CN100547466C

CN100547466C - Liquid crystal indicator, optical compensating gage and polarizer and the liquid crystal indicator that uses polarizer

Info

Publication number: CN100547466C
Application number: CNB2005800451787A
Authority: CN
Inventors: 杉山享; 网中英一郎; 中山元; 齐藤之人
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2004-12-28
Filing date: 2005-12-28
Publication date: 2009-10-07
Anticipated expiration: 2025-12-28
Also published as: JP2006184640A; CN101107559A; JP4771692B2

Abstract

A kind of liquid crystal indicator, it comprises: liquid crystal board, in described liquid crystal board, between upper substrate and infrabasal plate, be inserted with the liquid crystal of band negative dielectric anisotropic, described liquid crystal is vertical orientated from the teeth outwards, being oriented in when not applying voltage of described liquid crystal is almost vertical, level almost when applying predetermined voltage, and when applying than the little voltage of described predetermined voltage, tilt; Be placed on first polarizer and second polarizer of described liquid crystal board both sides, the absorption axes of wherein said polarizer is perpendicular to one another; Be placed on first retardation films between described liquid crystal board and described first polarizer; And be placed on second retardation films between described liquid crystal board and described second polarizer; wherein said polarizer comprises polarization film and described polarization film is clipped in a pair of protective film between them, and wherein at least one described protective film is the cellulose acylate film that satisfies following relational expression: 0≤Re ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25.

Description

Liquid crystal indicator, optical compensating gage and polarizer and the liquid crystal indicator that uses polarizer

Technical field

The present invention relates to a kind of the have excellent display characteristic and the liquid crystal indicator of viewing angle characteristic.

The invention still further relates to a kind of when the optical compensating gage that has improved aberration (color shift) at the dark state downwards angle of visibility during with positive face tilt, use the polarizer of this optical compensating gage and use the liquid crystal indicator of this polarizer.

Background technology

Because its toughness and anti-flammability, so cellulose acylate film be usually used in taking a picture supporter and various optical material.Particularly, in recent years, cellulose acylate film frequently is used as the optical clear film of liquid crystal indicator.Therefore cellulose acylate film has high optical clarity and high high optical isotropy, and as the device that the relates to polarization optical material of the excellence of liquid crystal indicator for example.Therefore, cellulose acylate film as the polarizer protective film, perhaps as the supporter of optical compensating film, can improve from the observed demonstration of vergence direction (viewing angle compensation) so far thus.

Polarizer is one of element that constitutes liquid crystal indicator, and it is to constitute by at least one side that the polarizer protective film is adhered to polarizer.Polarizer usually can be by obtaining polyvinyl alcohol (PVA) (PVA) the film dyeing that stretches with iodine or dichroic dye.

Under many situations, as the polarizer protective film, use can directly be bonded in the cellulose acylate film on the PVA, particularly tri acetyl cellulose film.This polarizer protective film should have excellent optical isotropy, and the characteristic of polarizer depends on the optical characteristics of polarizer protective film greatly.

Nearest liquid crystal indicator needs to improve viewing angle characteristic more urgently.Therefore, need for example polarizer protective film or retardation films (being also referred to as optical compensating film) optical isotropy more of optical clear film.With regard to regard to optically isotropic optical thin film, the length of delay of film is very important for a short time, the product representation of birefringence and film thickness of this length of delay.Particularly, in order to improve from the observed demonstration of vergence direction the delay (Re) of essential reduction frontal and the delay (Rth) of thickness direction.More particularly, when estimating the optical property of optical clear film, require at the positive Re that measures of film little, even and when measuring angle and change Re do not change yet.

So far, the cellulose acylate film that existing positive Re value reduces, but it is little with the angle variation to be difficult to make Re,, has the cellulose acylate film of little Rth that is.Therefore; proposed that by using polycarbonate film or thermoplasticity cycloolefin film to replace cellulose acylate film Re (is for example had optical clear film that the angle of reduction changes; JP-A2001-318233 and 2002-328233, the product that can ZEONOR (Japanese Zeon Corp.), ARTON (JSR Corp.) etc. obtains).Yet when when the polarizer protective film, these optical clear films are because hydrophobic and in existing problems when bonding with PVA.Another problem that exists is that the interior optical property of the whole face of film is inhomogeneous.

A solution as these problems presses for further improved cellulose acylate film, thereby obtains the excellent adaptability that is adhered to PVA by reducing optical anisotropy.More particularly, described solution is a kind of optically isotropic optical clear film, it is to be reduced to almost nilly by the positive Re with cellulose acylate film, and reduces the variation of delay angle,, Rth is reduced to almost nil acquisition that is.

During the preparation cellulose acylate film, add the compound that is called plastifier usually and improve filming performance.The known embodiment of plastifier comprises phosphotriester class for example triphenyl phosphate and phosphoric acid xenyl diphenyl, with the phthalic acid ester class (referring to, for example, Lecture on PlasticMaterials, the 17th volume, Nikkan Kogyo Shinbun, Ltd., " Cellulose Resins ", the 121st page (1970)).Known, some have the optically anisotropic effect that reduces cellulose acylate film in these plastifier, and for example, known specific fatty acid ester (referring to, for example, JP-A 2001-247717).Yet, use these conventionally known compounds to reduce the optically anisotropic effect deficiency of cellulose acylate film.

And, also more and more require nearest liquid crystal indicator to have improved Show Color.Therefore, require the optical clear film for example the visible region of supporter in the wavelength coverage of 400-800nm of polarizer protective film or optical compensating film have less Re or Rth, and depend on the Re of wavelength or Rth and change lessly, that is, chromatic dispersion is less.

In general, liquid crystal indicator (LCD) comprises liquid crystal cell and polarizer.Polarizer comprises protective film and polarization film, and polarizer is following acquisition: the polarization film dyeing by will being made by polyvinyl alcohol film with iodine, this polarization film stretched and at the laminated protective film in the both sides of described polarization film.In transmissive liquid crystal display apparatus, described polarizer is installed in the both sides of liquid crystal cell, and also can disposes one or more optical compensating gages.In reflection LCD device, with same sequence configuration reflecting plate, liquid crystal cell, one or more optical compensating gage and polarizer.Liquid crystal cell comprises liquid crystal molecule, with described molecular seal in two plate bases between them with described liquid crystal molecule is applied the electrode layer of voltage.Liquid crystal cell carries out the ON/OFF demonstration with the basis that is not all of the state of orientation of liquid crystal molecule, and proposed display mode for example TN (twisted nematic), IPS (face internal conversion), OCB (optical compensation curved), VA (homeotropic alignment) and ECB (ECB electrically controlled birefringence), they both can be used for transmission-type and also can be used for reflection-type.

Among these LCDs, in order to need the purposes of high display quality, the main 90 ° of twisted nematic liquid crystal display device (this paper back is referred to as the TN type) of using, yet this device employing has the nematic liquid crystal molecules of positive dielectric anisotropy and operates by thin film transistor (TFT), the TN type shows such viewing angle characteristic, although these devices have excellent display characteristic during promptly from top view, but when their display characteristic deterioration when vergence direction is observed, cause contrast to reduce, the tone reversal that brightness is put upside down when perhaps occurring in gray level display, or the like.Therefore, press for these characteristics of improvement.

In recent years, the form that improved LCD is arranged as this viewing angle characteristic, homeotropic alignment nematic liquid crystal display device (this paper back is referred to as the VA type) has been proposed, wherein use nematic liquid crystal molecules to make on substrate, roughly arranging of when not applying any voltage liquid crystal molecule, and operate these liquid crystal molecules (referring to JP-A11-258605) by thin film transistor (TFT) in vertical direction than major axis with negative dielectric anisotropic.Described VA type shows excellent display characteristic with the level suitable with the TN type when from top view, thereby and owing to adopts the retardation films at compensation visual angle also to show the viewing angle characteristic that enlarges.

Also known in the VA type, have the retardation films of the anisotropic uniaxial orientation of positive refracting power and the negative single shaft retardation films that has optical axis in the direction vertical by use, the viewing angle characteristic that can obtain to enlarge more (referring to JP-A 11-258605) with pellicular front.

Yet, in this VA type liquid crystal indicator,, just can not obtain gratifying viewing angle characteristic if will not keep the optical anisotropy of the transparent protective film (also finishing the effect of serving as supporter) of retardation films and polarizer to be designed to have appropriate value.And, when the PVA film that constitutes polarizer shrinks, on the transparent protective film that keeps polarizer, producing stress under hot and wet effect, the optical anisotropy of protective film itself changes thus.Therefore, there is defective, the display quality deterioration of so-called corner point particularly, this is the light leak of four corners of screen.

Therefore, first purpose of the present invention provides a kind of liquid crystal indicator with excellent display characteristic and viewing angle characteristic.

In addition, for the VA type, also known: by on liquid crystal cell with two negative single shaft retardation films that have optical axis in the direction vertical of following use with pellicular front, can obtain the characteristic at broad visual angle, and the uniaxial orientation retardation films that in described LCD, uses length of delay in the face with positive refracting power anisotropy and 50nm, can obtain to enlarge the characteristic (referring to SID 97DIGEST 845-848 page or leaf) at visual angle.

Yet, production cost also increases when using two retardation films (referring to SID 97DIGEST 845-848 page or leaf), and have the bonding problem that causes productive rate to reduce of a plurality of films, use the multi-disc film to cause thickness to increase, and the thickness of display device is reduced this is defective.And, bonding coat is used for laminated oriented film causes bonding coat contraction under the situation that temperature and humidity changes, and the defective of film layering or distortion may take place thus.As the method for improving these problems, a kind of method (referring to JP-A11-95208) and a kind of method (referring to JP-A 2003-15134 and 11-95208) of using cholesteric that reduces retardation films quantity disclosed.Yet, even these methods also need bonding a plurality of film, and therefore unsatisfactory from the angle that thickness reduces and production cost reduces.And the problem of existence has: can not suppress under the dark state light leak at the vergence direction of polarizer fully at visible region, and the visual angle enlarges not enough.More prior is that the incident angle of the vergence direction of relative polarizer is difficult to the full remuneration light leak at whole wavelength of visible light scope under dark state, and therefore has the dependent problem of azimuth direction that aberration takes place.The method (referring to JP-A 2002-221622) that a kind of chromatic dispersion by the control lag film prevents light leak is also proposed, but the problem that exists is the difference of not considering between the chromatic dispersion of the chromatic dispersion that postpones in the face and thickness direction retardation, and the effect deficiency of inhibition light leak.And, do not take into full account the influence that the birefringence of liquid crystal layer changes, and can not obtain to depend on enough effects of the birefringence value of liquid crystal layer.

Therefore, second purpose of the present invention provides a kind of liquid crystal indicator, particularly a kind of VA type liquid crystal indicator, and described device has high contrast because of the precise optical compensation of liquid crystal cell.Specifically, the purpose of this invention is to provide a kind of liquid crystal indicator, particularly a kind of VA type liquid crystal indicator, it has the light leak of reduction and therefore has improved visual angle contrast at vergence direction under dark state.

And; for example; Jap.P. 2587398 described that a kind of described optical compensating gage is discotic mesogenic to be coated on the tri acetyl cellulose film by optical compensating gage being used for the technology that TN type liquid crystal cell enlarges the visual angle, through arranging and time of day gets.Yet, at the liquid crystal indicator that is used for televisor, suppose from different perspectives and watch that it is difficult requiring view angle dependency thus, even and adopt said method also can not satisfy this requirement by giant-screen.Therefore, studying the liquid crystal indicator different, for example IPS (face internal conversion) type, OCB (optical compensation curved) type and VA (homeotropic alignment) type with the TN type always.Particularly, the VA type receives publicity as the liquid crystal indicator of TV, and this is because it has high contrast and quite high productive rate when preparation large scale screen.

As the optical compensating gage of VA type, known a kind of compensating plate, it has: have optical axis in the face as the film (plate A) of the positive single shaft of optics with have the film (plate C) of the optical axis of film normal direction as the optical negative single shaft; Can realize the compensating plate (referring to JP-A 11-258605 and 11-133413) that the visual angle enlarges with a kind of by use optics biaxial films.Yet, the improvement of aberration when these documents are not mentioned dark state downwards angle of visibility and positive face tilt.In the optical compensating gage of this VA type, by with Re _(λ)Chromatic dispersion as inverse (reciprocal the chromaticdispersion) (Re of shorter wavelength side that looses _(λ)Re less than longer wavelength side _(λ)), and with Rth _(λ)Chromatic dispersion as positive dispersion (chromatic dispersion the proper) (Re of shorter wavelength side _λRe greater than longer wavelength side _(λ)), the aberration in the time of can improving dark state downwards angle of visibility and positive face tilt situation, and the optics biaxial films (WO2004/068226A1) with this dispersion characteristics is disclosed.

An embodiment as the optical compensating gage of VA type; JP-A 11-95208 discloses a kind of optical compensating gage; comprising the vertical single axle drawn membrane of norbornene polymer (trade name: ARTON) with in tri acetyl cellulose film (trade name: be formed on hydrophobic resin (trade name: the film that contains the layer of organic adhesive composite (trade name: Lucentite STN, Lucentite SPN) Denkabutyral#3000-K) FUJITACKSH-80).Yet, the Re of the vertical single axle drawn membrane of ARTON _(λ)Wavelength is not depended in chromatic dispersion, although it is uniformly, and the Rth of tri acetyl cellulose film _(λ)Chromatic dispersion is anti-Wavelength distribution (reciprocalwavelength distribution).Therefore, from improve the angle of aberration under the situation of dark state downwards angle of visibility and positive face tilt, described performance is unsatisfactory.And the optical anisotropic layer that contains organic adhesive composite in hydrophobic resin is not durable and is soft, and therefore the processibility of described layer is bad.

As an embodiment of VA type optical compensating gage, JP-A 2002-311243 has described a kind of by tri acetyl cellulose (trade name: contain the optical anisotropic layer of rod-like nematic liquid crystal and the optical compensating gage that another optical anisotropic layer that contains cholesteric crystal is made FUJITACK T-50SH); The optical compensating gage that a kind of optical anisotropic layer of being made up of the polyimide layer on the tri acetyl cellulose and another rod-like nematic liquid crystal layer are made; With a kind of polarizer that comprises optical compensating layer, state arbitrary optical compensating gage using tri acetyl cellulose to close as the polarizer upper strata of protective film.Even, comprise the Re of the optical anisotropic layer of rod-like nematic liquid crystal with regard in these two kinds of polarizers that comprise optical compensating gage with regard to any one _(λ)Chromatic dispersion is positive dispersion, and the tri acetyl cellulose film Rth _(λ)Chromatic dispersion is that inverse looses.Therefore, from improve the angle of aberration under the situation of dark state downwards angle of visibility and positive face tilt, described performance is unsatisfactory.

Therefore, the 3rd purpose of the present invention provides a kind of optical compensating gage, wherein can improve the desirable dispersion characteristics of aberration under the situation of the dark state downwards angle of visibility that is attained at liquid crystal indicator by laminated a plurality of retardation films and positive face tilt; And provide a kind of polarizer that uses optical compensating gage as protective film; With a kind of liquid crystal indicator that uses this polarizer.

Summary of the invention

First purpose of the present invention is that (this paper back is referred to as " first embodiment ") realizes in the following manner.

[1] a kind of liquid crystal indicator, it comprises: liquid crystal board, in described liquid crystal board, between upper substrate and infrabasal plate, be inserted with the liquid crystal of band negative dielectric anisotropic, described liquid crystal is vertical orientated from the teeth outwards, being oriented in when not applying voltage of described liquid crystal is almost vertical, level almost when applying predetermined voltage, and when applying than the little voltage of described predetermined voltage, tilt; Be placed on first polarizer and second polarizer of described liquid crystal board both sides, the absorption axes of wherein said polarizer is perpendicular to one another; Be placed on first retardation films between described liquid crystal board and described first polarizer; And be placed on second retardation films between described liquid crystal board and described second polarizer; wherein said polarizer comprises polarization film and described polarization film is clipped in a pair of protective film between them, and wherein at least one described protective film is the cellulose acylate film that satisfies following relational expression:

0≤Re ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25.

[2] as the liquid crystal indicator of [1], wherein said first retardation films satisfies:

50≤Re ₍₅₈₉₎≤ 100 and 30≤Rth ₍₅₈₉₎≤ 80 and

Described second retardation films satisfies:

Re ₍₅₈₉₎≤ 20 and 100≤Rth ₍₅₈₉₎|≤300.

[3] as the liquid crystal indicator of [1] or [2], wherein said cellulose acylate film satisfies:

0≤Re ₍₆₃₀₎≤ 5 Hes | Rth ₍₆₃₀₎|≤10.

[4] as each liquid crystal indicator of [1]-[3], wherein said cellulose acylate film satisfies:

0≤Re ₍₆₃₀₎≤ 3 Hes | Rth ₍₆₃₀₎|≤5.

[5] as each liquid crystal indicator of [1]-[4], wherein said cellulose acylate film contains the compound of the delay Rth of at least a reduction film thickness direction, and the amount of described compound satisfies following formula (I) and (II):

(I)(Rth(A)-Rth(0))/A≤-1.0，

(II)0.01≤A≤30

Wherein Rth (A) is the Rth (nm) of film of compound that contains the described reduction Rth of A%, Rth (0) is the Rth (nm) of film that does not contain the compound of described reduction Rth, and A is the weight (%) in the described compound of 100 weight % of the raw polymer of described film.

[6] as each liquid crystal indicator of [1]-[5]; wherein said cellulose acylate film is that the cellulose acylate of 2.85-3.00 is made by the acyl substituted degree; and described cellulose acylate contains the compound of at least a reduction Re (λ) and Rth (λ); with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

[7] as each liquid crystal indicator of [1]-[6], wherein said cellulose acylate film contains at least a this film of reduction | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎| compound, with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

[8] as each liquid crystal indicator of [1]-[7], the thickness of wherein said cellulose acylate film is 10-120 μ m.

Second purpose of the present invention is that (this paper back is referred to as " second embodiment ") realizes in the following manner.

[9] a kind of liquid crystal indicator, it comprises:a pair of substrate that faces with each other and place, and be inserted in nematic liquid crystal material between the described a pair of substrate, at least one in the described substrate has electrode; And described liquid crystal indicator has liquid crystal cell; This liquid crystal cell has liquid crystal layer; In described liquid crystal layer; The surperficial near normal ground of the liquid crystal molecule of described nematic liquid crystal material and described a pair of substrate is arranged under dark state; Through installing so that described liquid crystal cell is inserted in the first polarization film and the second polarization film between them; Be installed in respectively between described liquid crystal layer and described the first polarization film and the optical compensating film between described liquid crystal layer and described the second polarization film

Wherein between at least one in described optical compensating film and described polarization film and described liquid crystal layer cellulose acylate film is installed,

Wherein the thickness when described liquid crystal layer is that (unit: nm), (unit: the refractive index anisotropy nm) is Δ n to wavelength X to d _(λ), postponing sum in the face of described optical compensating film and described cellulose acylate film under the wavelength X is Re _{Sum (λ)}, and described optical compensating film and described cellulose acylate film are Rth in the delay sum of thickness direction under the wavelength X _{Sum (λ)}The time, with respect at least two in the wavelength coverage of 380nm-780nm different wavelength, satisfy following formula (I)-(IV):

(I)200≤Δn _(λ)xd≤1000，

(II)Rth _sum(λ)/λ＝AxΔn _(λ)xd/λ+B，

(III) Re _{Sum (λ)}/ λ=Cx λ/{ Δ n _(λ)X d}+D and

(IV)0.488≤A≤0.56，

B＝-0.0567，

-0.041≤C≤0.016 and

D=0.0939; And

Wherein (unit: postponing in the face nm) is Re in wavelength X when described cellulose acylate film _{2 (λ)}, and wavelength X (unit: nm) down described cellulose acylate film is Rth in the delay of thickness direction _{2 (λ)}The time, satisfy following formula (IX) and (X):

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(X) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

[10] as the liquid crystal indicator of [9], the axis of homology of the polarization film that more close described optical compensating film is placed in slow axis and described first polarization film and described second polarization film in the face of wherein said optical compensating film is substantially parallel.

[11] as the liquid crystal indicator of [9] or [10], wherein, satisfy following formula (I)-(IV) with respect to differing 50nm or at least two bigger wavelength.

[12] as each liquid crystal indicator of [9]-[11], wherein, satisfy following formula (I)-(IV) with respect to 450nm, 550nm and these three wavelength of 650nm.

[13] a kind of liquid crystal indicator, it comprises: a pair of substrate that faces with each other and place, and be inserted in nematic liquid crystal material between the described a pair of substrate, at least one in the described substrate has electrode; And described liquid crystal indicator has liquid crystal cell; this liquid crystal cell has liquid crystal layer; in described liquid crystal layer; the surperficial near normal ground of the liquid crystal molecule of described nematic liquid crystal material and described a pair of substrate is arranged under dark state; make described liquid crystal cell be clipped in first polarization film and second polarization film between them through installation; be installed in the optical compensating film between described liquid crystal layer and one of described first polarization film and described second polarization film; and be installed in the cellulose acylate film between at least one in described liquid crystal layer and described first polarization film and described second polarization film

Wherein the thickness when described liquid crystal layer is that (unit: nm), (unit: the refractive index anisotropy nm) is Δ n to wavelength X to d _(λ), postponing sum in the face of described optical compensating film and described cellulose acylate film under the wavelength X is Re _{Sum (λ)}, and described optical compensating film and described cellulose acylate film are Rth in the delay sum of thickness direction under the wavelength X _{Sum (λ)}The time, with respect at least two in the wavelength coverage of 380nm-780nm different wavelength, satisfy following formula (V)-(VIII):

(V)200≤Δn _(λ)xd≤1000，

(VI)Rth _sum(λ)/λ＝ExΔn _(λ)xd/λ，

(VII) Re _{Sum (λ)}/ λ=Fx λ/{ Δ n _(λ)Xd}+G and

(VIII)0.726≤E≤0.958，

0.0207≤F≤0.0716 and

G=0.032; And

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(X) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

[14] as the liquid crystal indicator of [13], the axis of homology of the polarization film that more close described optical compensating film is placed in slow axis and described first polarization film and described second polarization film in the face of wherein said optical compensating film is substantially parallel.

[15] as the liquid crystal indicator of [13] or [14]; angle between the axis of homology of the polarization film that more close described cellulose acylate film is installed in slow axis and described first polarization film and described second polarization film in the face of wherein said cellulose acylate film; between-10 ° to 10 °, perhaps between 80 ° to 110 °.

[16] as each liquid crystal indicator of [13]-[15], wherein, satisfy following formula (V)-(VIII) with respect to differing 50nm or at least two bigger wavelength.

[17] as each liquid crystal indicator of [13]-[16], wherein, satisfy following formula (V)-(VIII) with respect to 450nm, 550nm and these three wavelength of 650nm.

The 3rd purpose of the present invention is that (this paper back is referred to as " the 3rd embodiment ") realizes in the following manner.

[18] a kind of optical compensating gage, it has the transparent supporting body that satisfies following formula (1) and (2), the optical anisotropic layer C that is installed on the described transparent supporting body and satisfies the optical anisotropic layer A of following formula (3) and satisfy following formula (4) successively:

(1) 0≤Re ₍₅₉₀₎≤ 10 Hes | Rth ₍₅₉₀₎|≤25,

(2) | Re ₍₄₅₀₎-Re ₍₆₅₀₎|≤10 Hes | Rth ₍₄₅₀₎-Rth ₍₆₅₀₎|≤35,

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200,

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400

Re wherein _(λ)It is the front length of delay (unit: nm), and Rth under the wavelength X nm _(λ)Be in the length of delay (unit: nm) of thickness direction under the wavelength X nm.

[19] a kind of optical compensating gage, it has the transparent supporting body that satisfies following formula (1) and (2) successively, be installed on the described transparent supporting body and satisfy the optical anisotropic layer C of following formula (4) and be installed on the optical anisotropic layer A that described optical anisotropic layer C went up and satisfied following formula (3):

(1) 0≤Re ₍₅₉₀₎≤ 10 Hes | Rth ₍₅₉₀₎|≤25,

(2) | Re ₍₄₅₀₎-Re ₍₇₀₀₎|≤10 Hes | Rth ₍₄₅₀₎-Rth ₍₆₅₀₎|≤35,

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200,

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400

[20] as the optical compensating gage of [18] or [19], wherein said transparent supporting body contains at least a reduction Rth _(λ)Compound, its content satisfies following formula (5) and (6):

(5) (Rth _(λ)(A)-Rth _(λ)(0))/A≤-1.0 and

(6)0.01≤A≤30

Rth wherein _(λ)(A) be the described reduction Rth that contains A% _(λ)The Rth of transparent supporting body of compound _(λ)(nm); Rth _(λ)(0) be not contain described reduction Rth _(λ)The Rth of transparent supporting body of compound _λ(nm); And A is the weight (%) in the described compound of 100 weight % of the raw polymer of described transparent supporting body.

[21] as each optical compensating gage of [18]-[20], wherein said transparent supporting body contains at least a reduction | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎| compound, with respect to the solids content of the raw polymer of described supporter, the amount of described compound is 0.01-30 weight %.

[22] as each optical compensating gage of [18]-[21], wherein said transparent supporting body is formed by cellulose acylate film.

[23] as the optical compensating gage of [22]; wherein said cellulose acylate film is that the cellulose acylate of 2.85-3.00 is made by the acyl substituted degree; and described cellulose acylate film contains the compound of at least a reduction Re (λ) and Rth (λ); with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

[24] as each optical compensating gage of [18]-[23], the film thickness of wherein said transparent supporting body is 10-120 μ m.

[25] as each optical compensating gage of [18]-[24], wherein said optical anisotropic layer A is made by the thin polymer film that stretches.

[26] as each optical compensating gage of [18]-[24], wherein said optical anisotropic layer A is formed by liquid-crystal compounds.

[27] as each optical compensating gage of [18]-[26], wherein said optical anisotropic layer C is made by the thin polymer film that stretches.

[28] as each optical compensating gage of [18]-[26], wherein said optical anisotropic layer C is formed by liquid-crystal compounds.

[29] as each optical compensating gage of [18]-[26], wherein said optical anisotropic layer C is formed by non-liquid-crystal compounds.

[30] as each optical compensating gage of [18]-[29], the Re of wherein said optical anisotropic layer A _(λ)Wavelength dependency satisfy following formula (7) and (8):

(7) Re ₍₄₅₀₎/ Re ₍₅₅₀₎=0.60-0.98 and

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.00-1.60。

[31] as each optical compensating gage of [18]-[29], the Rth of wherein said optical anisotropic layer C _(λ)Wavelength dependency satisfy following formula (9) and (10):

(9) Rth ₍₄₅₀₎/ Rth ₍₅₅₀₎=1.02-1.60 and

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.60-1.00。

[32] as each optical compensating gage of [18]-[29], the Re of wherein said optical anisotropic layer A _(λ)Wavelength dependency satisfy following formula (7) and (8), and the Rth of described optical anisotropic layer C _(λ)Wavelength dependency satisfy following formula (9) and (10):

(7)Re ₍₄₅₀₎/Re ₍₅₅₀₎＝0.60-0.98，

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.00-1.60，

(9) Rth ₍₄₅₀₎/ Rth ₍₅₅₀₎=1.02-1.60 and

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.60-1.00。

[33] a kind of polarizer has protective film in the both sides of described polarizer, and wherein at least one described protective film is as each optical compensating gage of [18]-[32], and links to each other with described polarizer in the face of a side of described transparent supporting body.

[34] as the polarizer of [33], wherein said protective film contains and is selected from least a in plastifier, ultraviolet light absorber, short release agent, dyestuff, matting agent and the electrically conductive particles.

[35] as the polarizer of [33] or [34], wherein on the surface of at least one protective film, provide the one deck at least that is selected from hard conating, anti-glare layer, anti-reflecting layer, stain-proofing layer and the antistatic layer.

[36] a kind of liquid crystal indicator, it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides, and wherein at least one described polarizer is as each polarizer of [33]-[35].

[37] a kind of liquid crystal indicator; it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides; wherein said polarizer comprises polarizer and a pair of this polarizer is clipped in protective film between them, and at least one described protective film is the optical compensating gage as [18].

[38] a kind of liquid crystal indicator; it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides; wherein said polarizer comprises polarizer and a pair of this polarizer is clipped in protective film between them, and at least one described protective film is the optical compensating gage as [19].

[39] as each liquid crystal indicator of [36]-[38], wherein said liquid crystal cell is a VA type element.

First embodiment of the invention can provide the liquid crystal indicator of a kind of corner point with excellent viewing angle characteristic, reduction and high display quality.

Further investigate the knowledge of acquisition based on present inventor's inventors, second embodiment of the invention is finished, and by suitably selecting material or job operation, postpone in the face of optical compensating film controlling independently and the chromatic dispersion of the delay of thickness direction, so that determine best optical value, make thus that under any wavelength of visible region at liquid crystal cell, particularly the viewing angle compensation under the dark state of VA type liquid crystal cell becomes possibility.As a result, the liquid crystal indicator of second embodiment of the present invention has reduced light leak with respect to any wavelength under the angle that is tilting under the dark state, significantly improved the visual angle contrast thus.And the liquid crystal indicator of second embodiment of the present invention can suppress the light leak of vergence direction in any visible wavelength region under dark state, even also like this under the birefringence situation of other liquid crystal layer.

According to the 3rd embodiment of the present invention, can provide a kind of optical compensating gage, the aberration when it can improve visual angle and positive face tilt under the dark state of liquid crystal indicator with desirable dispersion characteristics.

Specifically, according to the 3rd embodiment of the present invention, by reducing the optical anisotropy (Re of the transparent supporting body that forms optical compensating gage _(λ), Rth _(λ)) can obtain desirable optical compensation, the optical compensation effect of the optical anisotropic layer that the optical property of transparent supporting body is caused is without any spinoff, and the aberration therefore can improve under the dark state visual angle especially with positive face tilt the time.

And; according to the 3rd embodiment of the present invention; by above-mentioned optical compensating gage and polarizer commonly used; for example; the polarizer that forms by the polyvinyl alcohol film that stretches; by using conventional cellulose acetate ester can prepare a kind of polarizer, and use this polarizer that a kind of liquid crystal indicator with high display quality can be provided as the method that protective film prepares polarizer.

Description of drawings

Fig. 1 is a synoptic diagram of describing a kind of illustration structure of conventional VA type liquid crystal indicator.

Fig. 2 is a synoptic diagram of describing a kind of illustration structure of conventional VA type liquid crystal indicator.

Fig. 3 is the synoptic diagram of illustration structure of describing the one type of liquid crystal display device of second embodiment.

Fig. 4 is the synoptic diagram of illustration structure of describing the another kind of liquid crystal indicator of second embodiment.

Fig. 5 is the figure that shows the optical characteristics of the illustration optical compensating film that is used for second embodiment.

Fig. 6 is the synoptic diagram of Poincare sphere of variation that is used for being described in the illustration liquid crystal indicator polarization of incident light state of second embodiment.

Fig. 7 is the synoptic diagram of Poincare sphere of variation that is used for being described in another illustration liquid crystal indicator polarization of incident light state of second embodiment.

Fig. 8 is a synoptic diagram of describing the illustration liquid crystal indicator of second embodiment.

In the accompanying drawings, 1 represents polarizer, and 2 represent polarizer; 3 represent liquid crystal cell; 4,5 and 6 represent optical compensating film, 11 and 101 represent polarization film, and 12 and 102 represent absorption axes; 13 and 103 represent protective film (cellulose acylate film); 13a and 103a represent slow axis in the face, and 15 and 19 represent optical compensating film, and 15a and 19a represent slow axis in the face; on behalf of substrate and 17,16 and 18 represent liquid crystal molecule.

Embodiment

To describe the present invention in detail below.The description of compositing factor described below may be based on representative example of the present invention, but the present invention is not limited to these examples.In addition, " " used herein numeric value represented scope is meant and comprises the scope of the described numerical value in symbol "-" front and back as the lower limit and the upper limit.

And in this manual, term " parallel " or " vertically " comprise relative position in accurate angle ± less than 5 ° scope.With the error of accurate angle preferably less than 4 °, be more preferably less than 3 °.As for angle, "+" is meant clockwise direction, and "-" is meant counterclockwise.Term " slow axis " is meant the direction of refractive index maximum." visible region " is 380nm-780nm.In addition, measure the value that the used wavelength of refractive index is λ=550nm in the visible region, except as otherwise noted.

In this manual, term " polarizer " both had been used in reference to the very long polarizer of length (as long as it is without specific cutting), was used in reference to again and cut into the polarizer (term " cutting " comprises " punching " and " cutting apart ") that is installed in the size in the liquid-crystal apparatus.And in this manual, " polarization film " and " polarizer " difference is used, and still " polarizer " is meant laminated thing, and " polarization film " has transparent protective film with the protection polarization film in its at least one side in this laminated thing.

In this manual, various films, for example cellulose acylate film and optical compensating film postpone Re in the face under the wavelength X _(λ)Delay Rth with thickness direction _(λ), be meant the value that obtains by following method.At first, Re _(λ)Be meant of the normal direction incident of the light of usefulness wavelength X nm, with the value of KOBRA-21ADH (Oji Scientific Instruments) mensuration from film.Rth _(λ)Be meant that with the length of delay three direction detections altogether be the value of basic calculation, for example above-mentioned Re of described length of delay _(λ), with slow axis (measuring) by KOBRA-21ADH as sloping shaft (turning axle) from the normal direction with film tilt+40 ° direction incident wavelength be λ nm light measurement length of delay and with slow axis as sloping shaft (turning axle) from the length of delay that-40 ° the light of direction incident wavelength λ nm measures with KOBRA-21ADH that tilts of the normal direction with film.Here, with regard to the default of mean refractive index, can use Polymer Handbook (John Wiley﹠amp; Sons, Inc.) and the value that provides in the various catalogues of optical thin film.With regard to have the mean refractive index value different with conventional value with regard to, can be with Abbe refractometer mensuration refractive index.Enumerate the mean refractive index value of optical thin film commonly used below: cellulose acylate (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49) and polystyrene (1.59).

When the default of importing these mean refractive indexs and film thickness, KOBRA-21ADH calculates nx, ny and nz.

Among whole the present invention, the mean refractive index that is used for cellulose acylate film is 1.48.

In the first embodiment, the mean refractive index that is used for first retardation films is 1.52, and the mean refractive index that is used for second retardation films is 1.6.

In second embodiment, postpone sum Re in the face of cellulose acylate film and optical compensating film _{Sum (λ)}And the delay sum Rth of its thickness direction _{Sum (λ)}, also be meant the value that obtains by said method.

First embodiment

First embodiment of the present invention is described below.

The liquid crystal indicator of first embodiment comprises: liquid crystal board, in described liquid crystal board, between upper substrate and infrabasal plate, be inserted with the liquid crystal of band negative dielectric anisotropic, described liquid crystal is vertical orientated from the teeth outwards, being oriented in when not applying voltage of described liquid crystal is almost vertical, level almost when applying predetermined voltage, and when applying than the little voltage of described predetermined voltage, tilt; Be placed on first polarizer and second polarizer of described liquid crystal board both sides, the absorption axes of wherein said polarizer is perpendicular to one another; Be placed on first retardation films between described liquid crystal board and described first polarizer; And being placed on second retardation films between described liquid crystal board and described second polarizer, wherein said polarizer comprises polarization film and described polarization film is clipped in a pair of protective film between them.With regard at least one described protective film, postpone Re in the face under wavelength 630nm ₍₆₃₀₎Be 10nm or littler (0≤Re ₍₆₃₀₎≤ 10), and the delay Rth of thickness direction ₍₆₃₀₎Absolute value be 25nm or littler (| Rth|≤25).And these are worth preferred 0≤Re ₍₆₃₀₎≤ 5 Hes | Rth|≤10nm, more preferably 0≤Re ₍₆₃₀₎≤ 3 Hes | Rth|≤5.In the present invention; a kind of VA (homeotropic alignment) type liquid crystal indicator can be provided; by use postponing in above-mentioned scope and have the cellulose acetate film of excellent durability as the protective film of polarizer, described liquid crystal indicator has the excellent viewing angle characteristic and the corner point of reduction.

Further describe cellulose acylate film below.

[cellulose acylate raw fibre]

Can be cotton linters or wood pulp (bardwood pulp, softwood pulp) as the used cellulose of cellulose acylate raw material in the first embodiment; and can use the cellulose acetate ester that obtains by any raw cellulose; and if necessary, can use by potpourri.Can be for example about the detailed description of these raw celluloses, Lecture on PlasticMaterials (17), Cellulose Resins (Marusawa and Uda, Nikkan KogyoShinbun, Ltd. (1970)) or Patent Studies of the Japanese Institute ofInvention and Innovation 2001-1745 (7-8 page or leaf) in find, and can use wherein said cellulose.The cellulose acylate film that is used as the protective film of polarizer in the first embodiment has no particular limits.

[degree of substitution of cellulose acylate]

Next, will describe the cellulose acylate that is used as the protective film of polarizer in the first embodiment, it is made by above-mentioned cellulosic material.The cellulose acylate that is used for first embodiment is the cellulose of its hydroxyl through acidylate, and operable substituting group comprises from acyl group with 2 carbon atoms (for acetyl group) to the acyl group with 22 carbon atoms.With regard to the cellulose acylate that is used for first embodiment; the degree of substitution of cellulosic hydroxyl has no particular limits, but the acetate of hydroxyl that can be by measuring substituted cellulose and/or conjugation (degree of bonding) with fatty acid of 3-22 carbon atom are then through calculating this degree of substitution of acquisition.This mensuration can be carried out according to ASTM D-817-91 method.

With regard to the cellulose acylate that is used for first embodiment, the degree of substitution of cellulosic hydroxyl has no particular limits, but the acyl substituted degree of cellulosic hydroxyl 2.50-3.00 preferably.And degree of substitution is 2.75-3.00 preferably, 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, the acyl group with 2-22 carbon atom can be aliphatic group or allyl, has no particular limits, and can use separately or two or more are used in combination.The example comprises cellulosic alkyl-carbonyl ester class, alkenyl carbonyl ester class or fragrant carbonyl ester class, aromatic alkyl carbonyl ester class, and they can further be substituted separately.The preferred embodiment of described 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, isobutyryl, uncle's bytyry, cyclohexane carbonyl, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl etc.Wherein, preferred acetyl group, propiono, bytyry, dodecane acyl group, octadecanoyl, uncle's bytyry, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl etc., more preferably acetyl group, propiono and bytyry.

Further investigation through inventors of the present invention; discovery is in the acyl substituent of the hydroxyl of above-mentioned substituted cellulose; acyl substituent consists essentially of under two kinds the situation that is selected from acetyl group/propiono/bytyry at least; when total degree of substitution is 2.50-3.00, can reduce the optical anisotropy of cellulose acylate film effectively.The acyl substituted degree is more preferably 2.60-3.00, even more preferably 2.65-3.00.

[degree of polymerization of cellulose acylate]

In viscosity average polymerization degree, the degree of polymerization that is preferred for the cellulose acylate of first embodiment is 180-700, and the degree of polymerization of cellulose acetate ester 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 dope of cellulose acylate increased, and therefore the film preparation by curtain coating becomes difficult.Cross when low when the degree of polymerization, the intensity of the film that makes reduces.Average degree of polymerization can be measured (Kazuo Uda and Hideo Saito by the limiting viscosity method of Uda etc., Bulletin of The Societyof Fiber Science and Technology, Japan, the 18th volume, No.1,105-120 page or leaf (1962)).It also has a detailed description in JP-A 9-95538.

And the molecular weight distribution of cellulose acylate that is preferred for first embodiment is by gel permeation chromatography, and preferred polydispersity index Mw/Mn (Mw: weight-average molecular weight, Mn: number-average molecular weight) little, narrow molecular weight distribution simultaneously.The occurrence of Mw/Mn preferably in the scope of 1.0-3.0, more preferably 1.0-2.0, most preferably 1.0-1.6.

Remove low-molecular-weight component and make mean molecular weight (degree of polymerization) increase, but viscosity is become is lower than cellulose acylate commonly used, therefore, this removal is useful.The cellulose acylate that low-molecular-weight component reduces can obtain by remove low-molecular-weight component from the synthetic cellulose acylate of known method.The removal of low-molecular-weight component can be by carrying out with the plain acylate of suitable organic solvent rinsing fiber.Under the situation of the cellulose acylate that the preparation low-molecular-weight component reduces, with respect to the cellulose of 100 mass parts, the amount of sulfuric acid catalyst preferably is adjusted in the scope of 0.5-25 mass parts in the acylation reaction.The amount of sulfuric acid catalyst can the suitable cellulose acylate (having uniform molecular weight distribution) of synthetic molecular weight distribution in above-mentioned scope.Preparation is when being used for the cellulose acylate of first embodiment, and the moisture of cellulose acylate is 2 quality % or littler preferably, more preferably 1 quality % or littler, preferred especially 0.7 quality % or littler.The plain acylate of known fiber contains the water of the amount of 2.5-5 quality % usually.In order to obtain the aforementioned moisture of cellulose acylate of the present invention, need carry out drying.With regard to cellulose acylate of the present invention; raw material cotton and synthetic method are described in detail in Japan Institute of Inventionand Innovation; Technical Publication (Technical Publication No.2001-1745; the 7-12 page or leaf; on March 15 calendar year 2001, Japan Institute of Inventionand Innovation publishes).

The cellulose acylate that is used for first embodiment can use separately or can use in two or more potpourri, and prerequisite is that substituting group, degree of substitution, the degree of polymerization and molecular weight distribution are in above-mentioned scope.

[adjuvant of cellulose acylate]

According to various objectives; in each preparation process; can (for example add various adjuvants to the cellulose acylate solution of the cellulose acylate film that is used for preparing first embodiment; reduce optically anisotropic compound, dispersion adjustment agent, UV resistant agent, plastifier, anti-degradation, particulate or optical property correctives), and will explain these adjuvants below.And this interpolation can carry out in the arbitrary steps of preparation dope, perhaps can be in the process of preparation dope be undertaken by increasing the step that these adjuvants are joined final preparation process.

It is Re that the cellulose acylate film that is preferred for first embodiment contains at least a optical anisotropy that can reduce _(λ)And Rth _(λ)Compound, the compound of the delay Rth of particularly at least a reduction film thickness direction, its amount satisfies following formula (I) and (II):

(I) (Rth (A)-Rth (0))/A≤-1.0 and

(II)0.01≤A≤30

Formula (I) and (II) preferably:

(I-a) (Rth (A)-Rth (0))/A≤-2.0 and

(II-a)0.05≤A≤25，

More preferably:

(I-b) (Rth (A)-Rth (0))/A≤-3.0 and

(II-b)0.1≤A≤20。

In the following formula, Rth (A) is the Rth (nm) of film of compound that contains the reduction Rth of A%, Rth (0) is the Rth (nm) that does not contain the film of the compound that reduces Rth, and A is the weight (%) based on the compound of 100 weight % of the raw polymer of film.

[reducing the architectural feature of the optically anisotropic compound of cellulose acylate film]

Explained later reduces the optically anisotropic compound of cellulose acylate film.Through further investigation; inventors of the present invention use following compound: described compound can suppress the arrangement of film inner cellulose acylate along direction in the face and film thickness direction, fully reduces optical anisotropy thus and makes that Re value and Rth value can be near 0.For this reason, reduce optically anisotropic compound can be fully compatible with cellulose acylate and compound itself not have club shaped structure or planar structure be useful.Particularly, have a plurality of planar functional groups for example under the situation of aromatic group at compound, compound has and do not have the non-planar structure of described functional group on identical faces is useful.

(Log P value)

When preparing the cellulose acylate film of first embodiment; suppressing film inner cellulose acylate along in direction in the face and the optically anisotropic aforesaid compound of the abundant thus reduction of film thickness direction arrangement, the preferred octanol-compound of water distribution coefficient (log P value) in the scope of 0-7.Log P value is wanting in the compatibility with cellulose acylate above 7 compound, therefore is easy to produce white casse or forms powder in film.And log P value is high and may reduce the water proofing property of cellulose acylate film thus less than the water wettability of 0 compound.Log P value more preferably in the scope of 1-6, preferred especially 1.5-5.

Octanol-water distribution coefficient (log P value) can be measured by the flask osmosis (flask permeation method) described in Japan Industrial Standards (JIS) Z7260-107 (2000).Replace practical measurement, also can estimate octanol-water distribution coefficient (log P value) by chemistry method or empirical method.As computing method, preferred Crippen ' s method (J.Chem.Inf.Comput.Sci. that breaks that uses, 27,21 (1987)), break method (J.Chem.Inf.Comput.Sci., 29 of Viswanadhan ' s, 163 (1989)) or Broto ' s method (Eur.J.Med.Chem.-Chim.Theor. that breaks, 19,71 (1984)) etc., more preferably use Crippen ' s method (J.Chem.Inf.Comput.Sci. that breaks, 27,21 (1987)).Under situation, preferably use Crippen ' s method of breaking to judge this compound whether within the scope of the invention according to determination method or the different log P of a kind of compound exhibits of computing method value.

[reducing the physical property of optically anisotropic compound]

Reduce that optically anisotropic compound can comprise or can not comprise aromatic group.The molecular weight that reduces optically anisotropic compound is 150-3000 preferably, more preferably 170-2000, preferred especially 200-1000.In the molecular weight of this scope, this compound can have the specific monomer structure or pass through a plurality of this monomeric units in conjunction with formed oligomer structure or polymer architecture.

Reducing optically anisotropic compound is that liquid or fusing point are 25 ℃-250 ℃ solid at 25 ℃ preferably, is that liquid or fusing point are 25 ℃-200 ℃ solid at 25 ℃ more preferably.Equally, reducing optically anisotropic compound does not preferably evaporate in the process of the dope that curtain coating and dry preparation cellulose acylate film are used.

The addition that reduces optically anisotropic compound is 0.01 quality %-30 quality % of cellulose acylate preferably, more preferably 1 quality %-25 quality %, preferred especially 5 quality %-20 quality %.Particularly, in the first embodiment, the optically anisotropic compound of at least a reduction preferably adds in the cellulose acylate that the acyl substituted degree is 2.85-3.00 with the amount of top scope.

Two or more the potpourri that reduces that optically anisotropic compound can use separately or can arbitrary proportion uses.

Reducing optically anisotropic compound can add in the random time in the process of preparation dope, perhaps can add when this process finishes.

Reducing optically anisotropic compound is the 80%-99% of this compound at the average content of cellulose acylate film core at the average content from the surface of cellulose acylate film at least to the part of 10% position of total film thickness.Reducing the amount of optically anisotropic compound can determine in the amount of surface portion and core by this compound of mensuration such as method that utilizes infrared absorption spectrum described in JP-A-8-5787.

Below, provide the instantiation of the optically anisotropic compound of the reduction cellulose acylate film that is preferred for first embodiment, but the compound that is used for first embodiment is not limited thereto.

Formula (1)

In formula (1), R ¹¹-R ¹³Representative independently of one another has the aliphatic group of 1-20 carbon atom.R ¹¹-R ¹³Can be connected with each other and form ring.

Formula (2) formula (3)

In formula (2) and (3), Z represent carbon atom, oxygen atom, sulphur atom or-NR ²⁵-, R wherein ²⁵Represent hydrogen atom or alkyl.The 5-or the 6-unit ring that comprise Z can contain substituting group.Y ²¹And Y ²²Represent ester group, alkoxy carbonyl, amide group or carbamyl independently of one another, wherein these groups have 1-20 carbon atom.A plurality of Y ²¹With a plurality of Y ²²Can form ring together separately.M is the integer of 1-5.N is the integer of 1-6.

In formula (4)-(12), Y ³¹-Y ⁷⁰Representative independently of one another has the ester group of 1-20 carbon atom, the alkoxy carbonyl with 1-20 carbon atom, the amide group with 1-20 carbon atom, the carbamyl with 1-20 carbon atom or hydroxyl.V ³¹-V ⁴³Represent hydrogen atom independently of one another or have the aliphatic group of a preferred 1-20 carbon atom.L ³¹-L ⁸⁰Representative independently of one another has the saturated bonding of divalence of 0-40 atom.Here, " L31-L80 with 0 atom " is meant that the group at the bonding two ends directly forms singly-bound.V ³¹-V ⁴³And L ³¹-L ⁸⁰Can also contain substituting group.

Formula (13)

In formula (13), R ¹Represent alkyl or aryl, and R ²And R ³Represent hydrogen atom, alkyl or aryl independently of one another.R ¹, R ²And R ³The total number of carbon atoms be 10 or bigger.Alkyl and aryl can have substituting group.

Formula (14)

In formula (14), R ⁴And R ⁵Represent alkyl or aryl independently of one another.R ⁴And R ⁵The total number of carbon atoms be 10 or bigger.Alkyl and aryl can have substituting group.

Formula (15)

In the above in the formula (15), R ¹, R ²And R ³Preferably be hydrogen atom or alkyl independently of one another.The divalent linker that X is made up of one or more groups that are selected from following linking group 1.Y is hydrogen atom, alkyl, aryl or aralkyl.R ⁴Be hydrogen atom, alkyl, aryl or aralkyl.

(linking group 1) singly-bound ,-O-,-CO-, alkylidene and arlydene.

Formula (16)

Q ¹, Q ²And Q ³Represent 5-or 6-unit ring independently of one another.X represents B, C-R (R represents hydrogen atom or substituting group), N, P and P=O.

Formula (17)

X wherein ²Represent B, C-R (R represents hydrogen atom or substituting group) and N.R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ³¹, R ³², R ³³, R ³⁴And R ³⁵Represent hydrogen atom or substituting group.

Formula (18)

In formula (18), R ¹Represent alkyl or aryl, and R ²And R ³Representative independently of one another

Hydrogen atom, alkyl or aryl.Alkyl and aryl can have substituting group.

The preferred compound of formula (18) is represented by following formula (19):

Formula (19)

In formula (19), R ⁴, R ⁵And R ⁶Represent alkyl or aryl independently of one another.Alkyl can be straight chain, cladodification or ring-type.The carbon number of alkyl is 1-20 preferably, more preferably 1-15, most preferably 1-12.Particularly preferred naphthenic base is a cyclohexyl.The carbon number of aryl is 6-36 preferably, more preferably 6-24.

Alkyl and aryl can have substituting group.Substituent preferred embodiment comprises halogen atom (for example chlorine atom, bromine atoms, fluorine atom and iodine atom), alkyl, aryl, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, sulfuryl amino, hydroxyl, cyano group, amino and acyl amino.Preferred example comprises halogen atom, alkyl, aryl, alkoxy, aryloxy group, sulfuryl amino and acyl amino.Particularly preferred example comprises alkyl, aryl, sulfo group amino and acyl amino.

The compound of formula (1) representative is described below.

Explain R in detail ¹¹-R ¹³R ¹¹-R ¹³Preferably has 1-20, more preferably 1-16 carbon atom, the especially preferably aliphatic group of 1-12 carbon atom.Here, aliphatic group is aliphatic hydrocarbyl preferably, and preferred alkyl (comprising straight chained alkyl, cladodification alkyl and naphthenic base), alkenyl or alkynyl.The example of alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl and dicyclo [2.2.2] octane-3-base etc.; The example of thiazolinyl comprises vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopentene-1-base and 2-cyclohexene-1-base etc.; The example of alkynyl comprises ethinyl, propargyl etc.

R ¹¹-R ¹³The aliphatic group of representative can be replacement or unsubstituted; and substituent example comprises halogen atom (fluorine atom; the chlorine atom; bromine atoms or iodine atom); alkyl (comprises straight chained alkyl; cladodification alkyl and naphthenic base; bicyclic alkyl; active methylene); thiazolinyl; alkynyl; aryl; heterocyclic radical (with substituted location independent); acyl group; alkoxy carbonyl; aryloxycarbonyl; the heterocyclic oxy group carbonyl; carbamyl; N-acyl group carbamyl; N-Herbicidal sulphonylamino formoxyl; N-carbamyl carbamyl; N-sulfamoyl carbamyl; carbazole acyl group (carbazoyl); carboxyl or its salt; oxalyl group; the oxamoyl base; cyano group; the carbonimidoyl base; formoxyl; hydroxyl; alkoxy (group that comprises repetitive) with ethyleneoxy or propenyloxy group unit; aryloxy group; heterocyclic oxy group; (alkoxy or aryloxy group) acyloxy; the ketonic oxygen base; carbamyl oxygen base; sulfonyl oxygen base; (alkyl; aryl or heterocycle) amino; amino; acyl amino; sulfoamido; urea groups; ghiourea group; (alkoxy or aryloxy group) imide; carbonylamino; sulfamoyl amino; amino urea groups; ammonium (ammonio); oxamoyl base amino; N-(alkyl or aryl) sulfonyl urea groups; N-acyl group urea groups; N-acyl group sulfamoyl amino; the heterocyclic radical that comprises quaternary nitrogen atoms (for example; pyridine radicals (pyridinio); pyrazolinyl (imidazolio); quinolyl (quinolinio); isoquinolyl (isoquinolinio)); isocyano group; (alkyl or aryl) imino group; (alkyl or aryl) sulfonyl; sulfinyl; sulfo group or its salt; sulfamoyl; N-acyl group sulfamoyl; N-Herbicidal sulphonylamino sulfonyl or its salt, phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino and silicyl etc.

These groups can be connected with each other and form compound substituting group, and described substituent example comprises ethoxy ethoxy ethyl, hydroxyl ethoxy ethyl and ethoxy carbonyl ethyl etc.And, R ¹¹-R ¹³Can contain phosphate-basedly as substituting group, and the compound of formula (1) also can contain a plurality of phosphate-based at same molecule.

The compound of formula (1) representative is described below.

In formula (2) and (3), Z represent carbon atom, oxygen atom, sulphur atom or-NR ²⁵-, R wherein ²⁵Represent hydrogen atom or alkyl.The 5-or the 6-unit ring that comprise Z can contain substituting group, and a plurality of described substituting groups can be connected with each other and form ring.The example that comprises the 5-of Z or 6-unit ring comprises tetrahydrofuran, oxinane, thiophane, thiane, pyrrolidine, piperidines, xylylenimine, isoindoline, chroman, heterochromatic full, tetrahydrochysene-2-furanone (furanone), tetrahydrochysene-2-pyrone, 4-butyrolactam (butane lactam) and 6-caprolactam etc.

And, comprise the 5-of Z or the example of 6-unit ring and comprise lactones structure or lactams structure, that is, in the adjacent carbons of Z, have the cyclic ester or the cyclic amides structure of oxo group.The example of cyclic ester or cyclic amides structure comprises 2-Pyrrolidone, 2-piperidones, 5-valerolactone (pentanolide) and 6-caprolactone (hexanolide).

R ²⁵Represent hydrogen atom or have a preferred 1-20 carbon atom, more preferably 1-16 carbon atom, the especially preferably alkyl (comprising straight chained alkyl, cladodification alkyl and naphthenic base) of 1-12 carbon atom.R ²⁵The example of the alkyl of representative comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, 1-adamantyl, 2-adamantyl and dicyclo [2.2.2] octane-3-base etc.R ²⁵The alkyl of representative can also contain substituting group, and described substituent example comprises with regard to R ¹¹-R ¹³The cited example of substituting group.

Y ²¹-Y ²²Represent ester group, alkoxy carbonyl, amide group or carbamyl independently of one another.Ester can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises acetoxyl group, ethyl ketonic oxygen base, propyl group ketonic oxygen base, normal-butyl ketonic oxygen base, isobutyl ketonic oxygen base, tert-butyl group ketonic oxygen base, sec-butyl ketonic oxygen base, n-pentyl ketonic oxygen base, tertiary pentyl ketonic oxygen base, n-hexyl ketonic oxygen base, the cyclohexyl-carbonyl oxygen base, 1-ethyl pentyl group ketonic oxygen base, n-heptyl ketonic oxygen base, n-nonyl ketonic oxygen base, n-undecane base ketonic oxygen base, benzyloxycarbonyl group oxygen base, 1-naphthalene ketonic oxygen base, 2-naphthalene ketonic oxygen base and 1-diamantane ketonic oxygen base etc.

Alkoxy carbonyl can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the n-butoxy carbonyl, tert-butoxycarbonyl, isobutoxy carbonyl, the sec-butoxy carbonyl, the n-pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl, 2-ethyl-hexyl-hydroxycarbonyl group, 1-ethyl propoxycarbonyl, the n-octyloxy carbonyl, 3,7-dimethyl-3-carbonyl octyloxy, 3,5, the positive hexyloxy carbonyl of 5-trimethyl, 4-tert-butyl group cyclohexyloxy carbonyl, 2,4-dimethyl amyl group-3-oxygen base carbonyl, 1-Buddha's warrior attendant alkoxy carbonyl, 2-Buddha's warrior attendant alkoxy carbonyl, dicyclopentadienyl oxygen base carbonyl, the n-decyloxy carbonyl, n-dodecane oxygen base carbonyl, n-tetradecane oxygen base carbonyl and n-hexadecane oxygen base carbonyl etc.

Amide group can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises acetamide, buserelin (ethylcarboxamide), the n-pro-pyl acid amides, the isopropyl acid amides, the normal-butyl acid amides, tert-butylamides, the isobutyl acid amides, the sec-butyl acid amides, the n-pentyl acid amides, te t-amylamide, the n-hexyl acid amides, cyclohexyl amide, 1-ethyl pentyl group acid amides, 1-ethyl propyl acid amides, the n-heptyl acid amides, the n-octyl acid amides, 1-diamantane acid amides, 2-diamantane acid amides, the n-nonyl acid amides, the dodecyl acid amides, n-pentadecane base acid amides and n-hexadecyl acid amides etc.

Carbamyl can preferably have 1-20 carbon atom; more preferably 1-16 carbon atom; preferred especially 1-12 carbon atom, and the example comprises the methyl carbamyl; the dimethylamino formoxyl; the ethyl carbamyl; the diethyl amino formoxyl; the n-pro-pyl carbamyl; the isopropyl carbamyl; the normal-butyl carbamyl; tert-butyl group carbamyl; the isobutyl carbamyl; the sec-butyl carbamyl; the n-pentyl carbamyl; the tertiary pentyl carbamyl; the n-hexyl carbamyl; the cyclohexyl carbamyl; 2-ethylhexyl carbamyl; 2-ethyl-butyl carbamyl; uncle's octyl group carbamyl; the n-heptyl carbamyl; the n-octyl carbamyl; 1-diamantane carbamyl; 2-diamantane carbamyl; positive decyl carbamyl; the dodecyl carbamyl; n-tetradecane base carbamyl and n-hexadecyl carbamyl etc.Y ²¹-Y ²²Can be connected with each other and form ring.Y ²¹-Y ²²Can also contain substituting group, and described substituent example comprises with regard to R ¹¹-R ¹³Cited those of substituting group.

The compound of formula (4)-(12) is described below.

In formula (4)-(12), Y ³¹-Y ⁷⁰Represent ester group, alkoxy carbonyl, amide group, carbamyl or hydroxyl independently of one another.Ester group can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises acetoxyl group, ethyl ketonic oxygen base, propyl group ketonic oxygen base, normal-butyl ketonic oxygen base, isobutyl ketonic oxygen base, tert-butyl group ketonic oxygen base, sec-butyl ketonic oxygen base, n-pentyl ketonic oxygen base, tertiary pentyl ketonic oxygen base, n-hexyl ketonic oxygen base, the cyclohexyl-carbonyl oxygen base, 1-ethyl pentyl group ketonic oxygen base, n-heptyl ketonic oxygen base, n-nonyl ketonic oxygen base, n-undecane base ketonic oxygen base, benzyloxycarbonyl group oxygen base, 1-naphthalene ketonic oxygen base, 2-naphthalene ketonic oxygen base and 1-diamantane ketonic oxygen base etc.

Alkoxy carbonyl can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises 1-ethyl propoxycarbonyl, carbonyl octyloxy, 3,7-dimethyl-3-carbonyl octyloxy, 3,5,5-trimethyl hexyloxy carbonyl, 4-tert-butyl group cyclohexyloxy carbonyl, 2,4-dimethyl amyl group-3-oxygen base carbonyl, 1-Buddha's warrior attendant alkoxy carbonyl, 2-Buddha's warrior attendant alkoxy carbonyl, dicyclopentadienyl oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl, dodecyloxy carbonyl, the tetradecyloxyaniline carbonyl, hexadecane oxygen base carbonyl has provided methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the n-butoxy carbonyl, tert-butoxycarbonyl, isobutoxy carbonyl, the sec-butoxy carbonyl, the n-pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, cyclohexyloxy carbonyl and 2-ethyl-hexyl-hydroxycarbonyl group etc.

Amide group can preferably have 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom, and the example comprises acetamide, buserelin, the n-pro-pyl acid amides, the isopropyl acid amides, the normal-butyl acid amides, tert-butylamides, the isobutyl acid amides, the sec-butyl acid amides, the n-pentyl acid amides, te t-amylamide, the n-hexyl acid amides, cyclohexyl amide, 1-ethyl-amyl group acid amides, 1-ethyl propyl acid amides, the n-heptyl acid amides, the n-octyl acid amides, 1-diamantane acid amides, 2-diamantane acid amides, the n-nonyl acid amides, the dodecyl acid amides, pentadecyl acid amides and n-hexadecyl acid amides etc.

Carbamyl can preferably have 1-20 carbon atom; more preferably 1-16 carbon atom; preferred especially 1-12 carbon atom, and the example comprises the methyl carbamyl; the dimethylamino formoxyl; the ethyl carbamyl; the diethyl amino formoxyl; the n-pro-pyl carbamyl; the isopropyl carbamyl; the normal-butyl carbamyl; tert-butyl group carbamyl; the isobutyl carbamyl; the sec-butyl carbamyl; the n-pentyl carbamyl; the tertiary pentyl carbamyl; the n-hexyl carbamyl; the cyclohexyl carbamyl; 2-ethylhexyl carbamyl; 2-ethyl-butyl carbamyl; uncle's octyl group carbamyl; the n-heptyl carbamyl; the n-octyl carbamyl; 1-diamantane carbamyl; 2-diamantane carbamyl; positive decyl carbamyl; the dodecyl carbamyl; n-tetradecane base carbamyl and n-hexadecyl carbamyl etc.Y ³¹-Y ⁷⁰Can also contain substituting group, and described substituent example comprises with regard to R ¹¹-R ¹³Cited those of substituting group.

V ³¹-V ⁴³Represent hydrogen atom independently of one another or have a preferred 1-20 carbon atom, more preferably 1-16 carbon atom, the especially preferably aliphatic group of 1-12 carbon atom.Here, aliphatic group is aliphatic hydrocarbyl preferably, more preferably alkyl (comprising straight chained alkyl, cladodification alkyl and naphthenic base), alkenyl or alkynyl.The example of alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, suberyl, 2,6-Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl and dicyclo [2.2.2] octane-3-base etc.; The example of thiazolinyl comprises vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopentene-1-base and 2-cyclohexene-1-base etc.; And the example of alkynyl comprises ethinyl and propargyl etc.V ³¹-V ⁴³Can also contain substituting group, and described substituent example comprises with regard to R ¹¹-R ¹³Cited those of substituting group.

L ³¹-L ⁸⁰Representative independently of one another has the saturated bonding of divalence of 0-40 atom.Here, this instructions, " L31-L80 with 0 atom " are meant that the group at the two ends of bonding directly forms singly-bound.L ³¹-L ⁷⁷Preferred embodiment comprise that alkylidene (for example, methylene, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, methyl ethylidene and ethyl ethylidene etc.), the ring divalent group (for example, cis-1,4-cyclohexylidene, anti-form-1,4-cyclohexylidene and 1,3-cyclopentylene etc.), ether, thioether, ester, acid amides, sulfone, sulfoxide, sulfide, sulfonamide, urylene and sulfo-urylene etc.Compound substituent example comprises-(CH ₂) ₂O (CH ₂) ₂-,-(CH ₂) ₂O (CH ₂) ₂O (CH ₂)-,-(CH ₂) ₂S (CH ₂) ₂-and-(CH ₂) ₂O ₂C (CH ₂) ₂-etc.L ³¹-L ⁸⁰Can also contain substituting group, and described substituent example comprises with regard to R ¹¹-R ¹³Cited those of substituting group.

Y ³¹-Y ⁷⁰, V ³¹-V ⁴³And L ³¹-L ⁸⁰The preferred embodiment of the compound that is combined to form comprises that citric acid ester type (for example; citric acid-O-acetyl group triethyl; citric acid-O-acetyl group tributyl; acetyl triethyl citrate; acetyl tributyl citrate and citric acid-O-acetyl group three (ethoxy carbonyl methylene) ester etc.); the oleate class (for example; ethyl oleate; butyl oleate; oleic acid-2-Octyl Nitrite; the oleic acid phenyl ester; oleic acid cyclohexyl and oleic acid monooctyl ester etc.); the monoricinolein class (for example; acetyl group methyl ricinoleate etc.); sebacic acid ester (for example; dibutyl sebacate etc.); the glycerine carboxylic acid esters (for example; glyceryl triacetate; tributyrin etc.); the glycolate class (for example; butyl benzene diformyl Glycolic acid butyl ester; ethylbenzene diformyl Glycolic acid ethyl ester; dimethylamino methyl phenyl acyl group Glycolic acid ethyl ester; dimethylamino methyl phenyl acyl group Glycolic acid methyl esters; propylbenzene diformyl Glycolic acid propyl ester; with octyl group phenyl-diformyl base Glycolic acid monooctyl ester etc.); the carboxylic acid esters of pentaerythrite (for example; tetraacethyl pentaerythritol ester etc.); the carboxylic acid esters of dipentaerythritol (for example; six acetate dipentaerythritol ester; six butyric acid dipentaerythritol ester and tetraacethyl dipentaerythritol ester etc.); the carboxylic acid esters of trimethylolpropane (triacetic acid trihydroxymethylpropanyl ester; the oxalic acid trihydroxymethylpropanyl ester; one propionic acid trihydroxymethylpropanyl ester; three propionic acid trihydroxymethylpropanyl esters; three butyric acid trihydroxymethylpropanyl esters; three neopentanoic acid trihydroxymethylpropanyl esters; three (butylacetic acid) trihydroxymethylpropanyl ester; trimethylolpropane two-2 ethyl hexanoic acid ester; trimethylolpropane four-2 ethyl hexanoic acid ester; oxalic acid one sad trihydroxymethylpropanyl ester; three sad trihydroxymethylpropanyl esters and three (cyclohexane-carboxylic acid) trihydroxymethylpropanyl ester etc.); glyceride type described in the JP-A 11-246704; double glyceride class described in the JP-A 2000-63560; citric acid ester type described in the JP-A 11-92574; 2-pyrrolidone-5-carboxylic acid's ester class (2-Pyrrolidone-5-carboxylate methyl ester; 2-Pyrrolidone-5-carboxylic acid, ethyl ester; 2-Pyrrolidone-5-butyl carboxylate; 2-Pyrrolidone-5-carboxylic acid-2-Octyl Nitrite); cyclohexanedicarboxyester ester class (1; 2-cis-cyclohexane dicarboxylic acid dibutyl ester; anti-form-1; 2-cyclohexane dicarboxylic acid dibutyl ester; cis-1; 4-cyclohexane dicarboxylic acid dibutyl ester; anti-form-1,4-cyclohexane dicarboxylic acid dibutyl ester); xylitol carboxylic acid esters (the pentaacetic acid ester of xylitol; the tetraacethyl ester of xylitol; the five propionic acid esters of xylitol.

Below, provide the examples for compounds of the present invention that formula (1)-(12) are represented.With regard to formula (1), provide Compound C-1 to C-76, with regard to formula (2)-(12), provide Compound C-201 to C-231, C-401 to C-448.LogP value in the table or described in the bracket is measured (J.Chem.Inf.Comput.Sci., 27,21 (1987) according to Crippen ' s method of breaking.

R wherein ¹-R ³Has R with above-mentioned formula (1) ¹¹-R ¹³Identical implication, and its instantiation shows to C-76 with Compound C-1 below.

The compound of formula (13) and (14) is described below.

In formula (13), R ¹Represent alkyl or aryl, and R ²And R ³Represent hydrogen atom, alkyl or aryl independently of one another.And, R ¹, R ²And R ³The total number of carbon atoms especially preferably 10 or bigger.In formula (14), R ⁴And R ⁵Represent alkyl or aryl independently of one another.And, R ⁴And R ⁵The total number of carbon atoms be 10 or bigger, and R ⁴And R ⁵Alkyl separately and aryl can be substituted.Substituting group is fluorine atom, alkyl, aryl, alkoxy, sulfuryl and sulfoamido preferably, special preferred alkyl, aryl, alkoxy, sulfuryl and sulfoamido.And, alkyl can be straight chain, cladodification or ring-type, and preferably have a 1-25 carbon atom, more preferably 6-25 carbon atom, preferred especially 6-20 carbon atom (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, didecyl).Aryl preferably has 6-30 carbon atom, preferred especially 6-24 carbon atom (for example, phenyl, xenyl, terphenyl, naphthyl, binaphthyl, triphenyl phenyl).Provide the preferred embodiment of the compound of formula (13) or formula (14) representative below.

The compound of formula (15) is described below.

In formula (15), R ¹, R ²And R ³Preferred is hydrogen atom or the alkyl with 1-5 carbon atom (for example, methyl, ethyl, propyl group, isopropyl, butyl, amyl group and isopentyl) independently of one another, and R ¹, R ²And R ³In at least one especially preferably has the alkyl (for example, methyl, ethyl, propyl group and isopropyl) of 1-3 carbon atom.X preferably by one or more be selected from singly-bound ,-O-,-CO-, alkylidene (preferably have 1-6 carbon atom, more preferably 1-3 carbon atom; For example, methylene, ethylidene and propylidene) or arlydene (preferably have 6-24 carbon atom, more preferably 6-12 carbon atom; For example, phenylene, biphenylene and naphthylene) the divalent linker that constitutes of group, especially preferably be selected from-divalent linker that the group of O-, alkylidene or arlydene constitutes by one or more.Y preferably hydrogen atom, alkyl (preferably has 2-25 carbon atom, more preferably 2-20 carbon atom; For example, ethyl, isopropyl, the tert-butyl group, hexyl, 2-ethylhexyl, uncle's octyl group, dodecyl, cyclohexyl, dicyclohexyl and adamantyl), aryl (preferably has 6-24 carbon atom, more preferably 6-18 carbon atom; For example, phenyl, xenyl, terphenyl and naphthyl) or aralkyl (preferably have 7-30 carbon atom, more preferably 7-20 carbon atom; For example, benzyl, tolyl, tert-butyl-phenyl, diphenyl methyl and trityl group), special preferred alkyl, aryl or aralkyl.With regard to the combination of-X-Y, the total number of carbon atoms of-X-Y is 0-40 preferably, more preferably 1-30, most preferably 1-25.Provide the preferred embodiment of the compound of formula (15) representative below, but being used for compound of the present invention is not limited thereto.

The compound of formula (16) is described below.

Q ¹, Q ²And Q ³Represent 5-or 6-unit ring independently of one another, described ring can be heterocyclic hydrocarbon ring, monocyclic hydrocarbon ring, and can form fused rings with other ring.The hydrocarbon ring preferably replaces or unsubstituted cyclohexane ring, replacement or unsubstituted cyclopentane ring, aromatic hydrocarbon ring, more preferably aromatic hydrocarbon ring.Heterocycle preferably 5-or 6-unit ring contain at least a ring that is selected from oxygen atom, nitrogen-atoms and the sulphur atom, more preferably contain at least a aromatic heterocycle that is selected from oxygen atom, nitrogen-atoms or the sulphur atom.

Q ¹, Q ²And Q ³Preferably aromatic hydrocarbon ring or aromatic heterocycle.The aromatic hydrocarbon ring preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus etc.) of 6-30 carbon atom; The aromatic hydrocarbon ring that more preferably has 6-20 carbon atom; Even more preferably has an aromatic hydrocarbon ring of 6-12 carbon atom; Especially preferred phenyl ring.

Aromatic heterocycle preferably contains the aromatic heterocycle of oxygen atom, nitrogen-atoms or sulphur atom.The instantiation of heterocycle comprises furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzotriazole, the purine (tetrazaindene) etc.The preferred embodiment of aromatic heterocycle has pyridine, triazine and quinoline.Q ¹, Q ²And Q ³Preferably aromatic hydrocarbon ring, more preferably phenyl ring.Q ¹, Q ²And Q ³Can be substituted, and substituting group can be illustrated by following substituting group T.

X represents B, C-R (R represents hydrogen atom or substituting group), N, P and P=O.X preferably B, C-R (R is aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, acyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino, hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom) and carboxyl preferably; More preferably aryl, alkoxy, aryloxy group, hydroxyl and halogen atom; Even more preferably alkoxy and hydroxyl; Preferred hydroxyl) and N especially.X is more preferably C-R and N, preferred especially C-R.

The compound of formula (16) representative is the compound of formula (17) representative preferably.

In formula (17), X ²Represent B, C-R (R represents hydrogen atom or substituting group) and N.R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ³¹, R ³², R ³³, R ³⁴And R ³⁵Represent hydrogen atom or substituting group.

X represents B, C-R (R represents hydrogen atom or substituting group), N, P and P=O.X preferably B, C-R (R is aryl, replacement or unsubstituted amino, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, acyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino, hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom) and carboxyl preferably; More preferably aryl, alkoxy, aryloxy group, hydroxyl and halogen atom; Even more preferably alkoxy and hydroxyl; Especially preferred hydroxyl), N and P=O.X is more preferably C-R and N, preferred especially C-R.

R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ³¹, R ³², R ³³, R ³⁴And R ³⁵Represent hydrogen atom or substituting group, and this substituting group can illustrate with following substituting group T.R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ³¹, R ³², R ³³, R ³⁴And R ³⁵Alkyl preferably, thiazolinyl, alkynyl, aryl, replace or unsubstituted amino, alkoxy, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, acyloxy, acyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfuryl amino, sulfamoyl, carbamyl, alkylthio group, arylthio, sulfonyl, sulfinyl, urea groups, the phosphoamide base, hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, the chlorine atom, bromine atoms and iodine atom), cyano group, sulfo group, carboxyl, nitro, the hydroxamic acid base, sulfino, diazanyl, imino group, heterocyclic radical (preferably has more preferably 1-12 carbon atom of 1-30 carbon atom, and has heteroatoms such as nitrogen-atoms, oxygen atom or sulphur atom; Particularly, for example, imidazole radicals, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl etc.), silicyl; More preferably alkyl, aryl, replacement or unsubstituted amino, alkoxy and aryloxy group; Even more preferably alkyl, aryl and alkoxy.

These substituting groups can also be substituted.When two or more substituting group, they can be identical or different.If possible, they can be connected with each other and form ring.

Above-mentioned substituting group T is described below.The example of substituting group T comprises that alkyl (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, especially preferably 1-8 carbon atom; For example, methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, especially preferably 2-8 carbon atom; For example, vinyl, allyl, 2-butenyl group, 3-pentenyl etc.), alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, preferred especially 2-8 carbon atom; For example, propargyl, 3-pentynyl etc.), aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom, preferred especially 6-12 carbon atom; For example, phenyl, p-methylphenyl, naphthyl etc.), replacement or unsubstituted amino (preferably has 0-20 carbon atom, more preferably 0-10 carbon atom, preferred especially 0-6 carbon atom; For example, amino, methylamino, dimethylamino, diethylamino, dibenzyl amino etc.), alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, preferred especially 1-8 carbon atom; For example, methoxyl, ethoxy, butoxy etc.), aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, phenoxy group, 2-naphthoxy etc.), acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, acetyl group, benzoyl, formoxyl, valeryl etc.), alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, preferred especially 7-10 carbon atom; For example, phenyloxycarbonyl etc.), acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, especially preferably 2-10 carbon atom; For example, acetoxyl group, benzoyloxy etc.), acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-10 carbon atom; For example, acetyl-amino, benzoyl-amido etc.), alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl amino etc.), aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, especially preferably 7-12 carbon atom; For example, phenyloxycarbonyl amino etc.), sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl amino, benzenesulfonyl amino etc.), (preferably have 0-20 carbon atom, more preferably 0-16 carbon atom especially preferably has 0-12 carbon atom to sulfamoyl; For example, sulfamoyl, methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base etc.), carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, carbamyl, methyl carbamyl, diethyl amino formoxyl, phenylamino formoxyl etc.), alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methyl mercapto, ethylmercapto group etc.), arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, thiophenyls etc.), sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl, tosyl etc.), sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methanesulfinyl, phenylsulfinyl base etc.), urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, urea groups, methyl urea groups, phenyl urea groups etc.), the phosphoamide base (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, diethyl phosphoamide, phosphenylic acid acid amides etc.), hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom), cyano group, sulfo group, carboxyl, nitro, hydroxamic acid base, sulfino, diazanyl, imino group, heterocyclic radical (preferably has 1-30 carbon atom, more preferably 1-12 carbon atom, and have heteroatoms for example nitrogen-atoms, oxygen atom or sulphur atom; Particularly, for example, imidazole radicals, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl etc.), silicyl (preferably has 3-40 carbon atom, more preferably 3-30 carbon atom, preferred especially 3-24 carbon atom; For example, trimethyl silyl, triphenyl silicyl etc.) etc.These substituting groups can also be substituted.When two or more substituting group, they can be identical or different.If possible, they can be connected with each other and form ring.

Provide the instantiation of the compound of formula (16) representative below, but being used for compound of the present invention is not limited thereto.

Provide the preferred embodiment of the compound of formula (18) or formula (19) representative below, but being used for compound of the present invention is not limited thereto.

Inventors of the present invention are through further investigation; even found that polyol ester compound, carbonate, many novel cycloalkenycarboxyliacid acids and bisphenol derivative (their octanol-water distribution coefficient (LogP value) is 0-7) are joined in the cellulose acylate that optical anisotropy also reduces.Provide the instantiation of octanol-water distribution coefficient (LogP value) below for the polyol ester compound of 0-7, carbonate, many novel cycloalkenycarboxyliacid acids and bisphenol derivative.

(polyol ester compound)

Octanol-water distribution coefficient (LogP value) is dibasic alcohol or more polyvalent alcohol and at least a monacid ester for the polyvalent alcohol of 0-7.Provide the polyol ester examples for compounds below, but being used for compound of the present invention is not limited thereto.

(polyvalent alcohol)

The preferred embodiment of polyvalent alcohol comprises ribitol, arabite, ethylene glycol, diglycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dibutylene glycol, 1,2,4-butantriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc.Preferred especially triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, D-sorbite, trimethylolpropane and xylitol.

(monoacid)

Monoacid in the polyol ester has no particular limits.Can use known aliphatic monoacid, alicyclic monoacid, fragrant monoacid etc.Preferably when using alicyclic monoacid and fragrant monoacid, improve water vapour permeability, moisture, the retentivity of cellulose acylate film.

Provide monacid preferred embodiment below, but being used for compound of the present invention is not limited thereto.

With regard to aliphatic monoacid, can use preferably to have 1-32 carbon atom, more preferably 1-20 carbon atom, the especially preferably straight chain or the cladodification aliphatic acid of 1-10 carbon atom.Because acetate improves the compatibility with cellulose esters, therefore preferably contain acetate.Also preferably use acetate and other monacid potpourri.

The monacid preferred embodiment of aliphatic series comprises saturated fatty acid for example acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-ethyl-cyclohexane carboxylic-acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid, nonadecylic acid, arachic acid, docosanoic acid, lignoceric acid, hexacosoic acid, carboceric acid, montanic acid, melissic acid, lacseric acid etc.; With unsaturated fatty acid for example undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid etc.They can also replace again.

Alicyclic monacid preferred embodiment comprises cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic acid or their derivant.

The monacid preferred embodiment of fragrance comprises that fragrant monoacid comprises benzoic acid, the acid of introducing alkyl in benzoic phenyl ring for example toluic acid, the fragrant monoacid for example biphenyl carboxylic acids, naphthalene-carboxylic acid and the tetralin carboxylic acid that comprise two or more phenyl ring, and their derivant.Preferred especially benzoic acid.

Carboxylic acid in the polyol ester of the present invention can use separately or two or more are used in combination.In addition, all the OH groups in the polyvalent alcohol can be esterified, and a part of OH group can former state exist.Preferably, in a molecule, can provide an aromatic rings or 3 or more cycloalkyl ring.

With regard to the polyol ester compound, can enumerate following compound, but being used for compound of the present invention is not limited thereto.

(carbonate)

For with regard to the carbonate of 0-7, can enumerate following compound with regard to octanol-water distribution coefficient (LogP value).Particularly, the example of carbonate comprises phthalic acid ester and citrate.The example of phthalic acid ester comprises rutgers, diethyl phthalate, dicyclo-hexyl phthlate, dioctyl phthalate and phthalic acid ethylhexyl.The example of citrate comprises acetyl triethyl citrate and acetyl tributyl citrate.In addition, the example of other carboxylic acid esters comprises butyl oleate, acetyl group methyl ricinoleate, dibutyl sebacate, glyceryl triacetate and three benzoic acid trihydroxymethylpropanyl esters.Also preferably alkyl benzene diformyl Glycolic acid Arrcostab is used for this purpose.The alkyl of alkyl benzene diformyl Glycolic acid Arrcostab is the alkyl of 1-8 carbon atom.The example of alkyl benzene diformyl Glycolic acid Arrcostab comprises dimethylamino methyl phenyl acyl group Glycolic acid methyl esters; ethylbenzene diformyl Glycolic acid ethyl ester; propylbenzene diformyl Glycolic acid propyl ester; butyl benzene diformyl Glycolic acid butyl ester; octyl group phenyl-diformyl base Glycolic acid monooctyl ester; dimethylamino methyl phenyl acyl group Glycolic acid ethyl ester; ethylbenzene diformyl Glycolic acid methyl esters; ethylbenzene diformyl Glycolic acid propyl ester; propylbenzene diformyl Glycolic acid ethyl ester; dimethylamino methyl phenyl acyl group Glycolic acid propyl ester; dimethylamino methyl phenyl acyl group Glycolic acid butyl ester; ethylbenzene diformyl Glycolic acid butyl ester; butyl benzene diformyl Glycolic acid methyl esters; butyl benzene diformyl Glycolic acid ethyl ester; propylbenzene diformyl Glycolic acid butyl ester; butyl benzene diformyl Glycolic acid propyl ester; dimethylamino methyl phenyl acyl group Glycolic acid monooctyl ester; ethylbenzene diformyl Glycolic acid monooctyl ester; octyl group phenyl-diformyl base Glycolic acid methyl esters and octyl group phenyl-diformyl base Glycolic acid ethyl ester.Preferably; can use dimethylamino methyl phenyl acyl group Glycolic acid methyl esters, ethylbenzene diformyl Glycolic acid ethyl ester, propylbenzene diformyl Glycolic acid propyl ester, butyl benzene diformyl Glycolic acid butyl ester and octyl group phenyl-diformyl base Glycolic acid monooctyl ester, especially preferably can use ethylbenzene diformyl Glycolic acid ethyl ester.And alkyl benzene diformyl Glycolic acid Arrcostab can two or more mix use.

Octanol-water distribution coefficient (LogP value) can illustrate by following compound for the example of the carbonate of 0-7, but being used for compound of the present invention is not limited thereto.

(porous carboxylic acid compound)

Octanol-water distribution the coefficient (LogP value) that is used for first embodiment for the porous carboxylic acid compound of 0-7 preferably molecular weight be 3000 or littler compound, special preferred molecular weight is the compound of 250-2000.As for ring texture, the preferred ring that forms by 3-8 atom, preferred especially 6-and/or 5-unit ring.Described ring can contain carbon, oxygen, nitrogen, sulphur or other atom, and a part of key of described ring can have unsaturated link, and for example, 6-unit ring can be phenyl ring or cyclohexane ring.Compound of the present invention is formed by a plurality of above-mentioned ring texturees.For example, compound can have any one in phenyl ring or the cyclohexane ring in molecule; Can have two cyclohexane rings; The derivant that perhaps can have naphthalene derivatives or anthracene or analog.More preferably, the compound that has three or more these ring texturees in molecule is preferred.And at least one key does not have unsaturated link in the preferred ring texture.Mentioned rosin acid derivative for example colophonic acid, dehydroabietic acid and parastric acid especially, provided their chemical formula below, but being used for compound of the present invention is not limited thereto.

(bisphenol derivative)

Be preferred for bisphenol derivative of the present invention and be molecular weight and be 10000 or littler compound, and in described scope, described compound can be monomer, oligomer or polymkeric substance.And described compound can be and the multipolymer of other polymkeric substance, perhaps can partly use the reactive substituents modification endways.Provide its chemical formula below, but being used for compound of the present invention is not limited thereto.

Be used for the instantiation of the octanol of first embodiment-water distribution coefficient (LogP value) for the bisphenol derivative of 0-7, R ¹-R ⁴Be hydrogen atom or alkyl independently of one another with 1-10 carbon atom.L, m and n are number of repeating units, and they have no particular limits.L, m and n be the integer of 1-100 preferably, more preferably the integer of 1-20.

[wavelength dispersion correctives]

In the first embodiment, the compound (this paper back is referred to as " dispersion adjustment agent ") that preferably will reduce the chromatic dispersion of cellulose acylate film joins in the film.

The dispersion adjustment agent is described below.

In the first embodiment, Re under the wavelength of 400nm and 700nm _(λ)And Rth _(λ)Poor, that is, | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Re ₍₄₀₀₎-Re ₍₇₀₀₎|, can reduce by adding compound, this compound has absorbance in the ultraviolet range of 200-400nm in case film is painted and can control the Re of film _(λ)And Rth _(λ)Chromatic dispersion.

In order to improve the chromatic dispersion of the Rth of cellulose acylate film in first embodiment, preferably add at least a compound, the chromatic dispersion of the Rth that this compound reduction following formula is (iv) represented, Δ Rth=|Rth ₍₄₀₀₎-Rth ₍₇₀₀₎|, condition be satisfy following formula (v) and (vi):

(iv)ΔRth＝|Rth ₍₄₀₀₎-Rth ₍₇₀₀₎|

(v)(ΔRth(B)-ΔRth(0))/B≤-2.0

(vi)0.01≤B ≤30；

More preferably following formula (v) and (vi) in the scope below:

(v-a)(ΔRth(B)-ΔRth(0))/B≤-3.0

(vi-a)0.05≤B≤25；

Even more preferably following formula (v) and (vi-b) in the scope below:

(v-b)(ΔRth(B)-ΔRth(0))/B≤-4.0

(vi-b)0.1≤B≤20。

Cellulose acylate film has such dispersion, and Re under longer wavelength and Rth value are usually greater than in the shorter wavelength side.Therefore, in order to increase relatively little Re and Rth, need make chromatic dispersion level and smooth in the shorter wavelength side.And the compound that has absorbance in the ultraviolet range of 200-400nm has in the absorbance of longer wavelength greater than the dispersion in the absorbance of shorter wavelength side.When described compound itself is present in the cellulose acylate film equably, suppose the birefringence of compound, that is, the chromatic dispersion of Re, Rth and absorbance are big in the shorter wavelength side.

As mentioned above, by using the compound that has absorbance at 200-400nm, and the chromatic dispersion of the Re of hypothesis compound itself and Rth is big in the shorter wavelength side, Re, Rth chromatic dispersion that so can controlling fiber element acylate film.Therefore, need the described compound of control chromatic dispersion fully and equably to be dissolved in the cellulose acylate.These compounds are at the absorbance scope of ultraviolet range 200-400nm preferably, more preferably 220-395nm, even more preferably 240-390nm.

Recently, for example in TV, laptop computer and the mobile cellular telephone, under less electric power, brightness increases at liquid crystal indicator.Therefore, need a kind of light element that is used for liquid crystal indicator and has excellent transmissivity (light element).In this, preferred compound has absorbance and reduction film in the ultraviolet range of 200-400nm | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎|, the cellulose acylate film that contains this compound has excellent spectral-transmission favtor.According to the cellulose acylate film of first embodiment, the spectral-transmission favtor under the wavelength of 380nm is 45%-95%; Yet, wish that the spectral-transmission favtor under the wavelength of 380nm is 10% or littler.

Therefore, the molecular weight that preferably is preferred for the dispersion adjustment agent of first embodiment in volatile angle is 250-1000.Be more preferably 260-800, in addition more preferably 270-800, preferred especially 300-800.Molecular weight is in these scopes, and the dispersion adjustment agent can be the form of specific monomer, or the oligomer that is formed by a plurality of bondings of monomeric unit or the form of polymkeric substance

Preferably in the dope curtain coating of cellulose acylate film preparation and dry run, do not emit the dispersion adjustment agent.

(addition of compound)

Relative cellulose acylate, the above-mentioned dispersion adjustment agent that is preferred for first embodiment is preferably added with the amount of 0.01-30 quality %, more preferably 0.1-20 quality %, especially preferably 0.2-10 quality %.

(adding method of compound)

And the dispersion adjustment agent can be used separately or two or more compounds are used in combination with arbitrary proportion.

Equally, the interpolation time of dispersion adjustment agent can be after the random time of dope preparation process or dope preparation process finish.

The instantiation that is preferred for dispersion adjustment agent of the present invention comprises the compound of benzotriazole cpd, benzophenone cpd, cyano-containing, oxidation of benzophenone (oxybenzophenone) compound, salicylate compound or nickel complex salt compound etc.

The example of the benzotriazole cpd that can preferably formula (101) be represented is as dispersion adjustment agent of the present invention, but the compound that can be used for first embodiment is not limited thereto.

Formula (101) Q ¹-Q ²-OH

Q wherein ¹Be nitrogenous aromatic heterocycle, Q ²It is aromatic rings.

Q ¹Be nitrogenous aromatic heterocycle, preferably represent the nitrogenous aromatic heterocycle of 5-to 7-unit, more preferably represent the nitrogenous aromatic heterocycle of 6-unit.The example comprises imidazoles, pyrazoles, triazole, tetrazolium, thiazole, oxazole, selenazoles, benzotriazole, benzothiazole, benzoxazole, benzo selenazoles, thiadiazoles, oxadiazole, aphthothiazoles, naphthalene and oxazole, azepine benzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, benzotriazole and the purine etc.More preferably, the nitrogenous aromatic heterocycle of 5-unit comprises imidazoles, pyrazoles, triazole, tetrazolium, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadiazoles, oxadiazole, preferred especially benzotriazole.

Q ¹The nitrogenous aromatic heterocycle of representative can also be substituted, and the preferably following substituting group T of substituting group.And, containing under a plurality of substituent situations at nitrogenous aromatic heterocycle, each substituting group can condensation form ring structure.

Q ²The aromatic rings of representative can be aromatic hydrocarbon ring or aromatic heterocycle.Equally, aromatic rings can be monocycle or can form fused rings with other ring.

The aromatic hydrocarbon ring preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus etc.) of 6-30 carbon atom, more preferably has the aromatic hydrocarbon ring of 6-20 carbon atom, even more preferably has the aromatic hydrocarbon ring of 6-12 carbon atom.Phenyl ring especially preferably.

Aromatic heterocycle preferably contains the aromatic heterocycle of nitrogen-atoms or sulphur atom.The instantiation of heterocycle comprises thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazines, naphthyridines (naphthylidine), quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzotriazole and the purine etc.The preferred embodiment of aromatic heterocycle comprises pyridine, triazine and quinoline.

Q ²The aromatic rings of representative is the aromatic hydrocarbon ring preferably, more preferably naphthalene nucleus or phenyl ring, especially preferably phenyl ring.Q ²Can also be substituted, and the preferably following substituting group T of substituting group.

The example of substituting group T comprises that alkyl (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, especially preferably 1-8 carbon atom; For example, methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, especially preferably 2-8 carbon atom; For example, vinyl, allyl, 2-butenyl group, 3-pentenyl etc.), alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, preferred especially 2-8 carbon atom; For example, propargyl, 3-pentynyl etc.), aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom, preferred especially 6-12 carbon atom; For example, phenyl, p-methylphenyl, naphthyl etc.), replacement or unsubstituted amino (preferably has 0-20 carbon atom, more preferably 0-10 carbon atom, preferred especially 0-6 carbon atom; For example, amino, methylamino, dimethylamino, diethylamino, dibenzyl amino etc.), alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, particularly 1-8 carbon atom; For example, methoxyl, ethoxy, butoxy etc.), aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, phenoxy group, 2-naphthoxy etc.), acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, acetyl group, benzoyl, formoxyl, valeryl etc.), alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, preferred especially 7-10 carbon atom; For example, phenyloxycarbonyl etc.), acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, especially preferably 2-10 carbon atom; For example, acetoxyl group, benzoyloxy etc.), acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-10 carbon atom; For example, acetyl-amino, benzoyl-amido etc.), alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl amino etc.), aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, especially preferably 7-12 carbon atom; For example, phenyloxycarbonyl amino etc.), sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl amino, benzenesulfonyl amino etc.), (preferably have 0-20 carbon atom, more preferably 0-16 carbon atom especially preferably has 0-12 carbon atom to sulfamoyl; For example, sulfamoyl, methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base etc.), carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, carbamyl, methyl carbamyl, diethyl amino formoxyl, phenylamino formoxyl etc.), alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methyl mercapto, ethylmercapto group etc.), arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, thiophenyls etc.), sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl, tosyl etc.), sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methanesulfinyl, phenylsulfinyl base etc.), urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, urea groups, methyl urea groups, phenyl urea groups etc.), the phosphoamide base (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, diethyl phosphoamide, phosphenylic acid acid amides etc.), hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom), cyano group, sulfo group, carboxyl, nitro, hydroxamic acid base, sulfino, diazanyl, imino group, heterocyclic radical (preferably has 1-30 carbon atom, more preferably 1-12 carbon atom, and have heteroatoms for example nitrogen-atoms, oxygen atom or sulphur atom; For example, imidazole radicals, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl etc.), silicyl (preferably has 3-40 carbon atom, more preferably 3-30 carbon atom, preferred especially 3-24 carbon atom; For example, trimethyl silyl, triphenyl silicyl etc.) etc.These substituting groups can also be substituted.When two or more substituting group, they can be identical or different.If possible, they can be connected with each other and form ring.

The compound of formula (101) representative is the compound of following formula (101-A) representative preferably:

Formula (101-A)

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Be hydrogen or substituting group independently of one another.

R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Represent hydrogen atom or substituting group independently of one another, and described substituting group can illustrate by above-mentioned substituting group T.These substituting groups can also replace with other substituting group, and described substituting group can condensation form 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, halogen atom; Even more preferably hydrogen atom, have the alkyl of 1-12 carbon atom; Especially preferably the alkyl (preferably having 4-12 carbon atom) that has 1-12 carbon atom.

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, halogen atom; Even more preferably hydrogen atom, have the alkyl of 1-12 carbon atom; Preferred especially hydrogen atom or methyl; 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, halogen atom; Even more preferably hydrogen atom, have the alkyl of 1-12 carbon atom; Preferred especially hydrogen atom or methyl; 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, halogen atom; Even more preferably hydrogen atom or halogen atom; Especially preferred hydrogen atom or chlorine atom.

The compound of formula (101) representative is the compound of following formula (101-B) representative preferably:

Formula (101-B)

R wherein ¹, R ³, R ⁶And R ⁷Have with formula (101-A) in identical implication, and identical in their preferable range and the formula (101-A).

Provide the instantiation of the compound of formula (101) representative below, but can be used for compound of the present invention is not limited thereto.

In the above in the benzotriazole cpd that provides in the example, consider the retentivity when making cellulose acylate film of the present invention, confirm not comprise molecular weight be 320 or littler compound be useful.

As another dispersion adjustment agent of the present invention, preferably use the benzophenone cpd of formula (102) representative:

Formula (102)

Q wherein ¹And Q ²Be aromatic rings independently of one another, and X is NR (wherein R is hydrogen atom or substituting group), oxygen atom or sulphur atom.

Q ¹And Q ²The aromatic rings of representative can be aromatic hydrocarbon ring or aromatic heterocycle.These substituting groups can be monocycles or can form fused rings with other ring.

Q ¹And Q ²The aromatic hydrocarbon ring of representative preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus etc.) of 6-30 carbon atom, more preferably has the aromatic hydrocarbon ring of 6-20 carbon atom, even more preferably has the aromatic hydrocarbon ring of 6-12 carbon atom.Phenyl ring especially preferably.

Q ¹And Q ²The aromatic heterocycle of representative preferably contains at least a aromatic heterocycle that is selected from oxygen atom, nitrogen-atoms and the sulphur atom.The instantiation of heterocycle comprises furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzotriazole and the purine etc.The preferred embodiment of aromatic heterocycle has pyridine, triazine and quinoline.

Q ¹And Q ²The aromatic rings of representative is the aromatic hydrocarbon ring preferably, more preferably has the aromatic hydrocarbon ring of 6-10 carbon atom, even more preferably replaces or unsubstituted phenyl ring.

Q ¹And Q ²Can also be substituted, and the preferably following substituting group T of substituting group.Yet described substituting group does not comprise carboxylic acid, sulfonic acid or quaternary ammonium salt.If possible, the described substituting group formation ring structure that can be connected with each other.

X is NR (wherein R is hydrogen atom or substituting group, and this substituting group can illustrate by following substituting group T), oxygen atom or sulphur atom.X is NR (wherein preferably acyl group or sulfonyl of R, and these substituting groups can also be substituted) or O preferably, preferred especially O.

The example of substituting group T comprises that alkyl (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, especially preferably 1-8 carbon atom; For example, methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, especially preferably 2-8 carbon atom; For example, vinyl, allyl, 2-butenyl group, 3-pentenyl etc.), alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, preferred especially 2-8 carbon atom; For example, propargyl, 3-pentynyl etc.), aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom, preferred especially 6-12 carbon atom; For example, phenyl, p-methylphenyl, naphthyl etc.), replacement or unsubstituted amino (preferably has 0-20 carbon atom, more preferably 0-10 carbon atom, preferred especially 0-6 carbon atom; For example, amino, methylamino, dimethylamino, diethylamino, dibenzyl amino etc.), alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, preferred especially 1-8 carbon atom; For example, methoxyl, ethoxy, butoxy etc.), aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, phenoxy group, 2-naphthoxy etc.), acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, acetyl group, benzoyl, formoxyl, valeryl etc.), alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, preferred especially 7-10 carbon atom; For example, phenyloxycarbonyl etc.), acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, especially preferably 2-10 carbon atom; For example, acetoxyl group, benzoyloxy etc.), acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-10 carbon atom; For example, acetyl-amino, benzoyl-amido etc.), alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl amino etc.), aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, especially preferably 7-12 carbon atom; For example, phenyloxycarbonyl amino etc.), sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl amino, benzenesulfonyl amino etc.), (preferably have 0-20 carbon atom, more preferably 0-16 carbon atom especially preferably has 0-12 carbon atom to sulfamoyl; For example, sulfamoyl, methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base etc.), carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, carbamyl, methyl carbamyl, diethyl amino formoxyl, phenylamino formoxyl etc.), alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methyl mercapto, ethylmercapto group etc.), arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, thiophenyls etc.), sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl, tosyl etc.), sulfinyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methanesulfinyl, phenylsulfinyl base etc.), urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, urea groups, methyl urea groups, phenyl urea groups etc.), the phosphoamide base (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, diethyl phosphoamide, phosphenylic acid acid amides etc.), hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms and iodine atom), cyano group, sulfo group, carboxyl, nitro, hydroxamic acid base, sulfino, diazanyl, imino group, heterocyclic radical (preferably has 1-30 carbon atom, more preferably 1-12 carbon atom, and have heteroatoms for example nitrogen-atoms, oxygen atom or sulphur atom; For example, imidazole radicals, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl etc.), silicyl (preferably has 3-40 carbon atom, more preferably 3-30 carbon atom, preferred especially 3-24 carbon atom; For example, trimethyl silyl, triphenyl silicyl etc.) etc.These substituting groups can also be substituted.When two or more substituting group, they can be identical or different.If possible, they can be connected with each other and form ring.

The compound of formula (102) representative is the compound of following formula (102-A) representative preferably:

Formula (102-A)

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Be 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, and described substituting group can illustrate by above-mentioned substituting group T.These substituting groups can also replace with other substituting group, and described substituting group can condensation form 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 separately; 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; Especially preferred hydrogen atom or methyl; 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; Especially preferably the alkoxy that has 1-12 carbon atom.

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, have the alkyl (preferably having 1-12 carbon atom, more preferably 1-8 carbon atom, even more preferably methyl) of 1-20 carbon atom; Especially preferable methyl or hydrogen atom.

The compound of formula (102) representative is more preferably the compound of following formula (102-B) representative:

Formula (102-B)

R wherein ¹⁰Be 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, and the substituting group on the aforementioned group can illustrate by 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, hexyl, 2-ethylhexyl, octyl group, decyl, dodecyl, benzyl etc.), preferred especially the replacement or unsubstituted alkyl (for example, 2-ethylhexyl, octyl group, decyl, dodecyl or benzyl) with 6-12 carbon atom.

The compound of formula (102) representative can be synthetic with the known method described in the JP-A11-12219.

Provide the instantiation of the compound of formula (102) representative below, but can be used for compound of the present invention is not limited thereto.

As being used for another dispersion adjustment agent of the present invention, preferably use the compound of the cyano-containing of formula (103) representative:

Q wherein ¹And Q ²Be aromatic rings independently of one another.X ¹And X ²Each is hydrogen atom or substituting group naturally, and at least one is cyano group, carbonyl, sulfonyl or aromatic heterocycle in them.Q ¹And Q ²Represented aromatic rings can be aromatic hydrocarbon ring or aromatic heterocycle.And they can be monocycles or can form fused rings with other ring.

The aromatic hydrocarbon ring preferably has the monocycle or the di-aromatics ring (for example, phenyl ring, naphthalene nucleus etc.) of 6-30 carbon atom, more preferably has the aromatic hydrocarbon ring of 6-20 carbon atom, even more preferably has the aromatic hydrocarbon ring of 6-12 carbon atom, preferred especially phenyl ring.

Aromatic heterocycle preferably contains the aromatic heterocycle of nitrogen-atoms or sulphur atom.The instantiation of heterocycle comprises thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiazole, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzoxazole, benzothiazole, benzotriazole and the purine etc.Aromatic heterocycle is pyridine, triazine or quinoline preferably.

Q ¹And Q ²Represented aromatic rings is the aromatic hydrocarbon ring preferably, more preferably phenyl ring.

Q ¹And Q ²Can also be substituted, and the substituting group T below preferred the use.The example of substituting group T comprises that alkyl (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, especially preferably 1-8 carbon atom; For example, methyl, ethyl, isopropyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl etc.), thiazolinyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, especially preferably 2-8 carbon atom; For example, vinyl, allyl, 2-butenyl group, 3-pentenyl etc.), alkynyl (preferably has 2-20 carbon atom, more preferably 2-12 carbon atom, preferred especially 2-8 carbon atom; For example, propargyl, 3-pentynyl etc.), aryl (preferably has 6-30 carbon atom, more preferably 6-20 carbon atom, preferred especially 6-12 carbon atom; For example, phenyl, p-methylphenyl, naphthyl etc.), replacement or unsubstituted amino (preferably has 0-20 carbon atom, more preferably 0-10 carbon atom, preferred especially 0-6 carbon atom; For example, amino, methylamino, dimethylamino, diethylamino, dibenzyl amino etc.), alkoxy (preferably has 1-20 carbon atom, more preferably 1-12 carbon atom, preferred especially 1-8 carbon atom; For example, methoxyl, ethoxy, butoxy etc.), aryloxy group (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, phenoxy group, 2-naphthoxy etc.), acyl group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, acetyl group, benzoyl, formoxyl, valeryl etc.), alkoxy carbonyl (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl, ethoxy carbonyl etc.), aryloxycarbonyl (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, preferred especially 7-10 carbon atom; For example, phenyloxycarbonyl etc.), acyloxy (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, especially preferably 2-10 carbon atom; For example, acetoxyl group, benzoyloxy etc.), acyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-10 carbon atom, for example, acetyl-amino, benzoyl-amido etc.), alkoxycarbonyl amino (preferably has 2-20 carbon atom, more preferably 2-16 carbon atom, preferred especially 2-12 carbon atom; For example, methoxycarbonyl amino etc.), aryloxycarbonyl amino (preferably has 7-20 carbon atom, more preferably 7-16 carbon atom, especially preferably 7-12 carbon atom; For example, phenyloxycarbonyl amino etc.), sulfuryl amino (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl amino, benzenesulfonyl amino etc.), sulfamoyl (preferably has 0-20 carbon atom, more preferably 0-16 carbon atom, preferred especially 0-12-carbon atom; Sulfamoyl, methyl sulfamoyl, dimethylamino sulfonyl, phenyl sulfamoyl base etc.), carbamyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, carbamyl, methyl carbamyl, diethyl amino formoxyl, phenylamino formoxyl etc.), alkylthio group (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methyl mercapto, ethylmercapto group etc.), arylthio (preferably has 6-20 carbon atom, more preferably 6-16 carbon atom, preferred especially 6-12 carbon atom; For example, thiophenyls etc.), sulfonyl (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, especially preferably 1-12 carbon atom; For example, mesyl, tosyl etc.), sulfinyl (preferably has 1-20 carbon atom, more preferably has 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, methanesulfinyl, phenylsulfinyl base etc.), urea groups (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, urea groups, methyl urea groups, phenyl urea groups etc.), the phosphoamide base (preferably has 1-20 carbon atom, more preferably 1-16 carbon atom, preferred especially 1-12 carbon atom; For example, diethyl phosphoamide, phosphenylic acid acid amides etc.), hydroxyl, sulfydryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atoms, iodine atom), cyano group, sulfo group, carboxyl, nitro, hydroxamic acid base, sulfino, diazanyl, imino group, heterocyclic radical (preferably has more preferably 1-12 carbon atom of 1-30 carbon atom, and has heteroatoms for example nitrogen-atoms, oxygen atom or sulphur atom; For example, imidazole radicals, pyridine radicals, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl etc.), silicyl (preferably has 3-40 carbon atom, more preferably 3-30 carbon atom, preferred especially 3-24 carbon atom; For example, trimethyl silyl, triphenyl silicyl) etc.These substituting groups can also be substituted.When two substituting groups, they can be identical or different.If possible, these substituting groups can be connected with each other and form ring.

X ¹And X ²Be that hydrogen atom or substituting group and at least one group are cyano group, carbonyl, sulfonyl, aromatic heterocycle.X ¹And X ²The substituting group of representative can illustrate by above-mentioned substituting group T.In addition, X ¹And X ²The substituting group of representative can also be replaced by other substituting group, and X ¹And X ²Annulation can take place and form ring structure in each substituting group of representative.

X ¹And X ²Preferably 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; Especially preferred cyano group or alkoxy carbonyl (C (=O) OR (R be the alkyl with 1-20 carbon atom, aryl, reach their combination) with 6-12 carbon atom.

The compound of formula (103) representative is the compound of following formula (103-A) representative preferably:

Formula (103-A)

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Be hydrogen atom or substituting group independently of one another.X ¹And X ²Have with formula (103) in identical in identical implication and their preferable range and the formula (103).

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, and described substituting group can illustrate by above-mentioned substituting group T.These substituting groups can also replace with other substituting group, and annulation formation ring structure can take place described substituting group.

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 separately; 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; Especially preferred hydrogen atom or methyl; 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 separately; 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, have the alkyl of 1-12 carbon atom or have the alkoxy of 1-12 carbon atom; Especially preferred hydrogen atom.

The compound of formula (103) representative is more preferably the compound of following formula (103-B) representative:

Formula (103-B)

R wherein ³And R ⁸Have with formula (103-A) in identical implication and their preferable range and formula (103-A) in identical.X ³Represent hydrogen atom or substituting group.

X ³Represent hydrogen atom or substituting group, and described substituting group can illustrate by above-mentioned substituting group T.If possible, described substituting group can also replace with 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; Especially preferred cyano group or alkoxy carbonyl (C (=O) OR (R be the alkyl with 1-20 carbon atom, aryl, reach their combination) with 6-12 carbon atom.

The compound of formula (103) representative is more preferably the compound of following formula (103-C) representative:

Formula (103-C)

R wherein ³And R ⁸Have with formula (103-A) in identical implication and their preferable range and 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, preferred especially octyl group, uncle's octyl group, 2-ethylhexyl, decyl or dodecyl, most preferably 2-ethylhexyl.

Work as R ³And R ⁸When being not hydrogen atom, the molecular weight of the compound of formula (103-C) representative is 300 or bigger, and R ²¹Preferably have 20 or the alkyl of carbon atom still less.

The compound of formula of the present invention (103) representative can pass through Journal of AmericanChemical Society, the 63rd volume, and the method described in the 3452nd page (1941) is synthetic.

Provide the instantiation of the compound of formula (103) representative below, but can be used for compound of the present invention is not limited thereto.

[particulate of matting agent]

The cellulose acylate film of preferred first embodiment contains particulate as matting agent.The example that can be used for the particulate of first embodiment 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.Because siliceous particulate has low turbidity, therefore preferred it.Preferred especially silicon dioxide.The average primary particle diameter of the particulate of preferred silicon dioxide is that 20nm or littler and apparent specific gravity are 70g/l or bigger.The particulate that more preferably has the little average primary particle diameter of 5-16nm, this is owing to can reduce the mist degree of gained film thus.Apparent specific gravity is 90-200g/l or bigger preferably, more preferably 100-200g/l or bigger.Higher apparent proportion can make the higher dispersion of concentration, improves mist degree and gathering thus.

It often is the secondary granule of 0.1-3.0 μ m that these particulates form mean grain size.In film, these particulates exist with the aggregation of primary granule and provide 0.1-3.0 μ the degree of irregularity of m at film surface.Preferred average secondary particle diameter 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.Primary particle diameter or secondary particle diameter are to determine as particle diameter by the particle in the viewing film under scanning electron microscope and with its external diameter of a circle.Observe 200 particles of diverse location and with its mean value as mean grain size.

As the particulate of silicon dioxide, can use commercially available prod for example AEROSIL R972, R972V, R974, R812,200,200V, 300, R202, OX50 and TT600 (all be by Dehussa Japan Co., Ltd. makes).As the particulate of Zirconium oxide, can use the commercially available prod, for example trade name AEROSIL R976 and R811 (all be by DehussaJapan Co., Ltd. makes).

In these products, preferred especially AEROSIL 200V and AEROSIL R972V, this is because their to be average primary particle diameter be 20nm or littler and apparent specific gravity are 70g/l or bigger and produce and reduce friction factor greatly simultaneously with the fine particles of silica of the effect of the turbidity of low-level maintenance optical thin film.

In order to obtain to have the cellulose acylate film of little average secondary size particles, some technologies can be proposed in the preparation process of particulate dispersion of the present invention.For example, under agitation particulate and solvent are obtained the particulate dispersion in advance.Then this particulate dispersion is added in the cellulose acylate solution that has made separately on a small quantity and also under agitation be dissolved in wherein.And then mix with main cellulose acylate dope.Cause the angle that fine particles of silica seldom reassociates simultaneously from the fine particles of silica that obtains polymolecularity, this is a kind of preferred manufacturing procedure.Another method comprises the plain ester of small amount of fibers is joined in the solvent, under agitation with its dissolving, to wherein adding particulate, in dispersion machine, disperse particulate to obtain the particulate additive solution then, in the on-line mixing device, the particulate additive solution is fully mixed with dope then.Although the present invention is not limited to these methods, fine particles of silica in solvent for example, mix and the step of disperseing in the concentration of preferred Si oxide at 5-30 weight %, preferred 10-25 weight % is most preferably in the scope of 15-20 weight %.Preferred higher dispersion concentration, this is because corresponding to described addition, solution turbidity reduces and improve thus mist degree and gathering.The final content of cellulose acylate in dope is preferably at 0.01-1.0g/m ²Scope in, more preferably 0.03-0.3g/m ², 0.08-0.16g/m most preferably ²

The preferred embodiment that can be used as the lower alcohol of solvent comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and butanols.As the solvent except that lower alcohol, preferred use already used solvent in forming cellulose ester film.

[plastifier, anti-degradation, release agent]

The cellulose acylate film of first embodiment; except optically anisotropic compound of above-mentioned reduction and dispersion adjustment agent; can also comprise various adjuvants (for example plastifier, UV resistant agent, anti-degradation, release agent and infrared absorbent), they can add in preparation process and can be solid or oily mater according to purpose.In other words, its boiling point and fusing point have no particular limits.For example, described in JP-A2001-151901, can be at 20 ℃ or lower or under 20 ℃ or higher temperature, mix ultraviolet absorption material, and mixed plasticizer.The infrared ray absorbing dyestuff has equally for example been described in JP-A 2001-194522.Can add in any time in the dope preparation process equally, perhaps add by in the last preparation process of this process, adding the step of adding adjuvant.Same is under the situation about being formed by multilayer at cellulose acylate film, and the type of adjuvant can be different with amount in each layer.These are known technologies, described in JP-A2001-151902.With regard to these technology, the preferred Japan Institute of Invention and Innovation that uses, Journal ofTechnical Disclosure (Technical Publication No.2001-1745, the 16-22 page or leaf, on March 15 calendar year 2001, Japan Institute of Invention and Innovation publishes) the middle material of describing in detail.

[adding proportion of compound]

In the cellulose acylate film of first embodiment, with respect to the weight of cellulose acylate, molecular weight is 3,000 or the total amount of littler compound 5-45% preferably, more preferably 10-40%, even more preferably 15-30%.These compounds comprise the optically anisotropic compound of aforesaid reduction, dispersion adjustment agent, UV resistant agent, plastifier, anti-degradation, particulate, release agent and infrared absorbent etc., and molecular weight is preferably 3,000 or littler, more preferably 2,000 or littler, even more preferably 1,000 or littler.When the total amount of these compounds is 5% or more hour, be tending towards only presenting the performance of cellulose acylate, this causes optical property and physical strength fluctuation when temperature and humidity changes.And the total amount of these compounds can surpass the limit of the solubleness of these compounds in cellulose acylate film greater than 45%, so causes precipitating and causing on film surface the white turbidity (oozing out from film) of film.

[organic solvent of cellulose acylate solution]

In the first embodiment, cellulose acylate film is preferably by the solvent cast method, and the utilization solution (dope) that the dissolving cellulos acylate makes in organic solvent makes.Being used for primary solvent of the present invention is preferably selected from ester, ketone and has the ether of 3-12 carbon atom and have the halogenated hydrocarbons of 1-7 carbon atom.Ester, ketone or ether can have ring structure.Also can use functional group with two or more esters, ketone or ether (promptly-O-,-CO-or-COO-) compound is as primary solvent, and can have another functional group such as alcoholic extract hydroxyl group.In having the primary solvent of two or more functional groups, the carbon atom number of this solvent can remain in the defined scope of compound that has in these functional groups any one relatively.

When the cellulose acylate film of preparation first embodiment; the halogenated hydrocarbons that can use the chlorine class is as primary solvent; perhaps can use non-chlorine solvent as primary solvent; as JapanInstitute of Invention and Innovation; Journal of Technical Disclosure; Technical Publication No.2001-1745 is described in the 12-16 page or leaf.

The solvent of cellulose acylate solution of the present invention and film; comprise dissolving method, be described in following patent documentation: 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 and 11-60752 as preferred implementation.These patent documentations have not only been described the solvent that is preferred for cellulose acylate of the present invention, and have described the performance of its solution and the material of existence, and also constitute preferred implementation of the present invention.

[preparation method of cellulose acylate film]

[dissolution method]

When the cellulose acylate film of preparation first embodiment, the solution of cellulose acylate (dope) is not limited to dissolution method, and can make in room temperature or by hot-cold lysis method or high-temperature digestion method or their combination.With regard to the preparation method of the cellulose acylate solution of first embodiment relevant and solution with dissolving method concentrate and filter method with regard to; can preferably use Japan Institute of Invention and Innovation; Journal of TechnicalDisclosure (Technical Publication No.2001-1745; the 22-25 page or leaf; on March 15 calendar year 2001, Japan Institute of Invention and Innovation publishes) the middle preparation method who describes in detail.

(transparency of dope)

In the first embodiment, cellulose acylate solution preferably has preferred 85% or higher, and more preferably 88% or higher, more preferably 90% or higher dope transparency.Confirm that various adjuvants fully are dissolved in the cellulose acylate solution (dope) of first embodiment.With regard to the concrete computing method of dope transparency, dope is full of 1cm ²Glass cell and measure absorbance under the 550nm with spectrophotometer (UV-3150, by Shimadzu Corporation make).The absorbance of measuring solvent in advance is as blank, and calculated the transparency of cellulose acylate by the ratio with the absorbance of blank.

[curtain coating, drying and turn-up process]

Next, the method for using cellulose acylate formulations prepared from solutions film of the present invention is described below.The cellulose acylate film of first embodiment can be according to solution casting method and solution casting apparatus by being usually used in preparing the method and apparatus preparation of cellulose triacetate film.At first, the dope (cellulose acylate solution) that makes in the dissolving tank (jar) is preserved in head tank, froth breaking also finally makes.Then, through the quantitative gear pump of punching press type dope is delivered to pressurizing mold from outlet, described pump can be accurately, for example, according to revolution, quantitatively send dope, and from the metal fittings of pressurizing mold (seam), with dope equably curtain coating on the metal support of the curtain coating part of circular flow., near rotation pick-up point once fully not dry dope film (being referred to as former) is peeled off from metal support in metal support.Fixing with when keeping width in the former both sides with anchor clamps, shift former and be dried with stenter, the cylinder with drying equipment shifts former continuously with abundant drying then, and rolls with predetermined length with up-coiler.The combination of the cylinder of stenter and drying equipment can change with purpose.Except solution casting apparatus,, also can use coating apparatus for for example processing of internal coating, antistatic layer, anti-dizzy layer and protective seam of film surface is provided.This is described in detail in Laid-open Technical Report, 25-30 page or leaf (No.2001-1745, March 15 calendar year 2001, Japan Institute ofInvention and Innovation) and be divided into curtain coating (comprising common curtain coating), metal support, drying and peel off, preferably use it for the present invention.The thickness of cellulose acylate film preferably in the scope of 10-120 μ m, more preferably 20-100 μ m, more preferably 30-90 μ m.

[variation of the optical property of film after the high humility processing]

[evaluation of the physical property of cellulose acylate film]

As for the variation of the cellulose acylate film of first embodiment with the optical property of environmental change; preferably handling 240 hours Re of film and the variation of Rth under 60 ℃ and 90%RH is 15nm or littler; more preferably 12nm or littler, more preferably 10nm or littler.[variation of the optical property of film after the pyroprocessing]

And, preferably handle 240 hours the Re of film and the variation of Rth is 15nm or littler, more preferably 12nm or littler, more preferably 10nm or littler at 80 ℃.

[amount of the compound of volatilization after the film thermal treatment]

With regard to compound of using with regard to the reduction Rth of the cellulose acylate film that can be preferred for first embodiment and the compound that reduces Δ Rth; be 30% or lower preferably from 80 ℃ of amounts of compound of handling 240 hours films volatilization; more preferably 25% or lower, more preferably 20% or lower.

And following evaluation is from the amount of the compound of film volatilization.Handling 240 hours film and untreated film with 80 ℃ is dissolved in the solvent respectively and uses the high performance liquid chromatography detection compound.Calculate the amount of residual compounds in the film by following equation with the peak area of compound.

Volatilization ratio (%)={ (amount of residual compound in the untreated prods)-(amount of residual compound in the treatment product)/(amount of residual compound in the untreated prods) x 100

[the glass temperature Tg of film]

The glass temperature Tg of the cellulose acylate film of first embodiment is 80-165 ℃.From stable on heating angle, preferably 100-160 ℃ of Tg, more preferably 110-150 ℃.Glass temperature Tg ℃ measures with intensification and the cooling rate of 5 ℃/min from room temperature to 200 by differential scanning calorimeter (DSC2910 is made by T.A Instrument) with the 10mg sample of the cellulose acylate film of first embodiment.

[mist degree of film]

The mist degree of the cellulose acylate film of first embodiment is 0.01-2.0% preferably, more preferably 0.05-1.5%, especially preferably 0.1-1.0%.For the film as optical thin film, its transparency is important.Mist degree is to use the cellulose acylate film sample of first embodiment that cuts into size 40mm x 80mm through haze meter (HGM-2DP; by Suga testinstruments Co., Ltd. makes) under the condition of 25 ℃ and 60%RH, measure according to JIS K-6714.

[the humidity dependence of the Re of film and Rth]

The delay Rth that postpones Re and thickness direction in the face of the cellulose acylate film of first embodiment preferably changes small those because of humidity.Particularly, in Rth value of measuring under the condition of 25 ℃ and 10%RH and the difference between the Rth value of measuring under 25 ℃ and 80% the condition, be Δ Rth (=Rth 10%RH-Rth 80%RH) preferably in the scope of 0-50nm, more preferably 0-40nm, more preferably 0-35nm

[equilibrium moisture content of film]

The equilibrium moisture content of the cellulose acylate film of first embodiment under 25 ℃ and 80% condition be 0-4% preferably; more preferably 0.1-3.5%; especially preferred 1-3%; irrelevant with film thickness, when as the protective film of polaroid, do not destroy and the water-soluble polymers cohesive of polyvinyl alcohol (PVA) for example.4% or bigger equilibrium moisture content be not preferred, this is because when as the supporter of optical compensating film, the dependence of the humidity variation of delay is too high.Moisture is to use the cellulose acylate film sample of first embodiment that cuts into size 7mm x 35mm through hygrometer and sample drying equipment (CA-03; VA-05 is made by MitsubishiChemical Corporation) according to Karl Fisher method the amount (g) of water is measured divided by sample quality (g).

[moisture-penetrability]

As the moisture-penetrability of the cellulose acylate film of the optical compensating film of first embodiment is to measure under the condition of 60 ℃ and 95%RH according to JIS Z-0208 method.Be converted to the film thickness of 80 μ m, moisture-penetrability is preferably at 400-2000g/m ²In the scope of 24h, more preferably 500-1800g/m ²24h, especially preferred 600-1600g/m ²24h.When described value greater than 2000g/m ²During 24h, the trend that the dependent absolute value of humidity of the Re value of film and Rth value surpasses 5nm/%RH improves.And; under the situation that optical compensating film is made up of the optical anisotropic film on the cellulose acylate film that is laminated in first embodiment; the trend that the dependent absolute value of humidity of the Re value of film and Rth value surpasses 5nm/%RH improves, and is not preferred therefore.When being installed to optical compensating gage or polarizer in the liquid crystal indicator, cause tonal variation and visual angle deterioration.Equally, make polarizer with the situation that is adhered to the polarization film both sides under, when moisture-penetrability is lower than 400g/m ²During 24h, it is bonding that defective takes place, and this is because cellulose acylate film stops the bonding agent drying.When cellulose acylate film was too thick, moisture-penetrability reduced, and thin film increases water permeability.Therefore, the sample that designs any film thickness all must be converted into 80 μ m.Film thickness is to convert by (film thickness/80 μ m that measure based on the water permeability x of water permeability=mensuration of 80 μ m).

With regard to this assay method, can adopt " The physical property of polymer II " (polymer experiment study 4, Kyoritsu Publication publishes) 285-294 page or leaf: the method described in the measurement of vapour transmission (metering method of quality method, temperature-hygrometer, vapor pressure method and absorption).The humidity control of 70mm φ cellulose acylate film sample that will this first embodiment under the condition of 25 ℃ and 90%RH and 60 ℃ and 5%RH 24 hours; and make described sample through moisture-penetrability analyzer (KK-709007; by Toyo SeikiSeisakusho; Ltd. make), with the moisture (g/m of following equation according to JIS Z-0208 method calculating per unit area ²).

Quality before quality after moisture-penetrability=humidity conditioning-humidity conditioning

[change in size of film]

Dimensional stability as for the cellulose acylate film of first embodiment; size changing rate under the high humility that under the condition of 60 ℃ and 90%RH, sample is kept measuring after 24 hours and under the condition of 90 ℃ and 5%RH, sample kept 24 hours after size changing rate preferably 0.5% or littler under the high temperature of mensuration; more preferably 0.3% or littler, more preferably 0.15% or littler.

Concrete assay method is as follows.Two samples of cellulose acylate film are made the size of 30mmx120mm, the humidity 24 hours of conditioning samples under 25 ℃ and 60%RH.Each end at sample is beaten 6mm φ hole with the interval of 100mm by automatic pin gauge (by Shinto ScientificCo., Ltd. makes), and measures the distance (L0) between these punchings.Be determined at and handle the distance (L1) between the punching after 24 hours under the condition of 60 ℃ and 90%RH and the distance (L2) between the punching after handling 24 hours under the condition of 90 ℃ and 5%RH.Measure to other minimum scale of 1/1000mm level.According to equation driven dimension rate of change.

Size changing rate under 60 ℃ and the 90%RH (high humility)=| L0-L1|/L0}x100;

Size changing rate under 90 ℃ and the 5%RH (high temperature)=| L0-L2|/L0}x100

[elastic modulus of film]

(elastic modulus)

The elastic modulus of cellulose acylate film is 200-500kgf/mm preferably ², more preferably 240-470kgf/mm ², more preferably 270-440kgf/mm ²Particularly, sample stretches under the rate of extension of 23 ℃ and 70% stretching condition and 10%/min with 0.5% pulling strengrth.Use general stretching analyzer (STM T50BP, by Toyo Baldwin Co., Ltd. makes) to measure stress, determine elastic modulus thus.

[the flexible coefficient of the optics of film]

(the optics elasticity of film)

The flexible coefficient of optics of the cellulose acylate of this first embodiment is 50x10 preferably ^-13Cm ²/ dyne or littler, more preferably 30x10 ^-13Cm ²/ dyne or littler, most preferably 20x10 ^-13Cm ²/ dyne.As concrete assay method; apply drawing stress at vertical cellulose acylate film sample to 12mmx12mm; and with ellipsometer (M150 JASCOCorporation) measures the delay of this moment, then by the flexible coefficient of change calculations optics that postpones with respect to stress.

(before stretching and the positive afterwards variation that postpones and the detection of slow axis)

The sample of preparation 100x100mm, and stretch in vertical (MD direction) or horizontal (TD direction) under the condition of 140 ℃ of temperature with fixing uniaxial tension machine.Use automatic birefringence meter KOBRA21ADH to measure and stretch before and the front delay of each sample afterwards.The angle of orientation that obtains during by the above-mentioned delay of mensuration is determined the detection of slow axis.The variation of the Re that preferred stretching causes is less, particularly, works as Re _(n)Represent interior (nm), the Re of postponing of front face of the film of the n (%) that stretched ₍₀₎When representing the interior delay of front face (nm) of non-stretched film, preferred | Re _(n)-Re ₍₀₎|/n≤1.0, more preferably | Re (n)-Re ₍₀₎|/n≤0.3 or littler.

(direction) with slow axis

Because polarization film has vertically (MD direction) absorption axes, therefore can be used for cellulose acylate film of the present invention and have preferred slow axis near MD or TD direction.If slow axis is parallel with polarization film or vertical, light leak and look become and can reduce so.Term " approaching " for example is meant angle between the slow axis and MD direction or the angle between slow axis and the TD direction in 0-10 ° scope, and preferred in 0-5 ° scope.

(intrinsic birefringence is positive cellulose acylate film)

When can be used for cellulose acylate film of the present invention has slow axis in pellicular front direction and stretch; positive postpone (Re) raises; and when cellulose acylate film with pellicular front in the direction vertical when stretching with direction with slow axis, positive postpone (Re) reduces.This display characteristic birefringence is positive, and is stretching in the direction vertical with slow axis that to remove aspect the delay that presents in the cellulose acylate film be effective.With regard to this method, for example think when film has vertically the slow axis of (MD direction), use stenter to stretch and will reduce positive the delay in the direction vertical (TD direction) with MD.As opposite example, think that when film has the slow axis of TD direction the tension force that the machine by strong stretching MD direction transports roller will reduce positive postpone (Re).

(intrinsic birefringence is the cellulose acylate film of bearing)

When can be used for cellulose acylate film of the present invention when the direction with slow axis stretches, positive postpone (Re) reduces, and when when the direction vertical with the direction with slow axis stretches, positive postpone (Re) raises, and also is fine.This display characteristic birefringence is born, and removes the delay that presents in the cellulose acylate film effectively in the direction stretching identical with slow axis.With regard to this method, for example think, when cellulose acylate film has the slow axis of MD direction, transport roller by brute force stretching machine and will reduce positive postpone (Re) at the tension force of MD direction.As opposite example, think when having the slow axis of TD direction, use stenter to stretch and will reduce positive the delay in the direction vertical (TD direction) with MD.

[evaluation method of cellulose acylate film]

In order to estimate the cellulose acylate film that can be used for first embodiment, measure according to the methods below.

(postpone Re in the face and along the delay Rth of thickness direction)

With the sample of 30mmx40mm conditioning humidity 2 hours under 25 ℃ and 60%RH, and by light at the normal direction incident λ of film nm wavelength, measure Re with automatic birefringence meter KOBRA21ADH (by Oji Scientific Instruments Co., Ltd. makes) _(λ)In addition, by the input default 1.48 of mean refractive index and film thickness to have following length of delay substrate: above-mentioned Re _(λ), and with regard to regard to the sloping shaft of slow axis in the face from the film normal direction tilt+40 ° direction incident wavelength λ nm light measurement length of delay and with regard to regard to the sloping shaft of slow axis in the face from calculating Rth with tilt-40 ° the length of delay of light measurement of direction incident wavelength λ nm of film normal direction _(λ)

(mensuration of the chromatic dispersion of Re and Rth)

With the conditioning 2 hours under the humidity of 25 ℃ and 60%RH of the sample of 30mm x 40mm, and by at the light of the normal direction incident 780nm-380nm of film wavelength, and measure the chromatic dispersion that Re under each wavelength measures Re with ellipsometer M-150 (by JASCO Corporation manufacturing).In addition, with regard to the chromatic dispersion of Re, based at the length of delay of three direction detections altogether, and calculate it by input default 1.48 of mean refractive index and film thickness, described three length of delays be above-mentioned Re, with regard to regard to the sloping shaft of slow axis in the face from the film normal direction tilt+40 ° direction incident 780-380nm light measurement length of delay and with regard to regard to the sloping shaft of slow axis in the face from tilt-40 ° the length of delay of light measurement of direction incident 780-380nm of film normal direction.

[evaluation method of cellulose acylate film]

In the evaluation method of this first embodiment, measure by following method.(mensuration of the chromatic dispersion of Re, Rth)

The sample of 30mmx40mm was 25 ℃, 60%RH conditioning humidity 2 hours, and in ellipsometer M-150 (making by JASCO Corporation) be that the photometry of 780-380nm is calculated the Re under the wavelength separately from film normal direction incident wavelength, measure the chromatic dispersion of Re thus.

(molecular orientation axis)

With the sample of 70mmx100mm conditioning humidity 2 hours under 25 ℃, 60%RH, and with automatic birefringence meter (KOBRA21DH, Oji Scientific Instruments Co., the sub-axis of orientation of phasemeter point counting during Ltd.) by the incident angle of change vertical incidence.

(axis shift)

And, use automatic birefringence instrumentation dead axle displacement of the lines angle.At 20 points of horizontal whole width measurements equal intervals and obtain average absolute.The mean value of the scope of phase retardation shaft angle (axis shift) four points that to be the mean value of four points beginning at 20 points of horizontal whole width measurements equal intervals with by the big absolute value of axis shift begin with less absolute value by axis shift poor.

(transmissivity)

Under 25 ℃, 60%RH, use transparency analyzer (AKA photoelectric tube tintmeter, KOTAKI Ltd.) to measure the transmissivity of visible light (615nm) of the sample of 20mmx70mm.

(spectral characterization)

Under 25 ℃, 60%RH, use spectrophotometer (U-3210, HITACHI LTD.) to measure the transmissivity of sample under the wavelength of 300-450nm of 13mmX40mm.Inclination width under the wavelength of the wavelength-5% of acquisition 75%.Limiting wave length appears under the wavelength of (pitch angle/2)+5%.Be absorption edge to occur under 0.4% the wavelength in transmissivity.Thus, the transmissivity under evaluation 380nm and the 350nm.

[performance of film surface]

Based on the JISB0601-1994 method, the arithmetic average roughness that the surface of the cellulose acylate film of preferred first embodiment has the surperficial irregularity of film is 0.1 μ m or littler, and maximum height (Ry) is 0.5 μ m or littler (Ra).More preferably, arithmetic average roughness (Ra) is that 0.05 μ m or littler and maximum height (Ry) are 0.2 μ m or littler.The irregularity of film surface can be used atomic force microscope (AFM) evaluation.

[irregular in the face of the delay of cellulose acylate film]

The cellulose acylate film of preferred first embodiment satisfies equation.| Re (MAX)-Re (MIN) |≤3 Hes | Rth (MAX)-Rth (MIN) |≤5 (wherein, Re (MAX), Rth (MAX) they are any 1m of cutting ²The maximum delay value of film, Re (MIN), Rth (MIN) they are respectively its minimum value).

[retention property of film]

With regard to the cellulose acylate film of first embodiment, require to join the retention property of all cpds in the film.Particularly, the mass change of film 0-5% preferably when the cellulose acylate film of first embodiment leaves standstill 48 hours under the condition of 80 ℃/90%RH.Be more preferably 0-3%, more preferably 0-2%.

(evaluation method of retention property)

Sample is cut into big or small 10cmx10cm, and under the environment of 23 ℃ and 55%RH, left standstill 24 hours, then quality measurement.Then it was left standstill 48 hours under the condition of 80 ± 5 ℃ and 90 ± 10%RH.This is handled the surface wiping gently of sample afterwards, and left standstill 1 day with 55%RH, measure its quality then at 23 ℃.Calculate retention property by following method.

Retention property (mass%)={ (quality before leaving standstill-after leaving standstill quality)/before leaving standstill quality } X100

[mechanical property of film]

(curling)

Cellulose acylate film of the present invention crimp values in the horizontal direction preferably-10/m is to+10/m.As described below; cellulose acylate film for first embodiment; when in coating and structure optical anisotropic layer, carrying out surface treatment; when promptly carrying out friction treatment; when perhaps long-time coating and structure or laminated alignment film or optical anisotropic layer etc.; if the cellulose acylate film of first embodiment crimp values in the horizontal direction exceeds above-mentioned scope, may bring problem when processing described film so or cause film to cut off.In addition and since film with transport roller at the edge of film or central part grade and contact strongly, so be easy to generate dust, the bonding increase of foreign matter on film, and the point defect of optical compensating film or the frequency that is coated with wiring can surpass acceptable value.In addition, if be crimped onto in the above-mentioned scope, can reduce incidental spot trouble when optical anisotropic layer is installed, bubble enters in the time of can preventing also that polarization film is laminated, is preferred therefore.

Crimp values can be measured according to the described assay method of American National Standards Institute (ANSI/ASCPH1.29-1985).

(tear strength)

With regard to the cellulose acylate film of first embodiment, in the thickness range of 20-80 μ m, based on the tear strength of tearing method of testing (Elmendorf tears method) of JISK 7128-2:1998 2g or bigger preferably.Be more preferably 5-25g, more preferably 6-25g.In addition, when becoming 60 μ m, tear strength is 8g or bigger preferably, more preferably 8-15g.Particularly, the humidity conditioning 2 hours under the condition of 25 ℃ and 65%RH of the sample fragment of 50mmX64mm can be measured tear strength with the tear strength analyzer of light load then.

[the residual solvent amount of film]

The cellulose acylate film of first embodiment is preferably dry under the condition that makes the residual solvent amount in the scope of 0.01-1.5 quality %.Be more preferably 0.01-1.0 quality %.The residual solvent amount of the transparent supporting body by will being used for first embodiment is adjusted to 1.5% or littler, can suppress curling.Be more preferably 1.0% or littler.Consider that major influence factors is to reduce freely and accumulate by reducing residual solvent amount when the above-mentioned solvent cast method film forming.

[the moisture expantion coefficient of film]

The moisture expantion coefficient of the cellulose acylate film of first embodiment is 30x10 preferably ^-5/ %RH or littler.This moisture expantion coefficient is more preferably 15x10 ^-5/ %RH or littler, more preferably 10x10 ^-5/ %RH or littler.In addition, the moisture expantion coefficient is preferably little, but often its value is 1.0X10 ^-5/ %RH or bigger.The variable quantity of sample length when the moisture expantion coefficient is meant relative humidity variations at a certain temperature.When the cellulose acylate film that uses first embodiment during as the optical compensating film supporter; by regulating the moisture expantion coefficient; can prevent that frame shape transmission (frame-shaped transmission) from increasing; promptly; the light leak that distortion causes increases, and keeps the optical compensation function of optical compensating film simultaneously.

[surface treatment]

By according to circumstances carrying out surface treatment, can be so that cellulose acylate film and the cohesive improvement of functional layer (for example, prime coat and bottom) separately.For example, can use glow discharge processing, UV-irradiation processing, corona treatment, flame treatment, acid or alkali treatment.It can be 10 that the glow discharge is here handled ^-3The low temperature plasma that the low-pressure gas of-20Torr produces down, also preferred Cement Composite Treated by Plasma under atmospheric pressure.Plasma exciatiaon gas is meant that under these conditions through the gas of plasma exciatiaon, for example, it is argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide and CFC for example tetrafluoromethane and their potpourri etc.About this point, especially at 30-32 page or leaf (the Laid-open technique NO.2001-1745 of the technicaldisclosure magazine of Japan Institute of Invention and Innovation, March 15 calendar year 2001, Japan Institute of Invention and Innovation publishes) details has been described, and can be preferred for first embodiment.

[contact angle of the film surface of process alkali soap processing]

When the cellulose acylate film that uses first embodiment during as the transparent protective film of polaroid, the alkali soap processing can be regarded as a kind of effective surface treatment mode.In this case, preferably 55 ° or littler of the contact angles of film surface after the alkali soap processing.Be more preferably 50 ° or littler, more preferably 45 ° or littler.As the evaluation method of contact angle, can use conventional method to estimate the hydrophilic/hydrophobic performance, wherein the water droplet with diameter 3mm drops on the alkali soap processing film surface afterwards, and measures the angle of film surface and water droplet.

(photostability)

As the index of the light permanance of the cellulose acylate of first embodiment, with super xenon light (super xenon light) the irradiation 240 hours aberration Δ E*ab preferably 20 or littler of film afterwards.It is more preferably 18 or littler, and more preferably 15 or littler.Aberration is measured with UV3100 (being made by Shimadzu Corporation).With regard to assay method, film is nursed one's health humidity 2 hours or longer in 25 ℃ down with 60%RH, carry out the colour examining of film before of xenon rayed then, measure initial value (L0 ^*, a0 ^*, b0 ^*).Then, at 150W/m ², 60 ℃ and 50%RH condition under in super xenon weather-o-meter SX-75 (by Suga test instruments, Co., Ltd. makes) with xenon light with film irradiation 240 hours.Through after the schedule time, from thermostatic bath, take out film, under 25 ℃ and 60%RH, regulate humidity 2 hours, and then colour examining, obtain through the value (L1 after the schedule time ^*, a1 ^*, b1 ^*).Thus, obtain aberration Δ E ^*Ab=((L0 ^*-L1 ^*) ^2+ (a0 ^*-a1 ^*) ^2+ (b0 ^*-b1 ^*) ^2) ^0.5.

[polarizer]

The liquid crystal indicator of first embodiment has first polarizer and second polarizer that is positioned at the liquid crystal board both sides.First and second polarizers are formed by polarization film with a pair of protective film that described polarization film is clipped between them respectively, and at least one described protective film (also as supporter) is to satisfy following above-mentioned cellulose acylate film:

0≤Re ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25.

According to first embodiment, the preparation method of polarizer has no particular limits, and can use conventional preparation method.That can mention has the cellulose acylate film that will obtain through alkali treatment; and the cellulose acylate film that will handle is adhered to the method for the both sides of polarizer with the aqueous solution of fully saponified poly-vinyl alcohol solution, and described polarizer is by soaking in iodine solution and stretching polyethylene alcohol film makes.Cellulose acylate film can replace alkali treatment through the good bonding processing described in JP-A6-94915 and 6-118232.

The bonding agent that is used for the surface treated of bonding protective film and polarization film can have been enumerated for example polyvinyl alcohol (PVA) or polyvinyl butyral or vinyl latex butyl acrylate etc. for example of polyvinyl alcohol-based adhesives.

Polarizer is made up of the protective film of the both sides of polarization film and protection polarization film, and can be by constituting at the bonding protector film of polarizer one side and at the bonding barrier film of opposite side.Protector film and barrier film are used for protecting polarizer during the transportation of polarizer and product detection etc.In this case, the protector film is through the bonding opposite side that is used to protect the surface of polarizer and is used for the surface that is adhered to liquid crystal board of polarizer.Barrier film is used to cover the bonding coat that links to each other with liquid crystal board, and is used for the side on the surface that polarizer links to each other with liquid crystal board.

In the liquid crystal indicator of first embodiment,, can obtain excellent display performance regardless of the installation site of the protective film of forming by the cellulose acylate film that satisfies following formula.Specifically, because the film of protection polarizer provides transparent hard conating, anti-glare layer or anti-reflecting layer etc. on the outmost surface of the demonstration side of liquid crystal indicator, therefore use the film of protection polarizer particularly preferably in this part.

[retardation films]

The liquid crystal indicator of first embodiment has first retardation films between the liquid crystal board and first polarizer, and has second retardation films between the liquid crystal board and second retardation films.

In the liquid crystal indicator of first embodiment, first retardation films preferably satisfies:

50≤Re ₍₅₈₉₎≤ 100 and 30≤Rth ₍₅₈₉₎≤ 80 and

Second retardation films preferably satisfies:

Re ₍₅₈₉₎≤ 20 and 100≤Rth ₍₅₈₉₎|≤300,

And first retardation films more preferably satisfies:

50≤Re ₍₅₈₉₎≤ 90 and 40≤Rth ₍₅₈₉₎≤ 60 and

Second retardation films more preferably satisfies:

Re ₍₅₈₉₎≤ 10 and 150≤Rth ₍₅₈₉₎|≤250.

When first and second retardation films have delay in above-mentioned scope, can obtain excellent display performance.Side or backlight side can observed in the position of first and second retardation films, but preferred each film of installing makes the retardation films of winning observe side, and second retardation films is in backlight side.

In the first embodiment, the angle that the polarizer and first retardation films make slow axis by the absorption axes of polarizer and first retardation films form preferably is installed and between 85 ° and 95 °, (comprises two end values).When the polarizer with optical compensation function through the described angle of formation is installed is used for VA type liquid crystal cell, the birefringence of this element is compensated effectively, therefore uses the visual angle of the liquid crystal indicator of the polarizer with optical compensation function can obtain enlarging.And the angle between the slow-axis direction of the direction of the absorption axes of polarizer and first retardation films is more preferably between 86 ° and 94 °, even more preferably between 87 ° and 93 °.

In the first embodiment, the thin polymer film that comprises in first retardation films can be formed by thin polymer film that stretches or liquid crystal film, and described stretching polymer film is by the formation that stretches of thin polymer film that proper method will not stretch.Equally, liquid crystal film is most preferably formed by nematic liquid crystal.

The thin polymer film of La Shening does not have no particular limits, but preferably can be endowed optically anisotropic material by film stretching, and described material has the controllability of birefringence, transparency and stable on heating excellence.The above-mentioned thin polymer film that does not stretch can use separately or two or more combinations of substances are used.For example, can use polyolefin (tygon, polypropylene etc.), polynorbornene polymkeric substance, polyesters, Polyvinylchloride, polystyrene, polyacrylonitrile, polysulfones, poly-allylat thing, polyvinyl alcohol (PVA), polymethacrylate, polyacrylate, cellulose esters and their multipolymer.

And, also can use the thin polymer film described in the JP-A 2001-343529 (WO 01/37007).With regard to this thin polymer film, for example, can use to contain to have and replace or the thermoplastic resin of unsubstituted imide and have at side chain replaces or the resin combination of the thermoplastic resin of unsubstituted phenyl and cyano group at side chain, can enumerate the alternating copolymer that contains isobutylene and N-methylene maleimide, and the resin combination of vinyl cyanide/styrol copolymer.

The preparation method of the thin polymer film of La Shening does not have no particular limits, and can use conventional method.Preferred extrusion molding or casting filming therapy, this is owing to can reduce the birefringent scrambling of thin polymer film afterwards that stretches.The thickness of the operable thin polymer film that does not stretch for example is 3mm or littler, preferred 1 μ m-1mm, preferred especially 5-500 μ m.

The drawing process of the thin polymer film of La Shening does not have no particular limits, but can use conventional method.That for example, can mention has a stenter cross directional stretch or biaxial stretch-formed.When biaxial stretch-formed, the draw ratio of preferred major axis (major axis) direction is less than the draw ratio of minor axis (minor axis) direction.Equally, biaxial stretch-formed can be when using biaxial stretch-formed or carry out based on the biaxial stretch-formed in succession of roller tentering type based on whole tentering type.

The draw ratio of the thin polymer film of La Shening can not change with drawing process, but with respect to length, the thin polymer film of La Shening is not stretched to 101-250% usually.With respect to the length of the thin polymer film that does not stretch, the draw ratio of the thin polymer film of La Shening 101-200% preferably not.

According to the type of adjuvant in the thin polymer film of the glass temperature (Tg) of the used thin polymer film that does not stretch or not stretching, suitably select the not draft temperature of the thin polymer film of stretching.The draft temperature of the thin polymer film of La Shening is not, for example, 80-250 ℃, preferred 120-220 ℃, preferred 140-200 ℃ especially.Particularly, the draft temperature of the thin polymer film that does not stretch is preferably near Tg or than the not Tg height of the thin polymer film of stretching to be stretched.

The thickness of the thin polymer film that stretches can suitably be selected according to the screen size of used image display apparatus.The thickness of the thin polymer film that stretches is, for example, and 1mm or littler, preferred 1-500 μ m, preferred especially 5-300 μ m.

Second retardation films can make with this liquid crystal arrangement and with the fixing cholesteric that forms of this ordered state by being coated with alignment layer with cholesteric crystal.

Cholesteric has no particular limits, and the layer that can use the method suitable with conventional liquid crystal arrangement technology to make.For example, at first on the alignment layer of substrate, be coated with cholesteric liquid crystal polymer and chiral reagent.Coating is heated to greater than glass temperature and less than the temperature of isotropy phase transition temperature, so that arrange liquid crystal polymer molecule in the coating.Afterwards, when coating is cooled to the temperature that is lower than glass temperature, can on substrate, form the cholesteric that the arrangement of liquid crystal polymer molecule is fixed.In addition, can mention a kind of method, the wherein liquid crystal monomer and the chiral reagent of coating Photocrosslinkable on above-mentioned alignment layer, and coating is heated to as mentioned above greater than glass temperature with less than the temperature of isotropy phase transition temperature, so that the liquid crystal monomer in the coating is arranged.Make it liquid crystal monomer is crosslinked to form cholesteric on substrate through rayed.

[liquid crystal board]

Liquid crystal board in the liquid crystal indicator of first embodiment is such liquid crystal board, wherein between upper substrate and infrabasal plate, be inserted with the liquid crystal of band negative dielectric anisotropic, they are vertical orientated from the teeth outwards, the orientation of these liquid crystal is almost vertical when not applying voltage, level almost when applying predetermined voltage, and when applying less than described predetermined voltage, tilt.The liquid crystal layer of liquid crystal board often forms by sealing liquid crystal in the formed gap of insertion sept between two substrates.On this substrate, can form transparent electrode layer as the transparent membrane that contains conductive material.Liquid crystal cell can also have gas barrier layer, hard conating or internal coating (being used for bonding transparent electrode layer).These layers often are provided on the substrate.The thickness of the substrate of liquid crystal cell is generally 50 μ m-2mm.VA type liquid crystal indicator can be, and for example, the subregion described in JP-A 10-123576 is arranged (partitioned alignment) type.The liquid crystal indicator of first embodiment can present excellent display characteristic and viewing angle characteristic, as transmission-type, reflection-type or transflective liquid crystal display device arbitrarily.

In the liquid crystal indicator of first embodiment, satisfy 0≤Re as mentioned above ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25 cellulose acylate film can be used as hard coat film, anti-dazzle film or anti-reflection film, to improve the visuality of liquid crystal indicator.The preferred implementation of this anti-dazzle film and anti-reflection film is described in detail in " Patent Studies " (Publicized Technology No.2001-1745 of Japanese Institute of Inventionand Innovation (JIII); publish March 15 calendar year 2001; JIII) 54-57 page or leaf, and can suitably use above-mentioned cellulose acylate film thus.

Satisfy 0≤Re as mentioned above ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25 cellulose acylate film has excellent transparency, and wherein optical anisotropy is approaching zero, and therefore can be used as the substitute of the liquid crystal cell glass substrate of liquid crystal indicator,, seals the transparency carrier of liquid crystal to be driven that is.

Have excellent gas barrier property owing to preferably seal the transparency carrier of liquid crystal, therefore if necessary, can on the surface of above-mentioned cellulose acylate film, provide gas barrier layer.The shape and the material of gas barrier layer have no particular limits, but can expect a kind ofly depositing SiO at least one surface of cellulose acylate film ₂Deng method or the method for the coating of the polymkeric substance (for example vinylidene chloride polymer or vinyl alcohol polymer) with quite high gas barrier property is provided, and can suitably use.

If use cellulose acylate film as the transparency carrier of sealing liquid crystal, can provide so by applying the transparency electrode of driven liquid crystal.Transparency electrode has no particular limits, but can provide transparency electrode by depositing metal films or metal-oxide film etc. at least one surface of cellulose acylate film.Wherein, from the angle preferable alloy sull of transparency, electric conductivity and mechanical property, wherein can preferably use the film of the indium oxide that mainly contains tin-oxide and 2-15% zinc paste.The detailed description of these films for example is disclosed among JP-A 2001-125079 or the 2000-227603 etc.

Second embodiment

Next, second embodiment of the present invention is described.

Below, describe the operation of second embodiment with reference to the accompanying drawings.

Fig. 1 is a synoptic diagram of describing the structure of conventional VA type liquid crystal indicator.VA type liquid crystal indicator has the liquid crystal cell 3 of band liquid crystal layer, and wherein when not applying voltage, that is, during black state, liquid crystal phase is for the substrate surface homeotropic alignment; Wherein be inserted with the polarizer 1 and the polarizer 2 of liquid crystal cell 3, and make their axis of homology (among Fig. 1 shown in the arrow) place each other in vertical direction through installing.In Fig. 1, from polarizer 1 side incident light.Do not applying under the voltage condition, when along normal direction, that is, during light incident that the z-direction of principal axis advances, the light by polarizer 1 keeps linear polarization state, and further by liquid crystal cell 3, is polarized device 2 at last fully and stops.The image that can show as a result, high-contrast.

Yet, as shown in Figure 2, the incident condition difference of irradiates light.When light not from the z-direction of principal axis but from vergence direction incident, promptly, when light during from direction (so-called off-axis (OFF the AXIS)) incident of tilting with respect to the polarization direction of

polarizer

1 and 2, be in the influence of the delay of vergence direction in the time of the homeotropic alignment liquid crystal layer of incident light by liquid crystal cell 3, polarization state changes thus.And the apparent axis of homology of polarizer 1 and polarizer 2 departs from vertically arranged direction.Because these two factors, be not polarized device 2 fully at light and stop, and under dark state, light leak takes place from the vergence direction incident of off-axis, contrast is reduced.

Here, polar angle and position angle are defined.Polar angle is the normal direction from film surface, that is, the angle that tilts from the z-axle of Fig. 1 and Fig. 2, for example, the normal direction of film surface is the direction of polar angle=0 °.The direction that is rotated counterclockwise of the forward of relative x-axle is represented at the position angle, and for example, the forward of x-axle is the direction of position angle=0, and the forward of y-axle is the direction of position angle=90 °.The vergence direction of above-mentioned off-axis is meant that polar angle is not 0 ° a situation, and mainly is meant position angle=45 °, 135 °, 225 ° or 315 °.

Fig. 3 shows the synoptic diagram of the illustration structure of the mechanism be used for describing an embodiment explaining second embodiment.Liquid crystal indicator shown in Figure 3 has following structure: wherein the structure of Fig. 1 also adds cellulose acylate film 6 and the optical compensating film 4 that is installed between liquid crystal cell 3 and the polarizer 1, and is installed in optical compensating film 5 and cellulose acylate film 7 between liquid crystal cell 3 and the polarizer 2.In the liquid crystal indicator of present embodiment, the refractive index anisotropy under the wavelength X (unit: nm, down together) of thickness d of liquid crystal layer in liquid crystal cell (unit: nm, down together) and liquid crystal layer, Δ n _(λ)Optical compensating film 4 and cellulose acylate film 6 and optical compensating film 5 and cellulose acylate film 7 postpone sum, Re in the face under the wavelength X _{Sum (λ)}With the delay sum of thickness direction under wavelength X, Rth _{Sum (λ)}, two different wave lengths in the wavelength coverage of 380nm-780nm satisfy following formula (I)-(IV) relatively:

(I)200≤Δn(λ)xd≤1000，

(II)Rth _sum(λ)/λ＝AxΔn _(λ)xd/λ+B，

(III) Re _{Sum (λ)}/ λ=Cx λ/{ Δ n _(λ)Xd}+D and

(IV)0.488≤A≤0.56，

B＝-0.0567，

-0.041≤C≤0.016 and

D＝0.0939。

And (unit: postponing in the face nm) is Re in wavelength X when cellulose acylate film _{2 (λ)}, and wavelength X (unit: the delay of the thickness direction nm) is Rth _{2 (λ)}The time, satisfy following formula (IX) and (X):

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(2) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

Fig. 4 shows the synoptic diagram of the illustration structure of the mechanism be used for describing another embodiment of explaining second embodiment.The position of optical compensating film 8 and cellulose acylate film 9 can exchange.In the liquid crystal indicator of present embodiment, the refractive index anisotropy under the wavelength X (unit: nm, down together) of thickness d of liquid crystal layer in the liquid crystal cell (unit: nm, down together) and liquid crystal layer, Δ n _(λ)Postpone sum, Re in the face under the wavelength X of optical compensating film 8 and cellulose acylate film 9 _{Sum (λ)}With the delay sum of thickness direction under the wavelength X, Rth _{Sum (λ)}, two different wave lengths satisfy following formula (I)-(IV) in the wavelength coverage of 380nm-780nm relatively:

(V)200≤Δn _(λ)xd≤1000，

(VI)Rth _sum(λ)/λ＝ExΔn _(λ)xd/λ，

(VII) Re _{Sum (λ)}/ λ=Fx λ/{ Δ n _(λ)Xd}+G and

(VIII)0.726≤E≤0.958、

0.0207≤F≤0.0716 and

G＝0.032。

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(X) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

In second embodiment; satisfy any one group liquid crystal layer, optical compensating film and cellulose acylate film in formula (I)-(IV) and the formula (V)-(VIII) by combination; can have the optical compensation of slow axis and be suitable for the delay of wavelength, even also like this under the situation of vergence direction incident at the light of predetermined wavelength with visible region.As a result, compare with conventional liquid crystal indicator, the visual contrast under the dark state significantly improves, and also significantly reduces at the aberration of dark state downwards angle of visibility direction.With respect at least two different wavelength, liquid crystal indicator of the present invention satisfies formula (I)-(IV) or formula (V)-(VIII).With respect to differing 50nm or two bigger wavelength, preferred liquid crystal indicator satisfies formula (I)-(IV) or formula (V)-(VIII).Which wavelength is above-mentioned condition satisfy can change with the purposes of liquid crystal indicator, and will select wavelength and wavelength coverage that display performance is had the greatest impact.In general, the wavelength of relative 650nm, 550nm and 450nm, they are corresponding to three main color redness (R), green (G) and blue (B), and liquid crystal indicator preferably satisfies formula (I)-(IV) or formula (V)-(VIII).In addition, although the wavelength of R, G and B mainly be can't help above-mentioned wavelength representative, think that these wavelength are fit to the optical property that definition produces the effect of second embodiment.

Next, describe the compensation principle of second embodiment in detail.In second embodiment, should note postponing the ratio with wavelength especially, that is, and Re/ λ and Rth/ λ.This is because Re/ λ is the birefringent parameter of representative with Rth/ λ and is that polarization state exists the most important parameter of determining when changing mutually.And, the ratio of Re/ λ and Rth/ λ, that is, and Re/Rth, two intrinsic polarization axles the during transmittance of determining to advance by the twin shaft birefringent medium with vergence direction.In Fig. 5, shown under the situation of the light incident of advancing by the twin shaft birefringent medium illustration result of direction of one of two intrinsic polarization axles of calculating and the relation of Re/Rth with vergence direction.In addition, suppose that light transmissive direction is position angle=45 ° and polar angle=34 °.Be understood that when determining Re/Rth, determine an intrinsic polarization axle by result shown in Figure 5.And Re/ λ has two intrinsic polarizations of change function mutually with Rth/ λ.

In association area, the chromatic dispersion of the film of compensation VA type is with Re, Rth or Re/Rth definition.In second embodiment, find under wavelength X, without the value of Re, Rth and Re/Rth etc., but, can compensate the principle of VA type by paying close attention to Re/ λ and Rth/ λ and making these parameter dimensionless.And, inventors of the present invention notice that also chromatic dispersion is present among the birefringence nd of liquid crystal layer of object to be compensated, and the relation between the chromatic dispersion of the birefringence nd of the liquid crystal layer of the object of the chromatic dispersion of the Re of optical compensating film and Rth and optical compensation is furtherd investigate.Therefore, they find to concern (I)-(IV) or (V)-(VIII) time, the viewing angle properties of liquid crystal indicator is significantly improved when satisfying.In the liquid crystal indicator of second embodiment, when satisfying the concerning of formula (I)-(IV) or formula (V)-(VIII), liquid crystal cell accurately obtains optical compensation, therefore and reduced the reduction of contrast, even also like this under the situation that following two kinds of factors are arranged: light is from vergence direction incident and under the influence of the delay of the vergence direction of liquid crystal layer and a pair of not arrangement of the apparent axis of homology of going up polarizer and following polarizer.

In addition, in the VA type, do not applying voltage, promptly under dark state, the liquid crystal homeotropic alignment.Therefore, in order can not to be subjected to the influence of the delay of optical compensating film under the dark state from the polarized state of light of normal direction incident, slow axis is vertical or parallel with the polarization axle of the polarizer of close described optical compensating film installation in the face of preferred optical compensating film.

Fig. 6 shows the figure that describes the compensatory michanism of embodiment shown in Figure 3 by Poincare sphere.Here, light transmissive direction is position angle=45 ° and polar angle=34 °.In Fig. 6, the S2 axle is the axle that sees through vertically downward from paper, and Fig. 6 is the figure that observes Poincare sphere from the forward of S2 axle.And, because Fig. 6 shows with plane, therefore represent by straight arrow among the figure with some displacement afterwards before polarization state changes, but in fact, use rotation because of the change of the polarization state that sees through liquid crystal layer or optical compensating film, represent by specific rotation angle according to the specific axis of each optical property decision of Poincare sphere.

The polarization of incident light state that sees through polarizer 1 among Fig. 3 is corresponding to the point 1 among Fig. 6, and is polarized polarization state that the absorption axes of device 2 stops among Fig. 3 corresponding to the point 2 among Fig. 6.In general, in VA type liquid crystal indicator, be attributable to a little 1 and the excentricity of point 2 at the light leak of vergence direction off-axis.Optical compensating film commonly used causes the polarization of incident light state variation, and the polarization state that comprises liquid crystal layer is from putting 1 variation to point 2.The liquid crystal layer of liquid crystal cell 3 presents positive refracting power anisotropy and homeotropic alignment.Therefore, incident light is represented and is shown as around the S1 axle to rotate (rotating to a B from an A among the figure) with the arrow shown in from top to bottom shown in Figure 6 because of the change of the polarization state that sees through liquid crystal layer on the Poincare sphere.The anglec of rotation and a value are proportional, described value be with under the wavelength X from effective delay of the vergence direction of liquid crystal layer, Δ n ' d ' obtains divided by this wavelength, that is, Δ n ' d '/λ.In order to compensate described liquid crystal layer, present embodiment is used optical compensating film 4 and 5 and cellulose acetate film 6 and 7.With regard to the combination of the combination of optical compensating film 4+ cellulose acetate film 6 and optical compensating film 5+ cellulose acetate film 7, at the length of the arrow of vergence direction (among the figure from putting 1 to an A arrow length and arrow length) from a B to point 2, promptly, rotation angle is almost with the combination of optical compensating film 4+ cellulose acetate film 6 and the combination Rth separately of optical compensating film 5+ cellulose acetate film 7 _Sum/ λ is proportional, so the turning axle of arrow is by aforesaid Re _Sum/ Rthsum decision.For by the optical compensating film 4 described in Fig. 6 and 5 and cellulose acetate film 6 and 7 realize the optical compensation of VA type liquid crystal cells, when use has the liquid crystal layer of big Δ n ' d '/λ, must make optical compensating film 4 and 5 and the Rth of cellulose acetate film 6 and 7 _Sum/ λ raises, and makes from the arrow length and the increase of the arrow length from a B to point 2 of putting 1 to an A.Equally, for make from put 1 to a direction of arrow of A vergence direction with more vertical to the direction of arrow of point 2 vergence directions from a B, can expect essential optical compensating film 4 and 5 and the Re of cellulose acylate film 6 and 7 of reducing _Sum/ Rth _Sum, that is, and Re _Sum/ λ.In the present embodiment, the Re of optical compensating film+cellulose acylate film _Sum/ λ and Rth _Sum/ λ is that the Δ n ' d '/λ according to liquid crystal layer determines under the condition that satisfies formula (I)-(IV), so that obtain accurate optical compensation.In the present embodiment, when Δ nd that is determined at the liquid crystal in the liquid crystal layer of the object for the treatment of optical compensation under the wavelength X and wavelength X, also determine Δ n ' d '/λ.Therefore, has the Re that satisfies top those formulas _Sum/ λ and Rth _SumTherefore the optical compensating film of/λ and cellulose acylate film can use valuably.Owing to have the optical compensating film of combination and the Re of cellulose acylate film _Sum/ λ and Rth _SumThe ideal value of/λ is useful, and Re/ λ that can not obtain in the single optical compensation film and the value of Rth/ λ can be regulated to obtain desirable value by the performance of cellulose acylate film.Embodiment shown in Figure 3 use optical compensating film and cellulose acylate film make one in the above and another below, be respectively two altogether therefore.Specifically, can see when top performance with following optical thin film is identical, arrow below the sensing liquid crystal layer stands the conversion of S1=0 because of symmetry on Poincare sphere, and the initial point of arrow and terminal point are symmetrically located at the episphere and the lower semisphere of Poincare sphere respectively under the liquid crystal layer, and the equator is arranged therebetween.

Fig. 7 shows the figure that describes the compensatory michanism of embodiment shown in Figure 4 by Poincare sphere.In addition, owing to have the implication identical with axle, therefore save their detailed description with top definition with the point of sign flag same as shown in Figure 6.As shown in Figure 7, for by optical compensating film 8+ cellulose acylate film 8 optical compensation VA type liquid crystal cells, when using the big liquid crystal layer of Δ n ' d '/λ, essential by increasing the Rth of optical compensating film 8 _Sum/ λ prolongs from putting the length of 1 to an A arrow.And, more vertical in order to make from putting 1 to an A the be inclined upwardly direction of arrow of direction, can expect the essential Re that reduces optical compensating film 8 _Sum/ Rth _Sum, that is, reduce Re _Sum/ λ.In the present embodiment, under the condition that satisfies formula (V)-(VIII), determine the Re of optical compensating film according to the Δ n ' d '/λ of liquid crystal layer _Sum/ λ and Rth _Sum/ λ is so that obtain the precise optical compensation.In the present embodiment, when measuring, also determine Δ n ' d '/λ in the Δ nd of the liquid crystal in the liquid crystal layer of the object for the treatment of optical compensation under the wavelength X and wavelength X.Therefore, can advantageously use Re thus with satisfied top those formulas _Sum/ λ and Rth _SumThe optical compensating film of/λ.

And Fig. 7 has structure same as shown in Figure 4.Use this structure, by liquid crystal cell 3 and the optical compensating film 8 that satisfies following formula (V)-(VIII), cellulose acylate film 8 and cellulose acylate film 9 combinations can be obtained accurate optical compensation.

As mentioned above; second embodiment is according to the spectral range or the spectral distribution of used light source, makes the optimization that concerns between the Resum/ λ of the so-called birefringence nd/ λ of liquid crystal layer of VA type and this birefringent optical thin film of compensation and cellulose acylate film and the Rthsum/ λ.Consider and theoretical infer and clear this optimum range of definition, the different optical compensations that are the VA type of second embodiment and common process.When with the combination of liquid crystal layer and optical compensating film so that satisfy following formula (I)-(VI) or (V)-(VIII) time, can compensate the chromatic dispersion of liquid crystal layer by the chromatic dispersion of optical compensating film.As a result, can reduce the visual contrast of the plate that uses the VA type greatly.Equally, because can be at the light leak under any wavelength coverage inner control dark state, therefore the aberration with the visual angle that causes because of light leak under specific wavelength also can reduce.

Second embodiment is represented by the above-mentioned relation formula so that show the optimum value of film, the illustration actual effect that develops simultaneously fruit.In those formulas, parameter A, B, C and D or parameter E, F and G definition obtain the scope of effect of the present invention in the above.Yet, B and D or G easily with the integer representation of optimum value so that show the scope of film effect, and A and C or E and F represent scope with the effect that shows second embodiment with numerical range.

Second embodiment provides a kind of optical compensating film, and the relatively any birefringence and the chromatic dispersion of liquid crystal, the chromatic dispersion of described optical compensating film can reduce the visual angle contrast and greatly with the aberration at the visual angle of the plate that uses the VA type; Yet second embodiment also can be used for using the liquid crystal cell of the different wave length of R, G and B.For example, even be used to have at the film with second embodiment under the situation of transflective liquid crystal element of structure of different R, G and B, use above-mentioned those formulas can obtain optical compensation, the result can obtain the effect of wide visual angle contrast.And, even under situation, with the optical compensating film of the formula that satisfies second embodiment, for example for the liquid crystal board of the conventional light source that uses mixing with a plurality of wavelength, by represent the performance of liquid crystal board with the wavelength of G, can obtain the effect of wide visual angle contrast.

The scope of second embodiment is not subjected to the restriction of the display type of liquid crystal layer, and can be used for having the liquid crystal indicator of the liquid crystal layer of any display type, for example VA type, IPS type, ECB type, TN type and OCB type.

Next, describe optical property, raw material and the preparation method etc. of the optical compensating film that can be used for second embodiment in detail.

[optical compensating film]

In second embodiment, optical compensating film helps improving the visual angle contrast and reduces with liquid crystal indicator, particularly the aberration at the visual angle of VA type liquid crystal indicator.The optical compensating film of second embodiment can be installed between the polarizer and liquid crystal cell of observer's side, perhaps is installed between the polarizer and liquid crystal cell of rear side, perhaps even be installed in above-mentioned both sides.For example; optical compensating film can be used as independent component and is installed in the liquid crystal indicator, and an element that perhaps also can be used as polarizer is installed in and works to give the optical compensating film of the protective film of protection polarization film with above-mentioned optical property in the liquid crystal indicator.

As mentioned above, in optical compensating film, with respect to any wavelength X of being used by light source or observer in the wavelength of visible region, Re/ λ has different preferable range with Rth/ λ, and this depends on the shape and the wavelength X of liquid crystal layer.For example, wavelength with respect to 550nm, this optical compensating film (for example is being used for VA type liquid crystal cell, the VA type liquid crystal cell that comprises liquid crystal layer, wherein thickness d (μ m) and refractive index anisotropy Δ n are long-pending, and Δ nd is 0.2-1.0 μ m) the situation of optical compensation under, Re/ λ is 0.04-0.13nm preferably, more preferably 0.05-0.1nm, even more preferably 0.06-0.09nm.Rth/ λ is 0.05-1.1nm preferably, more preferably 0.1-1.0nm, even more preferably 0.13-0.91nm.

Optical compensating film has three mean refractive index nx, ny and nz in the direction of the x that is perpendicular to one another, y and z axle.The characteristic refractive index that these three values are optical compensating films, and Rth and Re are by these values and thickness d ₁Decision.The optical compensating film that satisfies above-mentioned optical property can pass through to select suitable raw material, combined amount and working condition etc., and parameter regulation to required scope is made.Because nx, ny and nz be with wavelength variations, so Rth and Re are also with wavelength variations.Above-mentioned optical compensating film can be by producing with this this characteristic.

In second embodiment, the material of optical compensating film has no particular limits.For example, described material can be the birefringent polymer film that stretches or by with the fixing optical anisotropic layer of liquid-crystal compounds formation of specific orientation.And optical compensating film is not limited to single layer structure, and can have the laminate structures of laminated multilayer.In the structure of laminate structures, the material that constitutes each layer can not be a same material, and for example, laminated thing can be thin polymer film and the laminated thing that contains the optical anisotropic layer of liquid-crystal compounds.In the structure of laminate structures, consider thickness, comprise that the laminated thing of application type of the layer that forms by coating is more preferred than the laminated thing of the thin polymer film that stretches.

When liquid-crystal compounds is used for the preparation of optical compensating film, because liquid-crystal compounds has different state of orientation, therefore by with the fixing optical anisotropic layer that makes of liquid-crystal compounds of specific orientation, present as individual layer or as the required optical property of multilayer layer compound.That is, optical compensating film can have the structure of at least one optical anisotropic layer that comprises supporter and form on this supporter.Bulk delay with optical compensating film of this structure can be regulated by the optical anisotropy of optical anisotropic layer.Liquid-crystal compounds can be divided into rod shaped liquid crystal compound and disc liquid-crystal compounds according to molecular shape.And each classification is divided into low-molecular-weight type and high molecular type once more, and these two types can be used.When liquid-crystal compounds is used to prepare optical compensating film, preferably uses rod shaped liquid crystal compound or disc liquid-crystal compounds, and more preferably use the disc liquid-crystal compounds that has the rod shaped liquid crystal compound of polymerizable groups or have polymerizable groups.

Optical compensating film can be made up of thin polymer film.Thin polymer film can be the thin polymer film of stretching or the combination of application type polymeric layer and thin polymer film.The material of operable thin polymer film can be synthetic polymer (for example, polycarbonate, polysulfones, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin, tri acetyl cellulose) usually.Also can be preferably by containing cellulose acylate and having the cellulose acylate film that the composition of the bar-shaped compound (aromatic that particularly, has two aromatic rings) of aromatic rings forms.Having the type of the aromatic that the thin polymer film of required optical property can add by control and the condition of amount and film stretching makes.

In the liquid crystal indicator of second embodiment, as mentioned above, use at least a following formula (IX) and (X) of satisfying, that is, have the cellulose acylate film of low optical anisotropy and low wavelength dispersibility.The details such as top first embodiment that comprise the preparation method of the cellulose acylate film that can be used for second embodiment and raw material etc. are described.

[adjuvant of cellulose acylate]

Cellulose acylate film preferably makes by the method for solution casting film forming, but the preparation method is not limited to this.By in the method for solution casting film forming, at first prepare the solution (dope) of cellulose acylate.According to the purposes in each preparation process; can in cellulose acylate solution, add various adjuvants (for example, reduce optically anisotropic compound, dispersion adjustment agent, ultraviolet blocking agent, plastifier, degraded and prevent agent, particulate, optical property correctives etc.).The interpolation time can be any stage of dope preparation process, but preferably at the last preparation process adding adjuvant of dope preparation process, further is prepared process then.

In second embodiment, the optical anisotropy of preferred at least a reduction cellulose acylate film particularly reduces the delay Rth of film thickness direction, compound, content satisfy following formula (ii) and (iii):

(ii) (Rth ₂(A)-Rth ₂(0))/A≤-1.0 and

(iii)0.01≤A≤30。

Formula (ii) and (iii) more preferably

(ii) (Rth ₂(A)-Rth ₂(0))/A≤-2.0 and

(iii)0.05≤A≤25，

Even more preferably

(ii) (Rth ₂(A)-Rth ₂(0))/A≤-3.0 and

(iii)0.1≤A≤20。

It is described to reduce the architectural feature of optically anisotropic compound of the cellulose acylate film can be used for second embodiment and performance such as top first embodiment.

The instantiation that reduces the optically anisotropic compound of the cellulose acylate film that is preferred for second embodiment comprises the compound of formula (13), (18) and (19) representative.

[wavelength dispersion correctives]

The compound (following also be referred to as " dispersion adjustment agent ") of the chromatic dispersion of cellulose acylate film will describe be reduced.In order to improve the Rth of cellulose acylate film ₂Chromatic dispersion, preferably contain at least a reduction following formula (iv), Δ Rth=|Rth ₂(400)-Rth ₂(700) | the Rth of representative ₂The compound of chromatic dispersion, its content satisfies following formula (v) and (vi).The details of dispersion adjustment agent is described in top first embodiment.

(vi)ΔRth＝|Rth ₂(400)-Rth ₂(700)|、

(v) (Δ Rth (B)-Δ Rth (0))/B≤-2.0 and

(vi)0.01≤B≤30。

Formula (v) and (vi) more preferably

(v) (Δ Rth (B)-Δ Rth (0))/B≤-3.0 and

(vi)0.05≤B≤25，

Even more preferably

(v) (Δ Rth (B)-Δ Rth (0))/B≤-4.0 and

(vi)0.1≤B≤20。

[matting agent particulate, plastifier, degraded prevent agent, release agent]

Preferably in cellulose acylate film, add particulate as matting agent.And; in second embodiment; except reducing optically anisotropic compound and dispersion adjustment agent; can also be according to the purposes of each production technology; in cellulose acylate film, add various adjuvants (for example, plastifier, ultraviolet blocking agent, degraded prevent agent, release agent, infrared absorbent etc.).Its details is as described in top first embodiment.

Cellulose acylate film preferably makes by the solvent cast method, and preferably by making with the solution (dope) that is dissolved in the cellulose acylate in the organic solvent.The details of organic solvent is as described in top first embodiment.And the details of the preparation technology of the cellulose acylate film of second embodiment and optical characteristics and performance is also as described in top first embodiment.

The cellulose acylate film that satisfies required optical property can be installed in the liquid crystal indicator of second embodiment as an independent component, perhaps can be used as with the integrated element of other element to install.For example; cellulose acylate film can be used as an element of polarizer the protective film that is used as polarization film is installed; comprise under the situation of the optical anisotropic layer that contains liquid-crystal composition at optical compensating film that perhaps cellulose acylate film can be used as an element of optical compensating film the supporter that is used as optical anisotropic layer is installed.And, even for the laminated situation of the thin polymer film with other optical property with the optical compensating film that satisfies the particular optical performance under, cellulose acylate film can be used as the polymer thin membrane component that constitutes optical compensating film and installs.

Also the cellulose acylate film that provides various functional layers can be installed in the liquid crystal indicator of the present invention.That for example, can mention has antistatic layer, curable resin layer (transparent hard conating), anti-reflecting layer, excellent bonds layer, anti-glare layer, optical compensating film, oriented layer and a liquid crystal layer etc.The functional layer and the material thereof that can be used for cellulose acylate film can be surfactant, antiseize paste, matting agent, antistatic layer and hard conating etc.; and its details is described in " Patent Studies " (Publicized technology No.2001-1745 of Japanese Institute of Invention and Innovation; publish March 15 calendar year 2001; JIII) 32-45 page or leaf, its information can be preferred for second embodiment.

As mentioned above, the cellulose acylate film with these optical properties can be used as the protective film of polarization film.In this case, the preparation method of polarizer has no particular limits, and polarizer can make by conventional method.That can mention makes the gained cellulose acylate film through alkali treatment, and is bonded in both sides by the polarizer that in iodine solution polyvinyl alcohol film immersion and stretching is made with the cellulose acylate film that the aqueous solution of fully saponified poly-vinyl alcohol solution will be handled.Cellulose acylate film can be handled through the excellent bonds described in JP-A6-94915 and the 6-118232 in this way and replace alkali treatment.

The bonding agent that is used for the surface treated of bonding protective film and polarizer can have been enumerated for example polyvinyl alcohol (PVA) or polyvinyl butyral or vinyl latex butyl acrylate etc. for example of polyvinyl alcohol-based adhesives.

Polarizer is by polarizer and protects the protective film of the both sides of this polarizer to constitute, and can pass through to constitute at the bonding protector film of polarizer one side and at the bonding barrier film of opposite side.Protector film and barrier film are used for the purpose at polarizer protection polarizer such as between the delivery period and between the product detection period of polarizer.In this case, bonding protector film is with the surface of protection polarizer and that be used in polarizer and the opposite side bonding surface of liquid crystal board.Barrier film is used to cover the bonding coat that links to each other with liquid crystal board, and is used in the side on the surface that polarizer links to each other with liquid crystal board.

As mentioned above, having the cellulose acylate film of above-mentioned optical property can be as part or all of optical compensating film.Specifically, in the optical compensating film that contains the optical anisotropic layer that is formed by liquid-crystal composition, cellulose acylate film can be used as the supporter of optical anisotropic layer.And, except function as supporter, the effect of the protective film of all right polarizing film of cellulose acylate film.In addition, optical compensating film is meant and is usually used in the optical material of liquid crystal indicator with compensating delay, and can exchange with retardation plate or optical compensating gage etc. and use.Therefore optical compensating film has birefringence and is used to eliminate display screen painted of liquid crystal indicator or improves viewing angle properties.The Re of cellulose acylate film under wavelength X _{2 (λ)}And Rth _{2 (λ)}At 0≤Re _{2 (630)}≤ 10nm and | Rth _{2 (630)}| in the scope of≤25nm, give less optical anisotropy, and also present | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes | Rth _{2 (400)}-Rth _{2 (700)}|≤35 relation, give less chromatic dispersion.Therefore, cellulose acylate film does not cause any unnecessary anisotropy, and when with have birefringent optical anisotropic layer when being used in combination, only can express the optics behavior of optical anisotropic layer.

Next, with reference to Fig. 8 an embodiment that second embodiment is used for VA type liquid crystal indicator is described.

[liquid crystal indicator]

Liquid crystal indicator shown in Figure 8 has liquid crystal cell 16-18, be inserted in wherein last polarization film 11 and following polarization film 101 with described liquid crystal cell, and between last polarization film 11 and liquid crystal cell 16-18, be inserted with optical compensating film 15, be inserted with optical compensating film 19 between polarization film 101 and the liquid crystal cell 16-18 down.As mentioned above, according to structure, optical compensating film 15 or optical compensating film 19 can only be positioned at a

side.Polarization film

11 and 101 is respectively by a pair of transparent protective film protection.Yet Fig. 8 only shows the transparent protective film of installing near

liquid crystal cell

13 and 103, and the transparent protective film of installing away from liquid crystal cell saves.Transparent

protective film

13 and 103 is formed by satisfying following formula (IX) and cellulose acylate film (X).

Liquid crystal cell comprises upper substrate 16, infrabasal plate 18, and forms and be inserted in liquid crystal layer between the substrate of up and down by liquid crystal molecule 17.The oriented film (not shown) is formed at the surface (below, can be referred to as " inside surface ") of the substrate 16 that contacts with liquid crystal molecule 17 and 18, and is controlled to be vertically in the orientation that does not apply under voltage or the low-voltage liquid crystal molecule 17.And, the inside surface in substrate 16 and 18, formation can apply the transparency electrode (not shown) of voltage to the liquid crystal layer that is formed by liquid crystal molecule 17.In second embodiment, the product Δ nd of thickness d of liquid crystal layer (μ m) and refractive index anisotropy Δ n is 0.1-1.0 μ m preferably.And the optimum value of Δ nd is more preferably 0.2-1.0 μ m, even more preferably 0.2-0.5 μ m.In these scopes, the brightness height that white shows, and the brightness of black state is low, therefore can obtain the high display device of luminance contrast.Operable liquid crystal material has no particular limits, but applies between up and down substrate 16 and 18 in the embodiment of electric field, uses to have the liquid crystal material of negative dielectric anisotropic so that liquid crystal molecule 17 responds with the direction of electric field is vertical.When only forming electrode with 18 either side so that when laterally applying electric field, can use liquid crystal material with positive dielectric anisotropy parallel with substrate surface at substrate 16.

For example, when liquid crystal cell is VA type liquid crystal cell, can between up and down

substrate

16 and 18, use to have negative dielectric anisotropic, the nematic liquid crystal material of Δ n=0.0813 and Δ ε=-4.6 or the like.The thickness d of liquid crystal has no particular limits, but when using the liquid crystal of the performance with above-mentioned scope, thickness can be adjusted to about 3.5 μ m.Because the brightness during white shows changes with the order of magnitude of the product Δ nd of thickness d and refractive index anisotropy Δ n, in order to obtain high-high brightness, preferably Δ nd is adjusted in the scope of 0.2-0.5 μ m.

And, in VA type liquid crystal indicator, seldom using the chiral reagent that is usually used in TN type liquid crystal indicator, this is will reduce dynamic response characteristics owing to add this reagent, arranges to reduce defective but add this reagent in some cases.Under the situation that is the multiple domain structure, it is useful using the arrangement of the liquid crystal molecule of the borderline region between chiral reagent control domain and the territory.The multiple domain structure is meant that a pixel of liquid crystal indicator is separated into the structure in a plurality of zones.For example, in the VA type, because liquid crystal molecule 17 tilts during white shows, therefore when the birefringence that has the varying number level at the reverse direction liquid crystal molecule 17 of vergence direction and vergence direction when vergence direction is observed, brightness and tone change thus.Yet, use the multiple domain structure, improved viewing angle characteristic with respect to brightness or tone, and be preferred therefore.Particularly, by at least two (preferred 4 or 8) of liquid crystal molecule, making up single pixel and making them average, can reduce brightness or tone deviation with the visual angle with different initial orientations.Perhaps, make up single pixel by direction of orientation with at least two zoness of different of voltage continually varying that apply and to obtain identical effect at liquid crystal molecule.

When formation liquid crystal molecule 7 has a plurality of zone of different orientation direction in a pixel, for example can using method on electrode, provide the slit, with by providing projection to change the direction of electric field, give electric field density deviation etc.In order to obtain at the uniform visual angle of all directions, the quantity that increases subregion will be useful, but promptly use four subregions or eight subregions or more, also can obtain almost visual angle uniformly.Specifically, preferred octant, this is because the absorption axes of polarizer can be set in any angle at random.The trend that exists liquid crystal molecule 7 to be difficult to respond on the border of individual domain.In normal black type for example in the VA type, owing to should keep black state, so brightness reduces and becomes problem.Therefore, can reduce borderline region between the territory by in liquid crystal material, adding chiral reagent.On the other hand, owing in the normal white type, keep white show state, make positive contrast reduce.Therefore, can provide and stop this regional photoresistance and cut layer for example at the bottom of the fast black base.

Be positioned at and leave polarization film 11 and polarization film 101 and preferably substantially parallel each other or vertical with 103 slow axis 13a with 103a near the slow axis 13 of the protective film of liquid crystal layer side.When the slow axis 13a of transparent

protective film

13 and 103 and 103a were perpendicular to one another, the birefringence of each protective film was cancelled each other, and therefore can reduce the deterioration with the optical property of the light of liquid crystal indicator vertical incidence.In the slow axis 13a embodiment parallel, when in liquid crystal layer, having residual retardance, can use birefringence-compensated this delay of protective film with 103a.

According to laminate structures of material used in each element, display type or element or the like; the slow-axis direction 13a of the absorption axes 12 and 102 of

polarization film

11 and 101,

protective film

13 and 103 and the direction of orientation of 103a and liquid crystal molecule 17 are adjusted to optimum range.That is, the absorption axes 102 of

polarization film

11 and 101 absorption axes 12 and polarization film 101 is through installing perpendicular each other.Yet liquid crystal indicator of the present invention is not limited to this structure.

The optical compensating film 15 and 19 that is installed in respectively between liquid crystal cell and polarization film 11 and the polarization film 101 is optical compensating films, and as mentioned above, for example, formed by the birefringent polymer film, perhaps the laminated thing by transparent supporting body and the optical anisotropic layer that is made of liquid crystal molecule that forms on transparent supporting body forms.In addition, in the face of optical compensating film 15 slow axis 15a preferably through installation with near absorption axes 12 perpendicular of the polarization film of installing 11.Similarly, in the face of optical compensating film 19 slow axis 19a preferably through installation with near absorption axes 102 perpendicular of the polarization film of installing 101.When by this way absorption axes being installed, optical compensating film 15 or 19 produces with respect to the light from normal direction incident and postpones, and does not therefore produce light leak, can fully realize effect of the present invention with respect to the light from vergence direction incident simultaneously.The combination of the combination of optical compensating film 15 and transparent protective film 13 and/or optical compensating film 19 and transparent protective film 103 can be made up the performance that makes the delay sum satisfy following formula (I)-(IV) and liquid crystal layer, optical compensation liquid crystal cell 16-18 thus.Transparent protective film 13 and 103 satisfies following formula (IX) and (X) and be the element with low optical anisotropy and low wavelength dispersibility, and therefore the design with the optical anisotropic layer combination is feasible.Equally, because the polarizer of backlight side (showing among Fig. 8) may be exposed under the high temperature that causes because of heat backlight, so the protective film of polarization film often is out of shape thus that optical property changes, and therefore light leak takes place in framework.The liquid crystal indicator of Fig. 8 uses the cellulose acylate with low optical anisotropy and low wavelength dispersibility as transparent protective film 13 and 103, and therefore can reduce this light leak in the framework.

In addition; when one of transparent

protective film

13 and 103 are when satisfying following formula (IX) and cellulose acylate film (X); obtain same effect, particularly preferably be formed on the transparent protective film (the transparent protective film of installing near liquid crystal cell) of the polarizer of backlight side installation by this cellulose acylate film.

Do not apply under the non-operating state of driving voltage in single transparency electrode (not shown) liquid

crystal cell substrate

16 and 18, liquid crystal molecule 17 in the liquid crystal layer is almost vertically arranged with the surface of

substrate

16 and 18, as a result, polarization state of transmitted light does not change in fact.Because absorption axes 12 is vertical mutually with 102, therefore the light from downside (for example, the backlight side electrode) incident keeps polarization state simultaneously through polarization film 101 polarizations and through liquid crystal cell 16-18, is polarized film 11 at last and stops.That is, in the liquid crystal indicator of Fig. 8, desirable black state is realized at non-operating state.The transparency electrode (not shown) is being applied under the mode of operation of driving voltage in this, liquid crystal molecule 17 is tilting with 18 surperficial parallel direction with substrate 16, and transmitted light polarization state under the effect of inclination liquid crystal molecule 17 changes.Therefore, through polarization film 101 polarizations and see through liquid crystal cell 16-18 polarization state is changed, see through polarization film 11 from the light of downside (for example, the backlight side electrode) incident at last.That is, can realize that to the mode of operation that applies voltage white shows.

The feature of VA type is its high contrast.Yet even the problem that conventional VA type liquid crystal indicator exists is positive contrast height, the contrast of vergence direction also reduces.Because liquid crystal molecule 17 is arranged with the Surface Vertical of

substrate

16 and 18 under black state, when from top view, liquid crystal molecule 17 does not almost have birefringence and therefore has low transmissivity, and can obtain high contrast.Yet when when vergence direction is observed, liquid crystal molecule 17 has birefringence.And up and down

polarization film

11 and 101 absorption axes 12 are vertical with 90 ° from the front with 102 the angle of the crossing, but when when vergence direction is observed greater than 90 °.Usually, the problem of existence is to have light leak and reduce because of these two factors make contrast at vergence direction.In having the liquid crystal indicator of the present invention of structure shown in Figure 8; because the optical property of liquid crystal layer 7; use optical compensating film 15 with the optical property that satisfies specified conditions and 19 and as the transparent

protective film

13 and 103 of cellulose acylate film reduced black state have a down dip direction light leak and improved contrast.Equally, also make the design of liquid crystal indicator easier.

Fig. 8 has described respectively liquid crystal cell both sides between liquid crystal cell and

polarization film

11 and 101 liquid crystal indicator of optical compensating

film

15 and 19 has been installed; Yet, an optical compensating film can only be arranged.In this embodiment, following formula (V)-(VIII) is satisfied in optical compensating film and liquid crystal layer combination, and therefore carries out the precise optical compensation of liquid crystal layer.In the present embodiment,, satisfy following formula (IX) and cellulose acylate film (X) and can be installed between optical compensating film and liquid crystal layer or the polarization film, to reduce the light leak in the framework as the structure of Fig. 8.And, can make the design of liquid crystal indicator easier.

The liquid crystal indicator of second embodiment is not limited to structure shown in Figure 8 and also can comprises other element.For example, can between liquid crystal cell and polarization film, color filter be installed.When as transmission-type, can be installed in backlight side with having cold cathode or thermic cathode fluorimetric pipe, light emitting diode, field emission apparatus or el light emitting device backlight as light source.

The liquid crystal indicator of second embodiment comprises the Direct observation type, image projection's type and light modulation type.For example the embodiment of TFT or MIM is effective especially at the active matrix liquid crystal display apparatus that display device of the present invention is used for use three ends or two ends semiconductor device in the present invention.Certainly, the embodiment that is used for the passive matrix liquid crystal indicator (be also referred to as time-division drive) of STN type representative in display device of the present invention also is effective.

Below, description can be used for the polarizer of the liquid crystal indicator of second embodiment.As mentioned above, can use utilization to have the polarizer of the cellulose acylate film of predetermined optical properties valuably as the protective film of polarization film.In the following description, be the situation of cellulose acylate film although do not mention protective film especially, below term also can be used for preparing and have the situation of cellulose acylate film as the polarizer of the protective film of polarization film.

[polarizer]

In second embodiment, can use by polarization film and this polarization film the polarizer that a pair of protective film is wherein formed is installed.For example, can use the polarization film that forms by polyvinyl alcohol film etc. by with iodine staining, with this film stretching, and with the polarizer of laminated this film both sides acquisition of protective film.Polarizer is installed in the outside of liquid crystal cell.The a pair of polarizer that preferred each free polarization film and this polarization film installation a pair of protective film are wherein formed is installed in the both sides of liquid crystal cell.

＜protective film 〉

The polarizer that can be used for second embodiment can have and is laminated in a pair of protective film in polarization film both sides (also being referred to as protective film).The type of protective film has no particular limits, and can use cellulose acetate ester, cellulose acetate-butyrate ester, cellulose esters for example cellulose propionate ester, polycarbonate-based, polyolefin, polystyrene and polyesters etc.As mentioned above, satisfy the thin polymer film of the required optical property of optical compensating film, can give the double action of protective film as optical compensating film and protective film by use.

Protective film preferably links to each other continuously with the polarization film of often supplying with web-like, and therefore has long length, and these films are at vertical consistency like this.Here, the axis of orientation of protective film (slow axis) can be an any direction, but from the angle of operation convenience, the axis of orientation of protective film preferably with parallel longitudinal.

With regard to the protective film that wherein is inserted with polarization film, can use slow axis basically with those consistent films of direction of the mean refractive index maximum of film surface.That is, at least one protective film is the film that concerns nx, ny=nz and nx＞ny by satisfying; Satisfy the film that concerns nx=ny, nz and nx＞nz; Deng what form, wherein nx, ny and nz are three mean refractive indexs in the direction of the x that is perpendicular to one another, y and z axle, and wherein the interior mean refractive index of face is designated as nx and ny, and the mean refractive index of thickness direction is designated as nz.As mentioned above; under the situation of giving protective film optical compensation ability; the ratio of Re and Rth under the wavelength of the 450nm of visible region; promptly; Re/Rth (450nm) is 0.4 to 0.95 times of Re/Rth (550nm) under the wavelength of 550nm; and the Re/Rth under the wavelength of 650nm (650nm) 1.05 to 1.9 times of the Re/Rth (550nm) under the wavelength of 550nm preferably, and the delay Rth of the thickness direction under the wavelength of 550nm 70nm-400nm preferably.

Simultaneously, do not play a part in the embodiment of optical compensating film at protective film, the delay of transparent protective film is preferably low.In the uneven embodiment of axis of orientation of the absorption axes of polarization film and transparent protective film; particularly when the length of delay of transparent protective film surpasses certain value; the polarization axle of transparent protective film and axis of orientation (slow axis) oblique arrangement; and linear polarization becomes oval polarization, thinks that it is not desirable.Therefore, with respect to 632.8nm, the delay of transparent protective film is, for example, and preferred 10nm or littler, more preferably 5nm or littler.With regard to postponing low thin polymer film, preferably use cellulose triacetate, polyolefin for example ZEONEX, ZEONOR (all being Nippon Zeon Co., the product of Ltd.) and ARTON (JSR Corp.).In addition, for example, also can mention the non-birefringence optics resin material described in JP-A 8-110402 and the 11-293116.In the present embodiment, when using the laminated thing be made up of supporter and the optical anisotropic layer that comprises liquid-crystal compounds on supporter as optical compensating film, protective film can play the supporter of optical anisotropic layer.

When protective film is adhered on the polarization film, preferably the absorption axes (tensile axis) of the laminated slow axis (axis of orientation) that makes at least one protective film (in being installed in liquid crystal indicator time install near liquid crystal cell protective film) of protective film and polarization film with polarization film intersected.Particularly, preferably 10 °-90 ° of the angles between the slow axis of the absorption axes of polarization film and protective film, more preferably 20 °-70 °, even more preferably 40 °-50 °, preferred especially 43 °-47 °.Angle between the slow axis of opposite side protective film and the absorption axes of polarization axle has no particular limits, and can suitably adjust according to the purpose of polarizer.Yet described angle is preferably in above-mentioned scope, and also preferred this slow axis to protective film is consistent with each other.

In addition, when the absorption axes of the slow axis of protective film and polarization film is parallel to each other, can improve the change in size of polarizer and the mechanical stability of polarizer (being referred to as to prevent to curl).When at least two axles of three films altogether of being made up of polarization film and a pair of protective film, the slow axis of the slow axis of a protective film and the absorption axes of polarization film or two protective films when substantially parallel, can obtain identical effect.

＜bonding agent 〉

The bonding agent that is used for polarization film and protective film has no particular limits; but can mention the aqueous solution of PVA resin (comprising PVAs) or boron compound with modifications such as acetoacetyl, sulfonic group, carboxyl or oxyalkylene groups; and in the middle of them, preferred PVA resin.The thickness of dry bonding coat afterwards is 0.01-10 μ m, preferred especially 0.05-5 μ m preferably.

The integral preparation process of＜polarization film and transparent protective film 〉

After the film stretching that polarization film is used, the polarizer that can be used for second embodiment is through dry run, and wherein film contraction and volatility partly reduce.Yet, preferably after dry run or in dry run, transparent protective film is adhered at least one surface of polarizer, add back heating process then.Play a part in the embodiment of supporter of optical anisotropic layer at transparent protective film; wherein said optical anisotropic layer is as the optical compensating film effect; preferably after the transparent supporting body that transparent protective film is adhered to polarizer one side and will has an optical anisotropic layer is adhered to the polarizer opposite side, carry out back heating process.As a kind of concrete adhesive bonding method; can utilize in the film drying process; when keeping two ends, transparent protective film is adhered on the polarization film with bonding agent; then two ends are repaired; perhaps after drying; take off the film that polarization film is used from the retaining part of end, with the finishing of film both sides, the method for bonding transparent protective film then.With regard to method for trimming, can use common process for example to use cutter such as blade cuts, adopt laser instrument etc.After bonding, preferably with plate heating with dry adhesive and improve polarization property.Heating condition can change with bonding agent, but under the situation that is Aquo System, preferred 30 ℃, more preferably 40 ℃-100 ℃, even more preferably 50 ℃-90 ℃.From the angle of performance and working (machining) efficiency, these processes are more preferably carried out with incorporate method.

The performance of＜polarizer 〉

With the superelevation contrast form of commercially available acquisition (for example; the HLC2-5618 of Sanritsu Corp. etc.) compare, preferably the optical property and the durability (short-term and long-term preservability) of the polarizer of being made up of transparent protective film, polarizer and transparent supporting body according to second embodiment show quite or more performance.More particularly, preferred transmission of visible light is 42.5% or bigger, (wherein Tp is parallel transmissivity to degree of polarization { (Tp-Tc)/(Tp+Tc) } 1/2 〉=0.9995, Tc is the intersection transmissivity), based on absolute value, polarizer under the environment of the humidity of 60 ℃ and 90%RH, leave standstill 500 hours then before leaving standstill 500 hours under 80 ℃ the dry environment and the variation ratio of transmissivity afterwards be 3% or littler, more preferably 1% or littler, and based on absolute value, the variation ratio of degree of polarization under the same conditions is 1% or littler, more preferably 0.1% or littler.

The 3rd embodiment

Next, explain the 3rd embodiment of the present invention.

The optical compensating gage (following also be referred to as " optical compensating gage I ") that is the form of the 3rd embodiment is to have transparent supporting body and optical anisotropic layer A that satisfies following formula (3) that forms in succession that satisfies following formula (1) and (2) and the optical compensating gage that satisfies the optical anisotropic layer C of following formula (4) thereon.

The optical compensating gage (following also be referred to as " optical compensating gage II ") that is another form of the 3rd embodiment is to have transparent supporting body and optical anisotropic layer C that satisfies following formula (4) that forms in succession that satisfies following formula (1) and (2) and the optical compensating gage that satisfies the optical anisotropic layer A of following formula (3) thereon.

(1) 0≤Re ₍₅₉₀₎≤ 10 Hes | Rth ₍₅₉₀₎|≤25,

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200,

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400.

In the 3rd embodiment, owing to form the transparent supporting body that satisfies following formula (1) and (2) of optical compensating gage, so the optical compensation that can realize ideal, and the optical property of transparent supporting body is free from side effects to the optical compensation effect of optical anisotropic layer, aberration when specifically, the black state downwards angle of visibility that can improve liquid crystal indicator is from positive face tilt.Following formula (1) is 0≤Re preferably ₍₅₉₀₎≤ 5 Hes | Rth ₍₅₉₀₎|≤10nm, preferred especially 0≤Re ₍₅₉₀₎≤ 3 Hes | Rth ₍₅₉₀₎|≤5nm.Following formula (2) is preferably | Re ₍₄₅₀₎-Re ₍₆₅₀₎|≤5 Hes | Rth ₍₄₅₀₎-Rth ₍₆₅₀₎|≤25, preferred especially | Re ₍₄₅₀₎-Re ₍₆₅₀₎|≤3 Hes | Rth ₍₄₅₀₎-Rth ₍₆₅₀₎|≤15.

Below, further describe transparent supporting body.

[transparent supporting body]

The transparent supporting body that is used for the 3rd embodiment is thin polymer film preferably, and material therefor preferably has the material of little intrinsic birefringence, for example the cycloalkenyl group polymkeric substance.The instantiation of cyclic olefin polymer comprises those described in JP-A 1-132625,1-132626,1-240517,63-145324,63-264626,63-218726,2-133413,60-168708,61-120816,60-115912,62-252406,60-252407, WO 2004/049011A1, WO2004/068226A1 and the WO 2004/070463A1 etc.Equally, the cycloalkenyl group polymkeric substance of operable commercially available acquisition comprises ARTON (JSR Corp.), ZEONOR (Nippon Zeon Co., Ltd.), ZEONEX (Nippon Zeon Co., Ltd.) and ESCENA (Sekisui Chemical Co., Ltd.).

With regard to the transparent supporting body that is used for the 3rd embodiment,, more preferably use cellulose acylate film from the conventional preparation technology's that can use polarizer angle.Its details for example can be used for the preparation method of cellulose acylate film of the 3rd embodiment and raw material as described in top first embodiment.

[adjuvant of cellulose acylate]

In the 3rd embodiment; can be according to each preparation technology's purposes; various adjuvants (for example, reduce optically anisotropic compound, dispersion adjustment agent, ultraviolet blocking agent, plastifier, degraded and prevent agent, particulate, optical property correctives etc.) are joined the cellulose acylate solution that is used for preparing cellulose acylate film.The interpolation time can be any stage of dope preparation process, but preferably adds adjuvant in the last preparation process of dope preparation process, further carries out production run then.

Transparent supporting body particularly preferably contains at least a reduction optical anisotropy, particularly Re by the transparent supporting body that is formed by cellulose acylate film that is used for the 3rd embodiment _(λ)And Rth _(λ), Rth especially _(λ), compound to the degree that satisfies following formula (5) and (6).

(5)(Rth _(λ)(A)-Rth(0))/A≤-1.0

(6)0.01≤A≤30。

Following formula (5) and (6) are more preferably

(5)(Rth _(λ)(A)-Rth(0))/A≤-2.0

(6)0.05≤A≤25，

Even more preferably

(5)(Rth _(λ)(A)-Rth(0))/A≤-3.0

(6)0.1≤A≤20，

Rth wherein _(λ)(A): the reduction Rth that contains A% _(λ)The Rth of transparent supporting body of compound _(λ)(nm), Rth _(λ)(0): do not contain and reduce Rth _(λ)The Rth of transparent supporting body of compound _(λ)(nm), A: the weight (%) of described compound when the weight of the raw polymer of transparent supporting body is 100.

Can be used for the architectural feature of optically anisotropic compound of reduction transparent supporting body (particularly, the transparent supporting body that forms by cellulose acylate film) of the 3rd embodiment and performance as described in top first embodiment.

The instantiation of optically anisotropic compound that is preferred for the reduction transparent supporting body (particularly, the transparent supporting body that is formed by cellulose acylate film) of the 3rd embodiment comprises the compound of following formula (13), (18) and (19) representative.

[wavelength dispersion correctives]

In the 3rd embodiment, preferably in transparent supporting body, add to reduce the compound (below also be referred to as the dispersion adjustment agent) of the chromatic dispersion of film.

And, according to the 3rd embodiment, preferably add the compound of the chromatic dispersion of the Rth that at least a reduction following formula (iv) represents, (iv) Δ Rth=|Rth ₍₄₀₀₎-Rth ₍₇₀₀₎|, to satisfying following formula (v) with (degree vi) is so that improve the chromatic dispersion of the Rth of transparent supporting body (preferred, cellulose acylate film).

(vi)ΔRth＝|Rth ₍₄₀₀₎-Rth ₍₇₀₀₎|

(v)(ΔRth(B)-ΔRth(0))/B≤-2.0

(vi)0.01≤B ≤30。

Following formula (v) and (vi) more preferably

(v)(ΔRth(B)-ΔRth(0))/B≤-3.0

(vi)0.05≤B≤25，

Even more preferably

(v)(ΔRth(B)-ΔRth(0))/B≤-4.0

(vi)0.1≤B≤20。

The details of dispersion adjustment agent such as top first embodiment are described.

[matting agent particulate, plastifier, degraded prevent agent, release agent]

Preferably particulate is joined and be used in the transparent supporting body of the present invention (preferred, cellulose acylate film) as matting agent.And; according to second embodiment; except reducing optically anisotropic compound and dispersion adjustment agent; can be according to the purposes of production technology separately; with various adjuvants (for example; plastifier, ultraviolet blocking agent, deterioration preventing agent, release agent, infrared absorbent etc.) join in the transparent supporting body (preferred, cellulose acylate film).Its details such as top first embodiment are described.

Be used for that transparent supporting body of the present invention (preferred, cellulose acylate film) preferably makes by the solvent cast method, and the preferred solution (dope) that is dissolved in the cellulose acylate in the organic solvent that uses prepares described supporter.The details of organic solvent is described as first embodiment.And the optical characteristics of the film of the preparation technology of cellulose acylate film, the 3rd embodiment and the details of performance are also described as first embodiment.

[optical compensating gage]

The optical compensating gage I of the 3rd embodiment is the optical compensating gage that has the optical anisotropic layer A that satisfies following formula (3) in succession and satisfy the optical anisotropic layer C of following formula (4) on transparent supporting body, and optical compensating gage II is the optical compensating gage that has the optical anisotropic layer C that satisfies following formula (4) in succession and satisfy the optical anisotropic layer A of following formula (3) on transparent supporting body.

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400.

Re wherein _(λ)Be under the wavelength X nm the front length of delay (unit: nm), Rth _(λ)It is the length of delay (unit: nm) of the thickness direction under the wavelength X nm.

In addition, optical compensating gage is meant and is usually used in the optical material of liquid crystal indicator with compensating delay, and has and identical implications such as retardation plate or optical compensating film.Therefore optical compensating gage has birefringence and is used to eliminate display screen painted of liquid crystal indicator or improves viewing angle properties.With regard to transparent supporting body, Re and Rth have little optical anisotropy, make 0≤Re ₍₅₉₀₎≤ 10nm and | Rth ₍₅₉₀₎|≤25nm, and have little chromatic dispersion and make | Re ₍₄₅₀₎-Re ₍₆₅₀₎|≤10 Hes | Rth ₍₄₅₀₎-Rth ₍₆₅₀₎|≤35, therefore can not cause any unnecessary anisotropy.When being used in combination when having birefringent optical anisotropic layer, can represent the only optical property of optical anisotropic layer.

And, according to the 3rd embodiment,, can make the visual angle wideer by laminated two-layer optical anisotropic layer described below on transparent supporting body, and the aberration also can reduce the dark state downwards angle of visibility from positive face tilt the time.Equally, even under the situation of the protective film that is used as polarizer,, also comprise its optical compensating gage as the 3rd embodiment when the time spent of doing that optical compensating gage finally plays optical compensating gage.

In optical compensating gage I, the optical anisotropic layer A that satisfies following formula (3) is combined on the transparent supporting body with the optical anisotropic layer C that satisfies following formula (4) successive layer successively, and in optical compensating gage II, the optical anisotropic layer C that satisfies following formula (4) is laminated in succession successively with the optical anisotropic layer A that satisfies following formula (3).Layer for example oriented film layer and bonding coat can be provided between each transparent supporting body, optical anisotropic layer A and optical anisotropic layer C.

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400.

In the optical compensating gage of first embodiment of the present invention, formula (3) and (4) are preferably

(3) 15≤Re ₍₅₉₀₎≤ 50 and 8≤Rth ₍₅₉₀₎≤ 50

(4) 0≤Re ₍₅₉₀₎≤ 10 and 50≤Rth ₍₅₉₀₎≤ 170.

In optical compensating gage II, formula (3) and (4) are preferably

(3) 50≤Re ₍₅₉₀₎≤ 130 and 25≤Rth ₍₅₉₀₎≤ 130

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 100.

Aberration when reducing the dark state downwards angle of visibility with positive face tilt, the Re of optical anisotropic layer A _(λ)Wavelength dependency preferably satisfy following formula (7) and (8), and the Rth of optical anisotropic layer C _(λ)Wavelength dependency preferably satisfy following formula (9) and (10).

(7)Re ₍₄₅₀₎/Re ₍₅₅₀₎＝0.60-0.98

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.00-1.60

(9)Rth ₍₄₅₀₎/Rth ₍₅₅₀₎＝1.02-1.60

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.60-1.00

Following formula (7), (8), (9) and (10) are more preferably

(7)Re ₍₄₅₀₎/Re ₍₅₅₀₎＝0.7-0.95

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.05-1.3

(9)Rth ₍₄₅₀₎/Rth ₍₅₅₀₎＝1.05-1.3

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.7-0.95。

Constitute the optical anisotropic layer A of optical compensating gage of the 3rd embodiment and C without limits, as long as material satisfies following formula (3) and (4), preferred formula (3), (4) and (7)-(10) to material.These layers can be formed by the composition that contains liquid-crystal compounds, perhaps can form by having birefringent thin polymer film.And optical anisotropic layer C also can be formed by non-liquid-crystal compounds.Non-liquid-crystal compounds has no particular limits, and can use known.

Liquid-crystal compounds is disc liquid-crystal compounds or rod shaped liquid crystal compound preferably.

In addition, optical anisotropic layer A the preparation method can be referring to for example JP-A2002-48919, and the preparation method of optical anisotropic layer C can be referring to for example JP-A2004-4474.

(disc liquid-crystal compounds)

The example that can be used for the disc liquid-crystal compounds of the 3rd embodiment comprises (C.Destrade etc., MoI.Crysr.Liq.Cryst., Vol.71, the 111st page (1981) in the various documents; KikanKagaku Sosetsu, No.22, Ekisho No Kagaku, the 5th chapter, the 10th chapter, the 2nd joint (edit and published) in 1994 by Nihon Kagaku Kai; 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)) described compound.

In optical anisotropic layer, discotic liquid-crystalline molecules is preferably fixed with ordered state, and most preferably crosses polyreaction and fix.The polyreaction of discotic liquid-crystalline molecules is described in JP-A8-27284.For by the fixing discotic liquid-crystalline molecules of polyreaction, polymerizable groups must be connected to the plate-like core of discotic liquid-crystalline molecules as substituting group.Yet, when polymerizable groups directly links to each other with the plate-like core, polyreaction is difficult to keep state of orientation.Therefore, between plate-like core and polymerizable groups, introduce linking group.Discotic liquid-crystalline molecules with polymerizable groups is described in JP-A 2001-4387.

(rod shaped liquid crystal compound)

The rod shaped liquid crystal examples for compounds that can be used for the 3rd embodiment comprises the phenyl pyrimidine class of azomethine class, azoxy base class, cyanobiphenyl class, cyano-phenyl ester class, benzoates, cyclohexane-carboxylic acid phenylester class, cyano-phenyl cyclohexanes, cyano group replacement, phenyl pyrimidine class, benzene base dioxane, diphenyl acetylene class and the thiazolinyl cyclohexyl benzonitrile class that alkoxy replaces.According to the 3rd embodiment, not only above-mentioned combinations of low molecular weight liquid crystals compound, and also the high molecular liquid-crystal compounds also can use.

In optical anisotropic layer, rod shaped liquid crystal molecule is preferably fixed with ordered state, most preferably fixes by polyreaction.Can be used for polymerizable rod shaped liquid crystal examples for compounds of the present invention and comprise Makromol.Chem., the 190th volume, the 2255th page (1989); AdvancedMaterials, the 5th volume, the 107th page (1993); Compound described in USP 4683327, USP 5622648, USP 5770107, WO 95/22586, WO 95/24455, WO 97/00600, WO98/23580, WO 98/52905, JP-A 1-272551, JP-A 6-16616, JP-A 7-110469, JP-A 11-80081 and the JP-A 2001-328973 etc.

(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 can form by expressing optically anisotropic polymkeric substance.The example of this polymkeric substance comprises that polyolefin (for example, tygon, polypropylene, norbornene polymer), polycarbonate, poly-allylat thing, polysulfones, polyvinyl alcohol (PVA), polymethacrylate, polyacrylate and cellulose esters (for example, cellulose triacetate, cellulose diacetate ester).Also can use the multipolymer or the polymeric blends of these polymkeric substance.

The optical anisotropy of thin polymer film preferably obtains by stretching.Preferably uniaxial tension or biaxial stretch-formed stretches.Particularly, preferably utilize two or more rollers rim speed difference vertical uniaxial tension, clamp two sides of thin polymer film and stretch or make up this two kinds biaxial stretch-formed at the stenter that Width stretches.In addition, can use two or more thin polymer films to make total optical property of these two or more films satisfy above-mentioned condition.Thin polymer film preferably prepares so that reduce birefringent scrambling by the solvent cast method.The thickness of thin polymer film is 20-500 μ m preferably, most preferably 40-100 μ m.

Equally, can preferably use such method: at least a polymeric material that will be selected from polyamide, polyimide, polyester, polyetherketone, polyamidoimide-polyester-imide and the PAEK is used as the thin polymer film that forms optical anisotropic layer, with the solution coat substrate that is dissolved in the polymkeric substance in the solvent with fall solvent from the coating drying and form and to film.Here, also advantageously use thin polymer film and substrate are stretched presenting optical anisotropy and to use the method for this product as optical anisotropic layer, and the transparent supporting body that is used for the 3rd embodiment can be advantageously used for substrate.And also preferred the use prepares thin polymer film on another substrate, from described substrate release polymers film, then this thin polymer film is adhered to method standby on the transparent supporting body.In the method, the thickness of thin polymer film can be done for a short time, and this thickness preferably 50 μ m or littler, more preferably 1-20 μ m.

[polarizer]

The polarizer of the 3rd embodiment is the polarizer that has protective film in the polarizer both sides; and be the polarizer of following feature: at least one protective film is the optical compensating gage of the 3rd embodiment, with and the surface on transparent support side link to each other with polarizer.When the optical compensating gage of the 3rd embodiment was used as the film of protection polarizer, the preparation method of polarizer had no particular limits, and can use conventional preparation method.For example; can mention a kind of gained cellulose acylate film that makes through alkali treatment, and the cellulose acylate film that uses the aqueous solution of fully saponified poly-vinyl alcohol solution to handle is adhered to by polyvinyl alcohol film being soaked and the method for the both sides of the polarizer that makes of stretching in iodine solution.Cellulose acylate film can be processed through the excellent bonds described in JP-A 6-94915 and 6-118232 and replace alkali treatment.

The bonding agent that is used for the surface treated of bonding protective film and polarizer can have been enumerated for example polyvinyl alcohol (PVA) or polyvinyl butyral or vinyl latex butyl acrylate etc. for example of poly (vinyl alcohol) binder.With regard to polarizer of the present invention, at least one surface of protective film, can provide the layer of the one deck at least that is selected from hard conating, anti-glare layer, anti-reflecting layer, stain-proofing layer and the antistatic layer.With regard to these layers, can use known.If necessary, also can in protective film, add various adjuvants for example plastifier, ultraviolet light absorber, short release agent, dyestuff, matting agent and electrically conductive particles.Its details as mentioned above.

Polarizer comprises the protective film on polarizer and two surfaces of protection polarizer, and polarizer can also be by constituting at the bonding protector film in a surface of polarizer and at the bonding barrier film of facing surfaces.Protector film and barrier film are used for waiting between the product detection period of transportation polarizer and polarizer protects polarizer.In this case, the protector film through bonding with the protection polarizer the surface and be used for the opposite side on the surface that links to each other with liquid crystal board of polarizer.Barrier film is used to cover the bonding coat that links to each other with liquid crystal board, and is used for the side on the surface that polarizer links to each other with liquid crystal board.

Liquid crystal indicator often has the substrate that contains liquid crystal at two polarizers, and the optical compensating gage of the 3rd embodiment is used for the protective film of liquid crystal cell side as polarizer.The protective film of the polarizer on the outmost surface of the demonstration side of liquid crystal indicator often provides transparent hard conating, anti-glare layer or anti-reflecting layer etc.

[liquid crystal indicator]

As the liquid crystal indicator (following also be referred to as " liquid crystal indicator I ") of the form of the 3rd embodiment is a kind ofly to have liquid crystal cell and a pair of liquid crystal indicator that is installed in the polarizer of liquid crystal cell both sides, and is the liquid crystal indicator that is characterised in that a kind of described at least one polarizer is the polarizer of the 3rd embodiment.

Liquid crystal indicator (following also be referred to as " liquid crystal indicator II ") as another form of the 3rd embodiment is a kind of have liquid crystal cell and a pair of liquid crystal indicator that is installed in the polarizer of liquid crystal cell both sides; and be that a kind of polarizer that is characterised in that comprises polarizer and a pair of protective film that accompanies this polarizer therebetween, and at least one protective film is the liquid crystal indicator of the optical compensating gage of the 3rd embodiment.

The liquid crystal indicator of the 3rd embodiment has the protective film of aforesaid optical compensating gage of the present invention as polarizer, and wherein the aberration when dark state downwards angle of visibility and positive face tilt improves, and therefore can realize high display quality.

The liquid crystal layer of liquid crystal cell often forms by sealing liquid crystal in the gap of inserting sept formation between two substrates.On substrate, can form transparent electrode layer as the transparent membrane that contains conductive material.Liquid crystal cell can also have glass gas barrier layer, hard conating or internal coating (being used for bonding transparent electrode layer).These layers often are provided on the substrate.The thickness of the substrate of liquid crystal cell is generally 50 μ m-2mm.

Liquid crystal cell in the liquid crystal indicator of the 3rd embodiment can be the liquid crystal cell of various display types.Can mention various display types for example TN (twisted nematic), IPS (face internal conversion), FLC (ferroelectric liquid crystals), AFLC (anti-ferroelectric liquid crystals), OCB (optical compensation curved), STN (STN Super TN), VA (homeotropic alignment) and HAN (mix and arrange) to row.Wherein, the liquid crystal cell in the liquid crystal indicator of the 3rd embodiment is VA type or OCB type preferably, preferred especially VA type.

In VA type liquid crystal cell, rod shaped liquid crystal molecule is substantially vertically arranged when not applying voltage.

VA type liquid crystal cell comprises (1) sense stricto VA type liquid crystal cell, wherein rod shaped liquid crystal molecule when not applying voltage substantially vertically arranged and when applying voltage substantial horizontal orientation (described in the JP-A 2-176625), (2) (MVA type) liquid crystal cell, wherein the VA type forms with multiple domain, be used for field-of-view angle and enlarge { " SID97; Digest of Tech.Papers (Proceedings); the 28th volume; the 845th page (1997); (3) (n-ASM type; CPA type) liquid crystal cell, wherein rod shaped liquid crystal molecule is substantially vertically arranged and arrange { Japan Liquid Crystal Symposium to reverse multiple domain when applying voltage when not applying voltage, Proceedings, 58-59 page or leaf (1998), SHARP Technical Journal, the 80th volume, described in the 11st page }, (4) SURVIVAL type liquid crystal cell, wherein make liquid crystal arrange { Display Monthly with multiple domain by gradient electric field, May periodical, the 14th page (1999) }, PVA type liquid crystal cell { " 18th; IDRC Proceedings ", the 383rd page (1998) }.

[embodiment]

Below, by embodiment and Comparative Examples the present invention is described in further detail.Below shown in material, content, ratio, processing content and processing sequence etc. can appropriate change, as long as purpose of the present invention is unaffected.Yet scope of the present invention is not limited to these following instantiations.

First embodiment

[preparation embodiment 1]

(preparation of cellulose acylate film)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare the cellulose acylate solution A thus.

The composition of＜cellulose acylate solution A 〉

Degree of substitution is 2.86 cellulose acetate ester 100 weight portions

Triphenyl phosphate (plastifier) 7.8 weight portions

Phosphoric acid xenyl diphenyl (plastifier) 3.9 weight portions

Methylene chloride (first solvent) 300 weight portions

Methyl alcohol (second solvent) 54 weight portions

1-butanols 11 weight portions

Following composition joined in other mixing channel and heated and stirred to dissolve each component, prepare additive solution B-1 to B-6 thus.

Table 1

The composition of＜additive solution B-1 to B-6 〉

Additive solution	Methylene chloride	Methyl alcohol	Optical anisotropy depressant (A-19)	Wavelength dispersion correctives (UV-102)
Additive solution	Methylene chloride	Methyl alcohol	Optical anisotropy depressant (A-19)	Wavelength dispersion correctives (UV-102)	B-1	80 weight portions	20 weight portions	Do not have	Do not have
B-2	The same	The same	Do not have	2 weight portions	B-1	80 weight portions	20 weight portions	Do not have	Do not have
B-2	The same	The same	Do not have	2 weight portions	B-3	The same	The same	Do not have	4 weight portions
B-4	The same	The same	20 weight portions	Do not have	B-3	The same	The same	Do not have	4 weight portions
B-4	The same	The same	20 weight portions	Do not have	B-5	The same	The same	40 weight portions	Do not have
B-6	The same	The same	40 weight portions	4 weight portions	B-5	The same	The same	40 weight portions	Do not have

The preparation of＜cellulose acetate film sample 001 〉

In the cellulose acylate solution A of 477 weight portions, add the additive solution B-1 of 40 weight portions and the gained potpourri fully stirred and obtain dope.From the curtain coating mouth, with this dope curtain coating to being cooled on 0 ℃ the rotating cylinder.Then, under the solvent of 70 weight % dope peeled off and with needle pin stenter (pin tenter) the film both sides are fixed (JP-A 4-1009's is shown in Figure 3) and under the solvent of 3-5 weight % drying to keep the horizontal draw ratio of (vertical with machine direction) simultaneously be 3% interval.Next, it is passed further drying between the roller of annealing device, obtaining thickness is the cellulose acetate film sample 001 of 80 μ m.

The preparation of＜cellulose acetate film sample 002-003 and 101-105 〉

Prepare cellulose acetate film sample 002-003 and 101-105 in the mode identical with cellulose acetate film sample 001, just being used for preparing the additive solution of cellulose acetate film sample 001 and thickness, to replace with table 2 listed.Measure the spectral-transmission favtor of these samples under wavelength 380nm and 350nm, result, the transmissivity of these samples under wavelength 380nm are 45% or bigger and 95% or littler.Yet, known have only add that the transmissivity of sample under wavelength 350nm of chromatic dispersion correctives arranged is 10% or littler.

Table 2

[preparation embodiment 2]

(preparation of cellulose acylate film)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare the cellulose acylate solution C thus.

The composition of＜cellulose acylate solution C 〉

Degree of substitution is 2.86 cellulose acetate ester 100 weight portions

Methylene chloride (first solvent) 300 weight portions

Methyl alcohol (second solvent) 54 weight portions

1-butanols 11 weight portions

Three kinds of following compositions are joined in other mixing channel and heated and stirred to dissolve each component, prepare additive solution B-7 to B-19 thus.The additive solution B-7 to 19 that adds 40 weight portions in the cellulose acylate solution C of 465 weight portions respectively, obtaining thickness is cellulose acetate film sample 004-007 and the 106-114 of 80 μ m.The transparency of dope that confirms these samples is good, is 85% or bigger, and is used to reduce optically anisotropic compound and dispersion adjustment agent and fully uses with the dope of cellulose acylate.When the mist degree that also confirms these samples was molded as film with box lunch in the scope of 0.01-2%, film had enough transparencies.And, measure the glass temperature (Tg) of these samples, the result, the Tg that confirms these samples is 80-165 ℃, but does not add except the comparative sample 004 of optical anisotropy depressant or dispersion adjustment agent.

[preparation embodiment 3]

(preparation of cellulose acetate ester solution)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, make the cellulose acetate ester solution D thus.

The composition of＜cellulose acetate ester solution D 〉

Degree of substitution is 2.86 cellulose acetate ester 100.0 weight portions

Methylene chloride (first solvent) 402.0 weight portions

Methyl alcohol (second solvent) 60.0 weight portions

(preparation of matting agent solution)

With the mean grain size of 20 weight portions is that the silica dioxide granule (AEROSILR972, by Nippon Aerosil Co., Ltd. makes) of 16nm and the methyl alcohol of 80 weight portions stir and abundant the mixing 30 minutes, obtains the silica dioxide granule dispersion.This dispersion is joined in the decollator with following composition, stirred again 30 minutes or the longer time to dissolve each component, prepare matting agent solution thus.

(composition of matting agent solution)

Mean grain size is silica dioxide granule dispersion 10.0 weight portions of 16nm

Methylene chloride (first solvent) 76.3 weight portions

Methyl alcohol (second solvent) 3.4 weight portions

Cellulose acetate ester solution D 10.3 weight portions

(preparation of additive solution)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare the cellulose acetate ester solution thus.As for reducing optically anisotropic compound and dispersion adjustment agent, use listed those of following table 4.

(composition of additive solution)

Reduce optically anisotropic compound 49.3 amount parts

Wavelength dispersion correctives 7.6 weight portions

Methylene chloride (first solvent) 58.4 weight portions

Methyl alcohol (second solvent) 8.7 weight portions

Cellulose acetate ester solution D 12.8 weight portions

(preparation of cellulose acetate film sample 115)

The above-mentioned cellulose acetate ester solution D of 94.6 weight portions, the matting agent solution of 1.3 weight portions and the additive solution of 4.1 weight portions are filtered mixing then separately respectively.With the belt casting machine with this potpourri curtain coating.The weight ratio that reduces optically anisotropic compound and dispersion adjustment agent and cellulose acetate ester in the above-mentioned composition is respectively 12% and 1.8%.Peel off down film from being with, wherein residual solvent content is 30%, and obtains cellulose acetate film in 40 minutes 140 ℃ of dryings.The residual solvent content of gained cellulose acetate film be 0.2% and film thickness be 40 μ m.

(preparation of cellulose acetate film sample 008-011 and 116-128)

Prepare cellulose acetate film sample 008-011 and 116-128 in the same manner, just reduce type and content those listed replacements in the table 4 of optically anisotropic compound and dispersion adjustment agent in the additive solution.Table 4 is also listed in the solution composition of preparation sample 115.Measure these samples at relative humidity 10% and 80% time poor (Δ Rth=Rth 10%RH-Rth 80%RH) in the delay of film thickness direction.The result, the comparative sample 008 and 009 and have plastifier (phosphoric acid xenyl diphenyl (BDP)) to replace the comparative sample 010 of optical anisotropy depressant and 011 Δ Rth to be not less than or equal 30nm that does not have the optical anisotropy depressant, and optically anisotropic humidity dependence is big.On the other hand, the Δ Rth of sample 115-128 that contains the optical anisotropy depressant and confirms that optically anisotropic humidity dependence reduces in the scope of 0-30nm.And; measure these samples at 25 ℃ of equilibrium moisture contents with 80%RH; the result confirms except sample 008; the equilibrium moisture content of all other samples is 4% or littler; and by adding optical anisotropy depressant and dispersion adjustment agent, all other cellulose acylate films become hydrophobic.Measure these samples 60 ℃ and the moisture-penetrability (based on 80 μ ms) of 95%RH after 24 hours, the result confirms that except sample 008, the moisture-penetrability of all other samples is 400g/m ²24hr or bigger and 2000g/m ²24hr or littler.Confirm that also all samples 115-128 that is added with optical anisotropy depressant and dispersion adjustment agent shows that moisture-penetrability improves when comparing with comparative sample 009 and 010.In addition, except comparative sample 011, all other samples do not form white casse in film, and obtain film with enough transparencies.Yet the total amount of additive compound surpasses the scope of 5-45% thus up to 49% of cellulose acylate in the comparative sample 011.In this case, film forms white casse, and compound precipitation (oozing out).Therefore, can not be evaluated as cellulose acylate film with transparency.

And, the weight change when working sample 126 and 127 leaves standstill 48 hours under 80 ℃ and 90%RH.As a result, the weight change of sample 126 is-0.12%, and the weight change of sample 127 is-0.02%.As for the dispersion adjustment agent, use benzotriazole cpd for example UV-21, UV-22 and UV-23.Yet, confirm not contain molecular weight be less than or equal to 320 UV-23 (molecular weight: sample 127 315.5), better from the angle of retentivity than sample 126.

[preparation embodiment 4]

(preparation of cellulose acylate film)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare the cellulose acylate solution E thus.At this moment, the use degree of substitution is three kinds of cellulose acylates (table 5) of 2.49,2.86 and 2.92.

The composition of＜cellulose acylate solution E 〉

Cellulose acetate ester 100 weight portions

Methylene chloride (first solvent) 300 weight portions

Methyl alcohol (second solvent) 54 weight portions

1-butanols 11 weight portions

Following 5 kinds of compositions are joined in other mixing channel and heated and stirred to dissolve each component, prepare additive solution B-20 to B-25 thus.The additive solution B-20 to 25 that adds 40 weight portions in the cellulose acylate solution E of 465 weight portions respectively, obtaining thickness is cellulose acetate film sample 129-132 and the comparative sample 012-013 of 40 μ m.As for these samples, be determined as follows: change in size and elastic modulus under the weight change under the moisture-penetrability (based on 80 μ m) under the equilibrium moisture content under 10% and 80% relative humidity under poor (the Δ Rth=Rth 10%RH-Rth 80%RH) of the delay of film thickness direction, 25 ℃ and 80%RH, 60 ℃ and the 95%RH after 24 hours, 80 ℃ and the 90%RH after 48 hours and 60 ℃ and the 95%RH after 24 hours in the mode identical with preparation embodiment 3.As a result, confirm using degree of substitution is the sample 129-132 (also containing optical anisotropy depressant and dispersion adjustment agent) of 2.92 cellulose acylate film, is that 2.49 comparative sample 012 is compared with degree of substitution, and all measurements all show improvement.

[preparation embodiment 5]

(preparation of cellulose acylate film)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare cellulose acylate solution F thus.At this moment; use two kinds of cellulose acylate films, wherein a kind of total degree of substitution is that 2.85 (degree of substitution with acetyl group is that 2.06+ propiono degree of substitution is 0.79) and alternative total degree of substitution are 2.70 (degree of substitution with acetyl group is that 1.93+ propiono degree of substitution is 0.77).

The composition of＜cellulose acylate solution F 〉

Cellulose acylate 100 weight portions

Methylene chloride (first solvent) 300 weight portions

Methyl alcohol (second solvent) 54 weight portions

1-butanols 11 weight portions

Join the composition of following table 6 in other mixing channel and heated and stirred to dissolve each component, prepare additive solution B-26 to B-31 thus.The additive solution B-26 to 31 that adds 40 weight portions in the cellulose acylate solution F of 465 weight portions respectively, obtaining thickness is the cellulose acylate film sample 133-139 of 40 μ m.As for these samples, be determined as follows: the moisture-penetrability (based on 80 μ m) under 10% and 80% the relative humidity after under the equilibrium moisture content under poor (the Δ Rth=Rth 10%RH-Rth 80%RH) of the delay of film thickness direction, 25 ℃ and the 80%RH and 60 ℃ and the 95%RH 24 hours in the mode identical with preparation embodiment 3.As a result, confirm using total degree of substitution is the sample 133-139 (also containing optical anisotropy depressant and dispersion adjustment agent) of 2.85 or 2.70 cellulose acylate, compares with the comparative sample 008-010 of preparation embodiment 3, and all measurements all show improvement.

[preparation embodiment 6]

(preparation of cellulose acylate film)

Using degree of substitution with acetyl group is 2.92 cellulose acylate, prepares the cellulose acetate film sample 140-145 that thickness is 80 or 40 μ m in the mode identical with preparation embodiment 3, only is to use following table 7 listed compositions (table 7).

Table 7

[preparation embodiment 7]

(preparation of cellulose acylate film)

Using total degree of substitution is the cellulose acylate of 2.70 (degree of substitution with acetyl group is 1.7 as 1.0+ bytyry degree of substitution); prepare the cellulose acetate film sample 146-150 that thickness is 80 or 40 μ m in the mode identical, only be to use the listed composition (table 8) of following table 8 with preparation embodiment 3.

Table 8

Table has been described the evaluation result of the optical characteristics of cellulose acylate film sample 101-139 that preparation embodiment 1-5 obtains and comparative sample 001-011 among the 9-12.Compare with 010 with the comparative sample 007 of 008-009 or use phosphoric acid xenyl diphenyl (BDP) (BDP is that Log P value is 7.3 conventional plastifier and exceeds the scope of the invention) with not using the comparative sample 001-006 that reduces optically anisotropic compound, use the sample 101-139 that reduces optically anisotropic compound to show that Re (630) and Rth (630) fully reduce, therefore near isotropy.Equally, compare the sample demonstration that is used in combination the compound of regulating chromatic dispersion and reduces optically anisotropic compound with comparative sample | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎| all fully reduce, therefore make chromatic dispersion near zero.

[with reference to embodiment 1]

(preparation of polarizer)

The cellulose acetate film sample 101 that preparation embodiment 1 is obtained soaked 2 minutes in the 1.5N sodium hydrate aqueous solution in 55 ℃.Described sample is washed under room temperature in washing is bathed, and with 0.1N sulfuric acid in 30 ℃ of neutralizations.The gained sample in bathing, is washed then 100 ℃ of heated-air dryings under room temperature in washing again.Thus, with the surperficial saponification of cellulose acylate film.

Then, be the web-like polyvinyl alcohol film of 80 μ m continuously elongated to its initial length 5 times in iodine aqueous solution with thickness, and drying obtain polarization film.Make two cellulose acylate film samples 101, wherein use 3% polyvinyl alcohol (PVA) (PVA-117H, Kuraray Co., Ltd.) aqueous solution as bonding agent with its alkali soapization.By accompanying polarization film betwixt these two films are adhered on the polarization film, obtain the polarizer of both sides thus with cellulose acylate film 101 protections.In this case, the cellulose acylate film sample 101 of both sides is bonding with polarization film so that the slow axis in the cellulose acylate film is parallel with the axis of homology in the polarization film.In the same manner, also make polarizer with respect to the sample 102-150 of preparation embodiment 1-7 and the comparative sample 004 of preparation embodiment 2.Cellulose acylate film sample 101-150 and comparative sample 004 are enough with the cohesive of the polyvinyl alcohol (PVA) that stretches, and the excellent workability of polarizer.Respectively these polarizers are referred to as polarizer 101-150 and polarizer 004 below.

(with reference to Comparative Examples 1)

For reference embodiment 1; prepare polarizer in the same manner, only be to use the polycarbonate film " PANLITE C1400 " (making) of two commercially available acquisitions to replace above-mentioned two cellulose acylate films to protect polarization film by Teijin Chemicals Ltd..Yet, the cohesive deficiency of the polyvinyl alcohol (PVA) of polarizer and stretching, and the effect of the protective film of described polycarbonate film on can not the polarizing film.And, the processibility existing problems of polarizer.

(with reference to Comparative Examples 2)

For reference embodiment 1, prepare polarizer in the same manner, only being to use two thickness is that the ARTON film (being made by JSR Corp.) of 80 μ m replaces two above-mentioned cellulose acylate films to be used to protect polarization film.Yet, the cohesive deficiency of the polyvinyl alcohol (PVA) of polarizer and stretching, and the effect of the protective film of described ARTON film on can not the polarizing film.And, the processibility existing problems of polarizer.

(durability of polarizer)

The polarizer that cellulose acylate film sample 101-150 that use makes with reference to embodiment 1 and comparative sample 004 make leaves standstill them 500 hours under the condition of 60 ℃ and 95%RH.Then, estimate degree of polarization.The result; confirm to use the polarization characteristic of the polarizer of sample 101-150 to be better than using the polarization characteristic of the polarizer of sample 004; and by add reducing optically anisotropic compound or dispersion adjustment agent (the two all not have to add in the comparative sample 004), with the durability raising of the polarizer of cellulose acylate film processing.

[embodiment 1] is installed in the evaluation on the VA type liquid crystal indicator

The preparation of＜polarizer 〉

Prepare polarization film by absorption iodine on the polyvinyl alcohol film that stretches, and by using polyvinyl alcohol-based adhesives, the predetermined cellulose acylate film of table 13 is adhered to polarization film one side as protective film 1.Then, cellulose acetate film (FUJITACK TF80UL in commercially available acquisition, by Fuji Photo Film Co., Ltd. carrying out saponification manufacturing) handles, and use polyvinyl alcohol-based adhesives that the film of saponification is adhered to the opposite side of above-mentioned polarization film, be formed for first polarizer of the device of the device of embodiment 1-6 and Comparative Examples 1-5 thus.

Next, use polyvinyl alcohol-based adhesives, the predetermined cellulose acylate film of table 13 is adhered to a side of polarization film as protective film 1.Then, cellulose acetate film (FUJITACK TF80UL in commercially available acquisition, by Fuji Photo Film Co., Ltd. carrying out saponification manufacturing) handles, and use polyvinyl alcohol-based adhesives that the film of saponification is adhered to the opposite side of above-mentioned polarization film, be formed for second polarizer of the device of the device of embodiment 1-6 and Comparative Examples 1-5 thus.

The preparation of＜retardation films 〉

Obtaining Re (589) in the mode identical with the optical compensating layer A described in the embodiment 1 of JP-A 2003-315556 is that 77nm and Rth (589) are the retardation films 1 of 47nm.And obtaining Re (589) in the mode identical with the optical compensating layer B described in the embodiment 2 of JP-A 2003-315556 is that 1.5nm and Rth (589) are the retardation films 2 of 207nm.(assay method that postpones the delay (Rth) of (Re) and film thickness direction in the face)

With the sample of 30mmx40mm conditioning humidity 2 hours under 25 ℃ and 60%RH, then by light at the normal direction incident wavelength λ of film nm, measure Re (λ) with automatic birefringence meter (KOBRA-21ADH is made by Oji Scientific Instruments).In addition, by using assumed average refractive index value 1.48 and film thickness, based on the length of delay of three direction detections, that is, and aforesaid Re _(λ), in the use face slow axis as sloping shaft from the film normal direction tilt slow axis in+40 ° the length of delay of light measurement of direction incident wavelength λ nm of angle and the use face as sloping shaft from determining Rth with tilt-40 ° the length of delay of light measurement of direction incident wavelength λ nm of angle of film normal direction _(λ)

For retardation films 1, use mean refractive index 1.52.

For retardation films 2, use mean refractive index 1.6.

＜be installed on the VA type liquid crystal indicator

Use bonding agent the retardation films 1 and first polarizer that obtain above is bonding with the combination shown in the table 13.They make that through bonding the nx direction of retardation films 1 is vertical with the absorption axes of first polarizer.Next, use bonding agent the retardation films 2 and second polarizer is bonding with the composition shown in the table 13.They make that through bonding the nx direction of retardation films 2 is parallel with the absorption axes of second polarizer.

As shown in table 13 will by the bonding product 1 of retardation films 1 and first polarizer with by retardation films 2 and bonding product 2 combinations of second polarizer, and use bonding agent respectively these compositions to be adhered on the VA type liquid crystal board.

Here, combination product 1 is installed in the horizontal direction that absorption axes that visible side makes the polarizer of winning is positioned at described plate.Simultaneously, combination product 2 is installed in backlight side and makes that the absorption axes of second polarizer is vertical with described plate.

And by adding bonding agent, the retardation films 1 with bonding product 1 is adhered to VA type liquid crystal board side respectively, and at the opposite side of liquid crystal cell the retardation films of bonding product 2 is adhered to VA type liquid crystal board side.

＜evaluation method 〉

For the liquid crystal indicator that obtains above, at the light leak under the direction detection black state of 45 ° of position angles of front device and 70 ° of polar angles.Described value is more little, and the light leak that takes place in the direction of 45 ° of angles is more little and display device contrast of display degree is good more.And, viewing angle characteristic that can the evaluating liquid crystal device.

◎: do not observe light leak

Zero: the light leak degree is little

△: the light leak degree is moderate

△ *: light leak big (can not accept)

*: light leak serious (can not accept)

For the black displacement, being determined at polar angle is all displacements (Δ uv) of azimuthal direction of 60 °.

◎: aberration is minimum

Zero: aberration is little

△: aberration is moderate

△ *: aberration (can not accept) takes place

*: aberration serious (can not accept)

For turning dyeing, by with liquid crystal indicator thermal treatment 120 hours under 50 ℃ and 95%RH, conditioning humidity is 20 hours under 25 ℃ and 60%RH, then with backlight lightening, estimates the light leak under the dark state.Should estimate, use 20 inches liquid crystal boards.

◎: do not have light leak at four turnings

Zero: any one in four turnings has a small amount of light leak

△: light leak takes place in 1-3 position at four turnings

△ *: light leak (can not accept) all takes place at four turnings

*: the light leak (can not accept) that can discern takes place at four turnings

＜evaluation result 〉

As shown in table 13,1-5 compares with Comparative Examples, and aspect light leak, black displacement and the turning dyeing of the device of embodiment 1-6 under dark state, all or any one aspect all is excellent.Therefore, by between each polarizer and liquid crystal board, retardation films being installed, perhaps satisfy 0≤Re by using ₍₆₃₀₎≤ 10 or | Rth ₍₆₃₀₎|≤25 cellulose acylate film is as the protective film of polarizer, can make up the liquid crystal indicator of turning dyeing with excellent viewing angle characteristic, reduction and excellent display characteristic.

Table 13

	Protective film 1	Protective film 2	Retardation films 1	Retardation films 2	Light leak in the black display	The black displacement	Turning dyeing
	Protective film 1	Protective film 2	Retardation films 1	Retardation films 2	Light leak in the black display	The black displacement	Turning dyeing	The device of embodiment 1	FUJITACK TF80UL Re3nm Rth45nm	Sample number 101 Re1.8nm Rth23nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	△
The device of embodiment 2	FUJITACK TF80UL Re3nm Rth45nm	Sample number 102 Re1.9nm Rth7.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	○△	The device of embodiment 1	FUJITACK TF80UL Re3nm Rth45nm	Sample number 101 Re1.8nm Rth23nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	△
The device of embodiment 2	FUJITACK TF80UL Re3nm Rth45nm	Sample number 102 Re1.9nm Rth7.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	○△	The device of embodiment 3	FUJITACK TF80UL Re3nm Rth45nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○△	○△	○
The device of embodiment 4	Sample number 101 Re1.8nm Rth23nm	Sample number 101 Re1.8nm Rth23nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○	○	○△	The device of embodiment 3	FUJITACK TF80UL Re3nm Rth45nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○△	○△	○
The device of embodiment 4	Sample number 101 Re1.8nm Rth23nm	Sample number 101 Re1.8nm Rth23nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○	○	○△	The device of embodiment 5	Sample number 102 Re1.9nm Rth7.2nm	Sample number 102 Re1.9nm Rth7.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○	○	○
The device of embodiment 6	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Re1.5nm Rth207nm	◎	◎	◎	The device of embodiment 5	Sample number 102 Re1.9nm Rth7.2nm	Sample number 102 Re1.9nm Rth7.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	○	○	○
The device of embodiment 6	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Re1.5nm Rth207nm	◎	◎	◎	The device of Comparative Examples 1	FUJITACKTF80UL Re3nm Rth45nm	Comparative sample number 008 Re5.8nm Rth35.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	×
The device of Comparative Examples 2	Comparative sample number 006 Re5.8nm Rth35.2nm	Comparative sample number 006 Re5.8nm Rth35.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	△×	The device of Comparative Examples 1	FUJITACKTF80UL Re3nm Rth45nm	Comparative sample number 008 Re5.8nm Rth35.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	×
The device of Comparative Examples 2	Comparative sample number 006 Re5.8nm Rth35.2nm	Comparative sample number 006 Re5.8nm Rth35.2nm	Re77nm Rth47nm	Re1.5nm Rth207nm	△	△	△×	The device of Comparative Examples 3	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Do not have	Re1.5nm Rth207nm	△×	△×	◎
The device of Comparative Examples 4	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Do not have	△×	△×	◎	The device of Comparative Examples 3	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Do not have	Re1.5nm Rth207nm	△×	△×	◎
The device of Comparative Examples 4	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Re77nm Rth47nm	Do not have	△×	△×	◎	The device of Comparative Examples 5	Sample number 107 Re0.5nm Rth-2.1nm	Sample number 107 Re0.5nm Rth-2.1nm	Do not have	Do not have	×	×	◎

Second embodiment

[embodiment 2]

Preparation has the liquid crystal indicator identical with member shown in Figure 8.Specifically; member for liquid crystal indicator; from the perspective direction (on) laminated last polarizer (protective film (not shown), polarization film 11, cellulose acylate film 13), optical compensating film 15, liquid crystal cell (upper substrate 16, liquid crystal layer 17, infrabasal plate 18), optical compensating film 19 and following polarizer (cellulose acylate film 101, protective film (not shown)) arranged; light source also is installed as (not shown) backlight, carries out optical analogy and verify its effect.As for optical computing, use LCD MASTER Ver.6.08 (making) by Shintech Inc..As for liquid crystal cell or electrode, substrate and polarizer, use the value of the used material of LCD association area, do not change.As for liquid crystal material, use the liquid crystal material of negative dielectric anisotropic with Δ ε=-4.2.Liquid crystal cell is installed with the direction of 89.9 ° of subvertical pre-tilt angles; The element gap of substrate is 3.6 microns; Liquid crystal retardation under the wavelength 450nm (being the thickness d (micron) of liquid crystal layer and refractive index anisotropy Δ n long-pending (Δ nd)) is 318nm, and the liquid crystal retardation under the wavelength 550nm is under 300nm and the wavelength 650nm to be 295nm.The Re of optical compensating film 15+ cellulose acylate film 13 under each wavelength and optical compensating film 19+ cellulose acylate film 101 and the value of Rth are adjusted to the listed value of table 14 respectively.And, as for cellulose acylate film, be not subjected to wavelength affects, and Rth ₂Be 3nm and Re ₂Be 1nm.As for light source, use the illuminant-C that links to each other with LCD MASTER.

In addition, the element according to the liquid crystal indicator of Fig. 8 can obtain identical result, even backlight and observer's position changes from top to bottom.

And, as a comparison case,, be the Re of optical compensating film 15+ cellulose acylate film 13 and optical compensating film 19+ cellulose acylate film 101 also to carry out optical analogy with the same way as of top identical in structure liquid crystal indicator _SumAnd Rth _SumValue constant, not with wavelength variations.And, this Comparative Examples can be called prior art, this is because conventional optical compensation technology is not considered the chromatic dispersion of Re and Rth.

The mensuration of light leak in the＜liquid crystal indicator 〉

Use above-mentioned value to carry out optical analogy and be displayed in Table 14 the result of calculation of light leak.In table 14, the analog result of the above-mentioned Comparative Examples of liquid crystal indicator 1 representative and the analog result that liquid crystal indicator 2-6 represents embodiment.

Be appreciated that any liquid crystal indicator 2-6 of embodiments of the invention from the result shown in the table 14, wherein when the Δ nd/ λ of liquid crystal under wavelength 450nm is 0.707, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.056-0.113 and its Rth _Sum/ λ is 0.291-0.329, and when the Δ nd/ λ of liquid crystal under wavelength 650nm is 0.454, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.089-0.129 and its Rth _Sum/ λ is 0.165-0.89, compares with liquid crystal indicator 1 as a comparison case, has low transmissivity under dark state under 60 ° of polar angles.Result by table 14 is appreciated that Re under wavelength 450nm _Sum/ λ=0.073 and Rth _Sum/ λ=0.311, Re under the wavelength 550nm _Sum/ λ=0.095 and Rth _SumRe under/λ=0.233 and the wavelength 650nm _Sum/ λ=0.108 and Rth _Sum/ λ=0.177 o'clock, the transmissivity minimum.

Be appreciated that with the liquid crystal indicator 1 that does not satisfy following formula (I)-(IV) from the analog result shown in the table 14 and compare that any liquid crystal indicator 2-6 that satisfies following formula (I)-(IV) has low transmissivity under dark state under 60 ° of polar angles.

[embodiment 3]

By calculating with the condition identical with embodiment 2 with LCD Master, obtain the optical characteristics of liquid crystal indicator, just the wavelength of the length of delay of liquid crystal layer becomes 371nm from 450nm, becomes 350nm and becomes 344nm from 650nm from 550nm.In addition, the Re of optical compensating film 15+ cellulose acylate film 13 and optical compensating film 19+ cellulose acylate film 101 _SumAnd Rth _SumAs shown in Table 15.

And, as a comparison case,, be the Re of optical compensating film 15+ cellulose acylate film 13 and optical compensating film 19+ cellulose acylate film 101 also to carry out optical analogy with the same way as of top identical in structure liquid crystal indicator _SumAnd Rth _SumValue constant, not with wavelength variations.And, this Comparative Examples can be referred to as prior art, this is because conventional optical compensation technology is not considered the chromatic dispersion of Re and Rth.

The mensuration of light leak in the＜liquid crystal indicator 〉

Use above-mentioned value to carry out optical analogy and be displayed in Table 15 the result of calculation of light leak.In table 15, the analog result of the above-mentioned Comparative Examples of liquid crystal indicator 7 representatives and the analog result that liquid crystal indicator 8-12 represents embodiment.

Be appreciated that any liquid crystal indicator 8-12 of embodiments of the invention from the result shown in the table 15, wherein when the Δ nd/ λ of liquid crystal under wavelength 450nm is 0.824, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.044-0.890 and its Rth _Sum/ λ is 0.355-0.405, and when the Δ nd/ λ of liquid crystal under wavelength 650nm is 0.529, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.078-0.115 and its Rth _Sum/ λ is 0.216-0.233, compares with liquid crystal indicator 7 as a comparison case, has low transmissivity under dark state under 60 ° of polar angles.Result by table 15 is appreciated that Re under wavelength 450nm _Sum/ λ=0.067 and Rth _Sum/ λ=0.38, Re under the wavelength 550nm _Sum/ λ=0.082 and Rth _SumRe under/λ=0.28 and the wavelength 650nm _Sum/ λ=0.097 and Rth _Sum/ λ=0.225 o'clock, the transmissivity minimum.

Be appreciated that with the liquid crystal indicator 7 that does not satisfy following formula (I)-(IV) from the analog result shown in the table 15 and compare that any liquid crystal indicator 8-12 that satisfies following formula (I)-(IV) has low transmissivity under dark state under 60 ° of polar angles.

[embodiment 4]

By calculating with LCD Master, acquisition has the optical characteristics of the liquid crystal indicator of structure shown in Figure 8, but in embodiment 4, does not use optical thin film 15.Specifically; from direction of observation (on) laminated polarizer (protective film (not shown), cellulose acylate film 11, protective film 13), liquid crystal cell (upper substrate 16, liquid crystal layer 17, infrabasal plate 18), optical compensating film 19 (also as protective film 103) and the following polarizer (polarizer 101, protective film (not shown)) gone up, the backlight (not shown) also is provided.In addition, the Re of optical compensating film 19 and Rth are shown in table 16.And, the Rth of the cellulose acylate film of last polarizer ₂Be 3nm, and Re ₂Be 1nm, do not depend on wavelength.And, in embodiment 4, provide optical compensating film, but obtain identical result, even the relation between backlight and the observer changes at source backlight.Identical among other condition and the embodiment 2.

And as a comparison case, also to carry out optical analogy with the same way as of top identical in structure liquid crystal indicator, just the value of the Re of optical compensating film 19+ cellulose acylate film 11 and Rth is constant, not with wavelength variations.And, this Comparative Examples can be referred to as prior art, this is because conventional optical compensation technology is not considered the chromatic dispersion of Re and Rth.

The mensuration of light leak in the＜liquid crystal indicator 〉

Use above-mentioned value to carry out optical analogy and be displayed in Table 16 the result of calculation of light leak.In table 16, the analog result of the above-mentioned Comparative Examples of liquid crystal indicator 13 representatives and the analog result that liquid crystal indicator 14-18 represents embodiment.

Be appreciated that any liquid crystal indicator 14-18 of embodiments of the invention from the result shown in the table 16, wherein when the Δ nd/ λ of liquid crystal under wavelength 450nm is 0.707, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.082-0.133 and its Rth _Sum/ λ is 0.513-0.531, and when the Δ nd/ λ of liquid crystal under wavelength 650nm is 0.454, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.123-0.163 and its Rth _Sum/ λ is 0.332-0.357, compares with liquid crystal indicator 13 as a comparison case, has low transmissivity under dark state under 60 ° of polar angles.Result by table 16 is appreciated that Re under wavelength 450nm _Sum/=0.107 and Rth _Sum/ λ=0.54, Re under the wavelength 550nm _Sum/ λ=0.125 and Rth _SumRe under/λ=0.424 and the wavelength 650nm _Sum/ λ=0.416 and Rth _Sum/ λ=0.351 o'clock, the transmissivity minimum.

Be appreciated that with the liquid crystal indicator 13 that does not satisfy following formula (V)-(VIII) from the analog result shown in the table 16 and compare that any liquid crystal indicator 14-18 that satisfies following formula (V)-(VIII) has low transmissivity under dark state under 60 ° of polar angles.

[embodiment 5]

By calculating with the condition identical with embodiment 4 with LCD Master, obtain the optical characteristics of liquid crystal indicator, just the wavelength of the length of delay of liquid crystal layer becomes 371nm from 450nm, becomes 350nm and becomes 344nm from 650nm from 550nm.In addition, the Re of optical compensating film 19+ cellulose acylate film 11 _SumAnd Rth _SumShown in table 17.

And, as a comparison case,, be the Re of optical compensating film 19+ cellulose acylate film 11 also to carry out optical analogy with the same way as of top identical in structure liquid crystal indicator _SumAnd Rth _SumValue constant, not with wavelength variations.And, this Comparative Examples can be called prior art, this is because conventional optical compensation technology is not considered the chromatic dispersion of Re and Rth.

The mensuration of light leak in the＜liquid crystal indicator 〉

Use above-mentioned value to carry out optical analogy and be displayed in Table 17 the result of calculation of light leak.In table 17, the analog result of the above-mentioned Comparative Examples of liquid crystal indicator 19 representatives and the analog result that liquid crystal indicator 20-24 represents embodiment.

Be appreciated that any liquid crystal indicator 20-24 of embodiments of the invention from the result shown in the table 17, wherein when the Δ nd/ λ of liquid crystal under wavelength 450nm is 0.824, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.059-0.115 and its Rth _Sum/ λ is 0.634-0.69, and when the Δ nd/ λ of liquid crystal under wavelength 650nm is 0.529, the Re of optical compensating film+cellulose acylate film _Sum/ λ is 0.099-0.141 and its Rth _Sum/ λ is 0.416-0.427, compares with liquid crystal indicator 19 as a comparison case, has low transmissivity under dark state under 60 ° of polar angles.Result by table 17 is appreciated that Re under wavelength 450nm _Sum/ λ=0.087 and Rth _Sum/ λ=0.662, Re under the wavelength 550nm _Sum/ λ=0.105 and Rth _SumRe under/λ=0.507 and the wavelength 650nm _Sum/ λ=0.12 and Rth _Sum/ λ=0.422 o'clock, the transmissivity minimum.

Be appreciated that with the liquid crystal indicator 19 that does not satisfy following formula (V)-(VIII) from the analog result shown in the table 17 and compare that any liquid crystal indicator 20-24 that satisfies following formula (V)-(VIII) has low transmissivity under dark state under 60 ° of polar angles.

The 3rd embodiment

(the positive mensuration that postpones the delay Rth of Re and film thickness direction)

With the sample of 30mmx40mm conditioning humidity 2 hours under 25 ℃ and 60%RH, then by light at the normal direction incident wavelength λ of film nm, measure Re (λ) with automatic birefringence meter (KOBRA-21ADH is made by Oji Scientific Instruments).In addition, by using described assumed average refractive index value of table 18 and film thickness, length of delay based on three direction detections, promptly, aforesaid Re (λ), in the use face slow axis as sloping shaft from the film normal direction tilt slow axis in+40 ° the length of delay of light measurement of direction incident wavelength λ nm of angle and the use face as sloping shaft from determining Rth (λ) with tilt-40 ° the length of delay of light measurement of direction incident wavelength λ nm of angle of film normal direction.

Preparation embodiment 8: structure with protective film (LR1) of anti-reflecting layer

[preparation of the coating fluid of light scattering layer]

The pentaerythritol triacrylate of 50g and the potpourri of pentaerythritol tetracrylate (PETA, by Nippon Kayaku Co., the Ltd. makes) dilution with toluene of 38.5g.And, add the polymerization initiator (IRGACURE 184, made by Ciba Specialty Chemicals) of 2g and the gained potpourri is mixed.By applying this solution and filming with UV cured acquisition, its refractive index is 1.51.

In addition, and the crosslinked polystyrene particle of adding 1.7g in described solution (refractive index 1.60, SX-350 is by Soken Chemical﹠amp; Engineering Co., Ltd. makes) 30% toluene dispersion, the mean grain size of described crosslinked polystyrene particle is 3.5 μ m and has disperseed 20 minutes under 10000rpm in the Polytron dispersion machine; (refractive index 1.55 is by Soken Chemical﹠amp with cross linked acrylic-styrene particle of 13.3g; Engineering Co., Ltd. makes) 30% toluene dispersion, the mean grain size of described cross linked acrylic-styrene particle is 3.5 μ m.At last, to the fluorine-based surface modifier (FP-1) that wherein adds 0.75g and; The silane coupling agent of 10g (KBM-5103, by Shin-Etsu Chemical Co., Ltd. makes).Gained potpourri via hole diameter is that the polypropylene filter of 30 μ m filters the coating fluid that obtains light scattering layer thus.

Fluorine-based surface modifier (FP-1)

(preparation of the coating fluid of low-index layer)

At first, be prepared as follows sol solution.

In the reactor that is equipped with stirrer and reflux condenser, add the methyl ethyl ketone of 120 weight portions, the acryloxy propyl trimethoxy silicane (KBM-5103 of 100 weight portions, by Shin-Etsu Chemical Co., Ltd. makes) and the ethyl acetoacetate base diisopropoxy aluminium and the mixing of 3 weight portions.Add after the ion exchange water of 30 weight portions, the gained potpourri was cooled to room temperature in 4 hours then 60 ℃ of reactions, obtain sol solution a.Its weight-average molecular weight is 1600, and molecular weight is the ingredients constitute oligomer component of 1000-20000 and the 100 weight % of Geng Gao.By gas chromatographic analysis, not remaining raw material propylene acyloxy propyl trimethoxy silicane.

The refractive index that under agitation adds 13g is 1.42 heat cross-linking fluoropolymer (JN-7228, solids content 6 weight %, make by JSR Corporation), silicasol (the Silica MEK-ST of 1.3g with different-grain diameter, mean grain size 45nm, solids content 30 weight %, by NISSAN CHEMICAL INDUSTRIES, LTD. manufacturing), the methyl ethyl ketone of sol solution a, the 5g of preparation as mentioned above of 0.6g and the cyclohexanone of 0.6g, via hole diameter is the polypropylene filter filtration of 1 μ m then, makes the coating fluid of low-index layer thus.

[structure] with protective film of anti-reflecting layer

To be the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) of 80 μ m as the thickness of basement membrane, launch from web-like.Use then that to have line density be that 180 the line/in. and the degree of depth are the nick version print roller (diameter: 50mm) and scraper, be that 30rpm and travelling speed are to apply the coating fluid of functional layer (light scattering layer) as mentioned above under the 30m/min at the gravure roll rotating speed of the intaglio printing pattern of 40 μ m.60 ℃ of dryings are used the air cooling metal halide lamp (by EYEGRAPHICS Co., Ltd. makes) of 160W/cm, at 400mW/cm after 150 seconds ²Illumination under under nitrogen flushing, use 250mJ/cm ²UV-irradiation coating is hardened.Form the functional layer that thickness is 6 μ m thus, then it is rolled.

Here; the cellulose acylate film of operable commercially available acquisition; except above-mentioned FUJITACK-TDY80UL; (top product is all by FUJI PHOTO FILM CO. with " FUJITACK-T40UZ " also to comprise " FUJITACK-TD80UL ", " FUJITACK-TF80UL ", " FUJITACK-TFY80UL ", " FUJITACK-T80UZ "; LTD. make); with " KC4UX2MW " and " KC80UVSFD " (top product is all by Konica Minolta Opto, and Inc. makes).

The tri acetyl cellulose film that is formed with functional layer (light scattering layer) on it is launched once more.In its light scattering layer side, it is that 180 the line/in. and the degree of depth are the nick version print roller (diameter: 50mm) and scraper, be that 30rpm and travelling speed are the coating fluid of the low-index layer that makes above the coating under the 15m/min at the gravure roll rotating speed of the intaglio printing pattern of 40 μ m that use has line density.120 ℃ of dryings are followed after 140 ℃ of dryings 8 minutes for 150 seconds, use the air cooling metal halide lamp (by EYEGRAPHICS Co., Ltd. makes) of 240W/cm, at 400mW/cm ²Illumination under under nitrogen flushing, use 900mJ/cm ²UV-irradiation coating is hardened.Form the low-index layer that thickness is 100nm thus, then it is rolled.Thus, make up protective film (LR1) with anti-reflecting layer.

The preparation of [embodiment 6] cellulose acetate film (CTA1, CTA2)

(preparation of cellulose acetate ester solution)

Following composition is joined in the mixing channel and stir, prepare the cellulose acetate ester solution D thus to dissolve each component.

(prescription of cellulose acetate ester solution D)

Degree of acetylation is 2.86 cellulose acetate ester 100.0 weight portions

Methylene chloride (first solvent) 402.0 weight portions

Methyl alcohol (second solvent) 60.0 weight portions

(preparation of matting agent solution)

With the mean grain size of 20 weight portions is that the silica dioxide granule (AEROSILR972 is made by Degussa) of 16nm and the methyl alcohol of 80 weight portions stir and abundant the mixing 30 minutes, obtains the dispersion of silica dioxide granule.This dispersion is joined in the decollator with following composition, further stirred 30 minutes or the longer time with each components dissolved, prepare matting agent solution thus.

(prescription of matting agent solution)

Mean grain size is dispersion 10.0 weight of the silica dioxide granule of 16nm

Part

Methylene chloride (first solvent) 76.3 weight

Part

Methyl alcohol (second solvent) 3.4 weight portions

Cellulose acetate ester solution D 10.3 weight

Part

(preparation of additive solution)

Following composition joined in the mixing channel and heated and stirred to dissolve each component, prepare the cellulose acetate ester solution thus.The following optically anisotropic compound of reduction is that foregoing A19 and dispersion adjustment agent are foregoing UV102.

(prescription of additive solution)

Reduce optically anisotropic compound (A19) 49.3 weight portions

Dispersion adjustment agent (UV102) 7.6 weight portions

Methylene chloride (first solvent) 58.4 weight portions

Methyl alcohol (second solvent) 8.7 weight portions

Cellulose acetate ester solution D 12.8 weight portions

(preparation of cellulose acetate film CTA1)

The additive solution of the matting agent solution of the above-mentioned cellulose acetate ester solution D of 94.6 weight portions, 1.3 weight portions and 4.1 weight portions is filtered respectively and mix, with belt casting machine curtain coating.The weight ratio that reduces optically anisotropic compound and dispersion adjustment agent and cellulose acetate ester in the above-mentioned prescription is respectively 12% and 1.8%.When the residual solvent amount is 30%, film is peeled off from being with, and, obtained cellulose acetate film CTA1 135 ℃ of dryings 40 minutes.The residual solvent amount of gained cellulose acetate film be 0.2% and film thickness be 80 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

Table 18

(preparation of cellulose acetate film CTA2)

The additive solution of the matting agent solution of the above-mentioned cellulose acetate ester solution D of 94.6 weight portions, 1.3 weight portions and 4.1 weight portions is filtered respectively and mix, and with belt casting machine curtain coating.The weight ratio that reduces optically anisotropic compound and dispersion adjustment agent and cellulose acetate ester in the above-mentioned prescription is respectively 12% and 1.8%.When the residual solvent amount is 30%, film is peeled off from being with, and, obtained cellulose acetate film CTA2 130 ℃ of dryings 40 minutes.The residual solvent amount of gained cellulose acetate film be 0.2% and film thickness be 40 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

Also to ARTON FLZR50 (making), ZEONOR ZF14 (making) by OPTES INC. by JSR Corporation as transparent supporting body, measure Re with FUJITACK-TDY80UL and FUJITACK-TFY80UL (by FUJI PHOTO FILM CO., LTD. makes) ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

The structure of [embodiment 7] polarizer PAC1

(making up optical anisotropic layer A1 by stretching)

Sodium hydrate aqueous solution and ion exchange water are poured into after the reactor that is equipped with stirrer, thermometer and reflux condenser, below will having shown in the monomer A of structure and B with the mol ratio dissolving of 55/45mol%, and to wherein adding a small amount of mercaptan.To wherein adding methylene chloride, and in about 60 minutes, in the gained potpourri, be blown into phosgene at 20 ℃.Add after the p-t-butyl phenol that emulsification uses, add triethylamine and 30 ℃ with this potpourri stir about 3 hours, finish reaction.After reaction finishes, separate organic phase and, obtain Copolycarbonate the methylene chloride evaporation.The ratio of components of gained multipolymer adds ratio much at one with monomer.

The gained multipolymer is dissolved in makes the dope that solids content is 15 weight % in the methylene chloride.Prepare film with the belt casting machine by this dope, and stretch, obtain optical anisotropic layer A1 with stenter cross directional stretch with 21% under 210 ℃ temperature.Film thickness after stretching is 83 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

(monomer A)

(monomers B)

(using non-liquid-crystal compounds to make up optical anisotropic layer C1)

Polyimide by 2,2 '-two (3,4-dicarboxyl phenyl) HFC-236fa and 2,2 '-two (trifluoromethyl)-4,4 '-the benzidine base is synthetic, and it is dissolved in the polyimide solution that makes 15 weight % in the cyclohexanone.On the surface of passing through the film A1 that carries out Corona discharge Treatment with the solid-state corona treatment of 6KVA type (can obtain) from Pillar Inc., the film thickness of coating polyimide solution after drying is 1.8 μ m, and, form the optical anisotropic layer C1 that comprises above-mentioned polyimide 150 ℃ of dryings 5 minutes.Thus, make optical compensating gage AC1.

On the glass substrate that makes separately, coating polyimide solution to the film thickness after dry is 1.8 μ m, and 150 ℃ of dryings 5 minutes, forms the optical anisotropic layer C1G that comprises above-mentioned polyimide.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

(structure of polarizer PAC1)

Polyvinyl alcohol (PVA) (PVA) film that with thickness is 80 μ m soaks 60 seconds and dyeing in 30 ℃ in iodine concentration is the iodine aqueous solution of 0.05 weight %.Then, at the described film of longitudinal stretching 5 times to its initial length, soaked for 60 seconds simultaneously in boric acid concentration is the boric acid aqueous solution of 4 weight %, 50 ℃ of dryings 4 minutes, obtaining thickness was the polarizer of 20 μ m afterwards.

The protective film LR1 that CTA1 that embodiment 6 is obtained and preparation embodiment 1 obtain with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

Use polyvinyl alcohol-based adhesives as mentioned above the CTA1 of saponification and protective film LR1 with anti-reflecting layer be bonded together and make and be inserted with polarizer between them, obtain polarizer thus.Here, carry out bonding feasible tri acetyl cellulose film side and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

By acrylic based binders optical compensating gage AC1 is adhered to polarizer CTA1 side, makes optical anisotropic layer A1 side be positioned at binder side, obtain polarizer PAC1F thus.And, also apply acrylic based binders in the optical anisotropic layer C1 of optical compensating gage side.At this moment because polarizer and the protective film in the polarizer both sides make with web-like, therefore respectively roll up the long limit of film parallel to each other and they be bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A1 is parallel with the axis of homology of polarizer.

And, make up polarizer PAC1R as polarizer PAC1R, but replace the protective film LR1 among the polarizer PAC1F with the tri acetyl cellulose film (FUJITACK-TDY80UL, by FUJI PHOTO FILMCO., LTD. makes) of commercially available acquisition.Here; the cellulose acylate film of operable commercially available acquisition; except above-mentioned FUJITACK-TDY80UL; (top product is all by FUJI PHOTO FILM CO. with " FUJITACK-T40UZ " also to comprise " FUJITACK-TD80UL ", " FUJITACK-TF80UL ", " FUJITACK-TFY80UL ", " FUJITACK-T80UZ "; LTD. make); with " KC4UX2MW " and " KC80UVSFD " (top product is all by Konica Minolta Opto, and Inc. makes).

The structure of [embodiment 8] polarizer PAC2

(structure of optical anisotropic layer C2)

On the surface of the optical anisotropic layer A1 that embodiment 7 makes, use the solid-state corona treatment of 6KVA type (can obtain) to carry out Corona discharge Treatment from Pillar Inc., be coated with device with 24ml/m by the #14 metal thread bar then ²Amount on it, apply the down coating fluid of surface compositions.Coating is used 90 ℃ 150 seconds of heated-air drying 60 seconds then with 60 ℃ heated-air drying, obtain film.

The prescription of the coating fluid of＜alignment film 〉

Below shown in modified polyvinylalcohol 40 weight portions

Water 728 weight portions

Methyl alcohol 228 weight portions

Glutaraldehyde (crosslinking chemical) 2 weight portions

(AS3 is by Sankyo Chemical Industries, 0.69 weight portion for citrate

Ltd. make)

Modified polyvinylalcohol

With the disc liquid-crystal compounds shown in 41.01 weight portions following, 4.06 the trimethyol propane triacrylate (V#360 of the oxirane modification of weight portion, make by Osaka OrganicChemical Industry Ltd.), 1.35 the Photoepolymerizationinitiater initiater (IRGACURE907 of weight portion, make by Ciba-Geigy AG), 0.45 the sensitizer (KAYACUREDETX of weight portion, by Nippon Kayaku Co., Ltd. make), be dissolved in the melamine based polyalcohol shown in 0.12 weight portion following and make coating fluid in the methyl ethyl ketone of 75 weight portions (MEGAFACEF780 is by DAINIPPON INK﹠amp to the multipolymer that contains fluorine-containing aliphatic group that wherein adds 0.1 weight portion then; CHEMICALS, INCORPORATED makes), and with the #2.8 metal thread bars of 391 rotations (391 rotations) with the direction identical with the film transporting direction with the surface of gained coating fluid continuously coating to the alignment film of the optical anisotropic layer A1 that transports with the speed of 20m/min.It is heated to continuously 100 ℃ process from room temperature with solvent seasoning, coating heats at 135 ℃ dry section and makes that the speed of wind on surface of bump disc liquid-crystal compounds is 1.5m/sec and parallel with the transporting direction of film 90 seconds then, arranges disc liquid-crystal compounds thus.Then, described layer is transported to 80 ℃ dry section, and is under 100 ℃ the state, to use ultraviolet lamp (uviol lamp: power in the temperature of film surface; 160W/cm, emission length: 1.6m) with illumination be 4 seconds of UV-irradiation of 600mW, thus disc liquid-crystal compounds is crosslinked and fixing with ordered state.Then, film is left standstill be cooled to room temperature and roll, obtain to contain the optical compensating gage AC2 of optical anisotropic layer A1 and C2 so that web-like is cylindrical.

On the glass substrate that makes separately, form alignment film and optical anisotropic layer C2, replace optical anisotropic layer A1, to obtain to comprise the optical anisotropic layer C2G of disc liquid-crystal compounds through corona treatment.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

Disc liquid-crystal compounds

Melamine polymkeric substance (repetitive)

(structure of polarizer PAC2)

Polyvinyl alcohol (PVA) (PVA) film that with thickness is 80 μ m soaks 60 seconds and dyeing in 30 ℃ in iodine concentration is the iodine aqueous solution of 0.05 weight %.Then, described film is being longitudinally stretched to 5 times of its initial length, was soaking for 60 seconds simultaneously in boric acid concentration is the boric acid aqueous solution of 4 weight %, 50 ℃ of dryings 4 minutes, obtaining thickness was the polarizer of 20 μ m afterwards.

The protective film LR1 that obtains among CTA1 that obtains among the embodiment 6 and the preparation embodiment 1 with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The CTA1 of saponification as mentioned above and protective film LR1 with anti-reflecting layer be bonded together with polyvinyl alcohol-based adhesives to make and is inserted with polarizer between them, obtains polarizer thus.Here, carry out bonding feasible tri acetyl cellulose film side and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

By acrylic based binders, optical compensating gage AC2 is adhered to polarizer CTA1 side, make optical anisotropic layer A1 side be positioned at binder side, obtain polarizer PAC2F thus.And, also apply acrylic based binders in the optical anisotropic layer C2 of optical compensating gage side.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A1 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TDY80UL, by FUJI PHOTO FILM CO., LTD. makes) with commercially available acquisition replaces the protective film LR1 among the polarizer PAC2R, structure polarizer PAC2F.

The structure of [embodiment 9] polarizer PAC3

(structure of optical anisotropic layer C3)

On the surface of the optical anisotropic layer A1 that embodiment 7 makes, use the solid-state corona treatment of 6KVA type (can obtain) to carry out Corona discharge Treatment from Pillar Inc., and with

Embodiment 8 identical modes form the alignment film layer.

Make described alignment film through after the friction treatment, add 41.01 weight portions following rod shaped liquid crystal compound, (ILGACURE 907 for the Photoepolymerizationinitiater initiater of 1.35 weight portions, by Ciba-Geigy Co., Ltd. manufacturing), sensitizer (the KAYACURE DETX of 0.45 weight portion, by Nippon Kayaku Co., Ltd. make) and have the reactive monomer of chiral structure as described below, make that the selection reflection wavelength is 300nm.Then, with the direction identical gained solution continuously coating is arrived the surface of the alignment film of the optical anisotropic layer A1 that transports with the speed of 20m/min with the transporting direction of film with the #2 metal thread bar of 391 rotations.It is heated to continuously 70 ℃ process from room temperature with solvent seasoning, heat at 90 ℃ dry section then and make that the speed of wind on surface of bump rod shaped liquid crystal compound is 1.5m/sec and parallel with the transporting direction of film 90 seconds, cholesteric is arranged the rod shaped liquid crystal compound thus.Then, described layer is transported to 80 ℃ dry section, and is under 80 ℃ the state, to use ultraviolet lamp (uviol lamp: power at film surface temperature; 160W/cm, emission length: 1.6m) with illumination be 4 seconds of UV-irradiation of 600mW, thus the rod shaped liquid crystal compound is crosslinked and fixing with ordered state.Then, this film is left standstill be cooled to room temperature and roll, obtain to contain the optical compensating gage AC3 of optical anisotropic layer A1 and C3 so that web-like is cylindrical.

On the glass substrate that makes separately, form alignment film and optical anisotropic layer C3, replace optical anisotropic layer A1, to obtain to comprise the optical anisotropic layer C3G of rod shaped liquid crystal compound through corona treatment.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

The rod shaped liquid crystal compound

Reactive monomer

(structure of polarizer PAC3)

The protective film LR1 that CTA1 that obtains among the embodiment 6 and preparation embodiment 1 obtain with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

By acrylic based binders optical compensating gage AC3 is adhered to polarizer CTA1 side, makes optical anisotropic layer A1 side be positioned at binder side, obtain polarizer PAC3F thus.And, also apply acrylic based binders in the optical anisotropic layer C3 of optical compensating gage side.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A1 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) with commercially available acquisition substitutes the protective film LR1 among the polarizer PAC3F, structure polarizer PAC3R.

The structure of [embodiment 10] polarizer PAC4

(structure of optical anisotropic layer C4)

Under 140 ℃ temperature, the ARTONZF14 of commercially available acquisition is also stretched 7% in the horizontal direction at longitudinal stretching 6% with successively biaxial-oriented machine, thereby make up film C4 (optical anisotropic layer).Film thickness after stretching is 88 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(structure of polarizer PAC4)

The protective film LR1 that the CTA1 that obtains among the embodiment 6 and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The optical anisotropic layer A1 of embodiment 7 structures is adhered to the CTA1 side of described polarizer by acrylic based binders.And, by acrylic based binders optical anisotropic layer C4 is adhered to optical anisotropic layer A1 to make up polarizer PAC4F.And, also apply acrylic based binders in the optical anisotropic layer C4 of optical compensating gage side.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical compensating layer A1 is parallel with the axis of homology of polarizer.

In addition, replace the protective film LR1 among the polarizer PAC4F, make up polarizer PAC4R with the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) of commercially available acquisition.

The structure of [embodiment 11] polarizer PAC5

(structure of optical anisotropic layer A2)

The solution of #5 metal thread bar spreader continuously coating polyimide as described below in N-Methyl pyrrolidone/butyl cellosolve is used on the surface of the cellulose acetate film CTA1 that makes up to embodiment 6, transports the web-like transparent supporting body simultaneously.It 140 ℃ of heating 3 minutes, is formed the alignment film that thickness is 0.5 μ m thus.

Polyimide (repetitive)

When design of transportation has the web-like transparent supporting body of alignment film, carry out friction treatment continuously at vertical (transporting direction).With the rod shaped liquid crystal molecule (N26) of 100 weight portions, (ILGACURE 907 for the Photoepolymerizationinitiater initiater of 1 weight portion, by Nippon Ciba-Geigy Co., Ltd. make), photopolymerization sensitizer (KAYACURE DETX with 0.3 weight portion, by NipponKayaku Co., Ltd. make) be dissolved in the methylene chloride of 900 weight portions, make coating fluid.Use #5 metal thread bar spreader with this coating fluid continuously coating to alignment film.Coating 110 ℃ the heating 2 minutes, and with ultraviolet light with 500mJ/cm ²Thereby irradiation makes rod shaped liquid crystal molecule polymerization, stationary arrangement state thus.Therefore, form optical anisotropic layer, and make up optical anisotropic layer A2.Rod shaped liquid crystal molecule is through arrange making vertical vertical than the direction of major axis and optical compensating gage.

On the glass substrate that makes separately, film thickness was that alignment film layer and the film thickness of 0.5 μ m are the rod shaped liquid crystal layer of 0.9 μ m after formation was dry, obtained containing the optical anisotropic layer A2G of rod shaped liquid crystal molecule thus.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

On optical anisotropic layer A2, it is 1.8 μ m that embodiment 7 described polyamide solution are applied to dry film thickness afterwards, and forms the optical compensating layer C1 that contains above-mentioned polyimide in 5 minutes 150 ℃ of dryings, makes up optical compensating gage AC5 thus.

On the glass substrate that makes separately, coating polyimide solution to dry film thickness afterwards is 1.8 μ m, and contains the optical anisotropic layer C1G of above-mentioned polyimide in 5 minutes with formation 150 ℃ of dryings.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(structure of polarizer PAC5)

The protective film LR1 that the optical compensating gage AC5 that makes up above and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The optical compensating gage AC5 of saponification and protective film LR1 with anti-reflecting layer are bonded together with polyvinyl alcohol-based adhesives and make and be inserted with polarizer between them as mentioned above, obtain polarizer PAC4F thus.Here, carry out the bonding cellulose acylate film CTA1 side of optical compensating gage AC5 and the tri acetyl cellulose film side of making and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

And, also apply acrylic based binders in the optical anisotropic layer C1 of optical compensating gage side, obtain polarizer PAC5F thus.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A2 is parallel with the axis of homology of polarizer.

In addition, use the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) of commercially available acquisition to replace the protective film LR1 among the polarizer PAC5F, make up polarizer PAC5R.

The structure of [embodiment 12] polarizer PAC6

The protective film LR1 that preparation embodiment 1 is obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked fully to rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

On the surface of ARTON FLZR50 (making), use the solid-state corona treatment of 6KVA type (can obtain) to carry out Corona discharge Treatment from Pillar Inc. by JSR Corp..

The protective film LR1 of ARTON FLZR50 that corona treatment is crossed and the saponification with anti-reflecting layer is bonded together with polyvinyl alcohol-based adhesives and makes and be inserted with polarizer between them.Here, carry out bonding feasible tri acetyl cellulose film side and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

The optical compensating gage AC1 that embodiment 7 is made by acrylic based binders is adhered to ARTON FLZR50 side, makes optical anisotropic layer A1 side be positioned at the polarizer side, obtains polarizer PAC6F thus.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A1 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) with commercially available acquisition replaces the protective film LR1 among the polarizer PAC6F, structure polarizer PAC6R.

The structure of [Comparative Examples 1] polarizer PAC7

Make up polarizer PAC7F and PAC7R in the mode identical with embodiment 7; be the tri acetyl cellulose film (FUJITACK-TDY80UL of the cellulose acetate film CTA1 of polarizer PAC1 among the embodiment 7 with commercially available acquisition; by FUJI PHOTO FILM CO., LTD) replace.

The structure of [Comparative Examples 2] polarizer PAC8

Make up polarizer PAC8F and PAC8R in the mode identical with embodiment 10; be the tri acetyl cellulose film (FUJITACK-TDY80UL of the cellulose acetate film CTA1 of polarizer PAC4 among the embodiment 10 with commercially available acquisition; by FUJI PHOTO FILMCO., LTD makes) replace.

The structure of [Comparative Examples 3] polarizer PAC9

Make up polarizer PAC9F and PAC9R in the mode identical with embodiment 11; be the tri acetyl cellulose film (FUJITACK-TDY80UL of the cellulose acetate film CTA1 of the polarizer PAC5 among the embodiment 11 with commercially available acquisition; by FUJI PHOTO FILMCO., LTD makes) replace.

The structure of [embodiment 13] polarizer PCA1

(making up optical anisotropic layer A3 by stretching)

Prepare film with the belt casting machine by the dope of the Copolycarbonate of embodiment 7, and under 210 ℃ temperature, stretch, obtain optical anisotropic layer A3 with cross directional stretch 7% with stenter.Film thickness after stretching is 93 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(using non-liquid-crystal compounds to make up optical anisotropic layer C5)

Polyimide, by 2,2 '-two (3,4-dicarboxyl phenyl) HFC-236fa and 2,2 '-two (trifluoromethyl)-4,4 '-the benzidine base is synthetic, and it is dissolved in the polyimide solution that makes 15 weight % in the cyclohexanone.On cellulose acetate film CTA2, the film thickness of coating polyimide solution after drying is 3.1 μ m, and 150 ℃ of dryings 5 minutes, formation comprises the optical anisotropic layer C5 of above-mentioned polyimide, obtains having on cellulose acetate film CTA2 the optical compensating gage CA1 of optical anisotropic layer C5 thus.

On the glass substrate that makes separately, coating polyimide solution to the film thickness after dry is 3.1 μ m, and 150 ℃ of dryings 5 minutes, forms the optical anisotropic layer C5G that comprises above-mentioned polyimide.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎, they the results are shown in Table 18.

(structure of polarizer PCA1)

The protective film LR1 that the optical compensating gage CA1 that makes up above and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The optical compensating gage CA1 of saponification and protective film LR1 with anti-reflecting layer are bonded together with polyvinyl alcohol-based adhesives and make and be inserted with polarizer between them as mentioned above, obtain polarizer thus.Here, carry out the bonding tri acetyl cellulose film side of protective film LR1 with anti-reflecting layer and the cellulose acetate film CTA2 side of optical compensating gage CA1 of making and be positioned at the polarizer side.

By acrylic based binders optical anisotropic layer A3 is adhered to the optical anisotropic layer C5 side of described polarizer, makes optical anisotropic layer A3 side be positioned at binder side, obtain polarizer PCA1F thus.And, on the optical anisotropic layer A3 of optical compensating gage, also apply acrylic based binders.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A1 is parallel with the axis of homology of polarizer.

In addition, the protective film LR1 that replaces among the polarizer PCA1F with the tri acetyl cellulose film (FUJITACK-TDY80UL, by FUJI PHOTO FILM CO., LTD makes) of commercially available acquisition makes up polarizer PCA1R.

The structure of [embodiment 14] polarizer PCA2

(structure of optical anisotropic layer C6)

On the surface of the cellulose acetate film CTA2 that embodiment 6 makes up, use the used solution of polyimide in N-Methyl pyrrolidone/butyl cellosolve among the #30 metal thread bar spreader continuously coating embodiment 11, transport the web-like transparent supporting body simultaneously.140 ℃ of heating 3 minutes, forming thickness thus was the optical anisotropic layer C6 of 15 μ m with it.

On the glass substrate that makes separately, coating polyimide solution film thickness after dry is 15 μ m, and 150 ℃ of dryings 5 minutes, forms the optical anisotropic layer C6G that contains above-mentioned polyimide thus.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

When design of transportation has the web-like transparent supporting body of optical anisotropic layer C6, carry out friction treatment continuously at vertical (transporting direction).With the above-mentioned rod shaped liquid crystal molecule (N26) of 100 weight portions, (ILGACURE 907 for the Photoepolymerizationinitiater initiater of 1 weight portion, by NipponCiba-Geigy Co., Ltd. make), photopolymerization sensitizer (KAYACUREDETX with 0.3 weight portion, by Nippon Kayaku Co., Ltd. make) be dissolved in the methylene chloride of 900 weight portions, make coating fluid.Use #2 metal thread bar spreader with this coating fluid continuously coating to alignment film.Coating 110 ℃ the heating 2 minutes, and with ultraviolet light with 500mJ/cm ²Thereby irradiation makes rod shaped liquid crystal molecule polymerization, stationary arrangement state thus.Therefore, form optical anisotropic layer A4, and make up optical compensating gage CA2.Rod shaped liquid crystal molecule is through arrange making vertical vertical than the direction of major axis and optical compensating gage.

On the glass substrate that makes separately, film thickness was that alignment film layer and the film thickness of 0.5 μ m are the rod shaped liquid crystal layer of 0.3 μ m after formation was dry, obtained containing the optical anisotropic layer A4G of rod shaped liquid crystal molecule thus.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(structure of polarizer PCA2)

The protective film LR1 that the optical compensating gage CA2 that makes up above and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The optical compensating gage CA2 of saponification as mentioned above and protective film LR1 with anti-reflecting layer be bonded together with polyvinyl alcohol-based adhesives to make and is inserted with polarizer between them, obtains polarizer PCA2F thus.Here, carry out the bonding cellulose acylate film CTA2 side of optical compensating gage AC2 and the tri acetyl cellulose film side of making and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

And, also on the optical anisotropic layer CA2 of optical compensating gage, apply acrylic based binders, obtain polarizer PCA2F thus.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A4 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TDY80UL, by Fuji Photo Film Co., Ltd. makes) with commercially available acquisition substitutes the protective film LR1 among the polarizer PCA2F, structure polarizer PCA2R.

The structure of [embodiment 15] polarizer PCA3

(using non-liquid-crystal compounds to make up optical anisotropic layer C5)

On the surface of ZEONOR ZF 14 (making), use the solid-state corona treatment of 6KVA type (can obtain) to carry out Corona discharge Treatment from Pillar Inc. by Optes Inc., and form optical anisotropic layer C5, and make up optical compensating gage CA3 in the mode identical with embodiment 13.

(structure of polarizer PCA3)

The protective film LR1 that the optical compensating gage CA3 that makes up above and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The optical compensating gage CA3 of saponification and protective film LR