acylate that the acyl substituted degree is 2.85-3.00.
20. as the optical compensating film of claim 2 and any item of 15-19,
Wherein said cellulose acylate film comprises at least a reduction | Rth (400)-Rth (700)| compound, with the solid content meter of described cellulose acylate, the content of described compound is 0.01-30 quality %.
21. as the optical compensating film of claim 2 and any item of 15-20, the thickness of wherein said cellulose acylate film is 10-120 μ m.
CNB2006800022803A 2005-01-13 2006-01-13 Optical compensating film, polaroid and liquid crystal indicator Active CN100573202C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005006314A JP4596927B2 (en) 2005-01-13 2005-01-13 Liquid crystal display
JP006314/2005 2005-01-13

Publications (2)

Publication Number Publication Date
CN101116017A true CN101116017A (en) 2008-01-30
CN100573202C CN100573202C (en) 2009-12-23

Family

ID=36677802

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006800022803A Active CN100573202C (en) 2005-01-13 2006-01-13 Optical compensating film, polaroid and liquid crystal indicator

Country Status (4)

Country Link
JP (1) JP4596927B2 (en)
KR (1) KR20070102508A (en)
CN (1) CN100573202C (en)
WO (1) WO2006075793A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104704404A (en) * 2012-10-12 2015-06-10 富士胶片株式会社 Optical film, method of manufacturing optical film, polarizing plate, and image display device
CN104854646A (en) * 2013-02-20 2015-08-19 Lg化学株式会社 Display device
CN108139529A (en) * 2015-10-15 2018-06-08 日本瑞翁株式会社 Phase difference film and its manufacturing method
CN108845451A (en) * 2012-07-30 2018-11-20 东洋纺株式会社 Liquid crystal display device, polarizer and polaroid protective film
CN110869824A (en) * 2017-07-28 2020-03-06 道康宁东丽株式会社 Optical member resin sheet, optical member including optical member resin sheet, layered body, or light-emitting device, and method for manufacturing optical member resin sheet

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008063536A (en) * 2006-09-11 2008-03-21 Fujifilm Corp Cyclic olefin-based resin film
US20080107832A1 (en) * 2006-09-29 2008-05-08 Fujifilm Corporation Optical Film, Process of Producing the Same, Polarizing Plate Including the Same, and Liquid Crystal Display
JP4881827B2 (en) * 2006-09-29 2012-02-22 富士フイルム株式会社 Optical film, manufacturing method thereof, polarizing plate and liquid crystal display device using the same
US20080113121A1 (en) * 2006-11-13 2008-05-15 Fujifilm Corporation Cyclic polyolefin film, and polarizing plate and liquid crystal display device using the same

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0659121A (en) * 1992-08-11 1994-03-04 Toray Ind Inc Phase difference film and its production
JP4067734B2 (en) * 2000-03-06 2008-03-26 富士フイルム株式会社 Plasticizer for cellulose ester, cellulose ester film and method for producing the same
JP4972836B2 (en) * 2000-09-12 2012-07-11 コニカミノルタホールディングス株式会社 Manufacturing method of polarizing plate
JP4248779B2 (en) * 2001-08-02 2009-04-02 富士フイルム株式会社 Liquid crystal display
JP2003322722A (en) * 2002-05-01 2003-11-14 Fuji Photo Film Co Ltd Optical film
JP2004212863A (en) * 2003-01-08 2004-07-29 Fuji Photo Film Co Ltd Liquid crystal display device
JP2004309598A (en) * 2003-04-03 2004-11-04 Fuji Photo Film Co Ltd Retardation plate, elliptical polarizing plate and liquid crystal display device
JP4172310B2 (en) * 2003-04-10 2008-10-29 Ｊｓｒ株式会社 Polarizer
JP2004315613A (en) * 2003-04-14 2004-11-11 Fuji Photo Film Co Ltd Cellulose acylate film, its manufacturing method, polarizing plate-protecting film, liquid crystal display device, and silver halide photographic photosensitive material
JP2004315756A (en) * 2003-04-18 2004-11-11 Fuji Photo Film Co Ltd Cellulose acylate film, manufacturing method thereof, and optical film, polarizing plate, liquid crystal display device and silver halide photographic photosensitive material obtained using film
JP2005004096A (en) * 2003-06-13 2005-01-06 Sekisui Chem Co Ltd Phase difference compensating film, method for manufacturing the same composite polarizing plate, polarizing plate, and liquid crystal display device

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108845451A (en) * 2012-07-30 2018-11-20 东洋纺株式会社 Liquid crystal display device, polarizer and polaroid protective film
CN104704404A (en) * 2012-10-12 2015-06-10 富士胶片株式会社 Optical film, method of manufacturing optical film, polarizing plate, and image display device
CN104854646A (en) * 2013-02-20 2015-08-19 Lg化学株式会社 Display device
CN104854646B (en) * 2013-02-20 2017-05-10 Lg化学株式会社 Display device
US9720267B2 (en) 2013-02-20 2017-08-01 Lg Chem, Ltd. Display device
CN108139529A (en) * 2015-10-15 2018-06-08 日本瑞翁株式会社 Phase difference film and its manufacturing method
CN108139529B (en) * 2015-10-15 2021-02-02 日本瑞翁株式会社 Retardation film and method for producing same
CN110869824A (en) * 2017-07-28 2020-03-06 道康宁东丽株式会社 Optical member resin sheet, optical member including optical member resin sheet, layered body, or light-emitting device, and method for manufacturing optical member resin sheet
US12060472B2 (en) 2017-07-28 2024-08-13 Dupont Toray Specialty Materials Kabushiki Kaisha Optical member resin sheet, optical member, layered body, or light-emitting device comprising optical member resin sheet, and method for manufacturing optical member resin sheet

Also Published As

Publication number Publication date
CN100573202C (en) 2009-12-23
KR20070102508A (en) 2007-10-18
WO2006075793A1 (en) 2006-07-20
JP4596927B2 (en) 2010-12-15
JP2006195157A (en) 2006-07-27

Similar Documents

Publication Publication Date Title
KR101264447B1 (en) Polymer film, optically-compensatory film, process for producing the same, polarizing plate and liquid-crystal display device
JP4856989B2 (en) Optical resin film, polarizing plate and liquid crystal display device using the same
CN100538403C (en) Optical resin film and Polarizer and the LCD of using this optical resin film
CN101300307B (en) Polymer film, method for producing polymer film, optical film and polarizing plate and liquid crystal display device using the same
CN101014885B (en) Polymer film, and optical compensation film, polarizing plate, and liquid crystal display using the same
CN101116017A (en) Optically-compensatory film, polarizing plate and liquid-crystal display device
CN101133108B (en) Cellulose acylate film, polarizing plate and liquid crystal display device
CN1946778B (en) Cellulose acylate film, polarizing plate and liquid crystal display
CN100590458C (en) Optical resin film and polarizing film and liquid crystal display device using the same
WO2006095927A1 (en) Cellulose acylate film, and polarizing plate and liquid-crystal display device useing the same
CN100578319C (en) Liquid crystal display
JP2006291186A (en) Cellulose acylate film, method for producing the same, optical compensating film, polarizing plate and liquid crystal display device
JP4142691B2 (en) Liquid crystal display
JP2008001893A (en) Cellulose acylate film, production method of cellulose acylate film, optical compensation film, polarizing plate and liquid crystal display device
CN101196572A (en) Cellulose acylate film, production method of cellulose acylate film, optical compensation film, polarizing plate and liquid crystal display device
JP2007279478A (en) Liquid crystal display
JP2006206826A (en) Cellulose acylate film, manufacturing method of cellulose acylate film, optical compensation film, polarizing plate, and liquid crystal display unit
CN100447594C (en) Transparent film and optical compensatory film, polarizing plate and liquid-crystal display device employing it
JP2006221155A (en) Optical film, optical compensation film using the same, polarizing plate and liquid crystal display device
US8227053B2 (en) Optically compensatory film, polarizing plate and liquid-crystal display
JP2006220971A (en) Optical compensation sheet, and polarizing plate, and liquid crystal display device using the same
JP2007106794A (en) Cellulose ester film, manufacturing method of the same, optical compensation film, polarizing plate and image display device
JP2006194923A (en) Bend alignment mode liquid crystal display device
JP2006317922A (en) Cellulose acylate film, optical compensating film, method of producing them, polarizing plate and liquid crystal display device
JP2007106884A (en) Cellulose acylate film, method for producing the same, optically compensating film, polarizing plate and liquid crystal display

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant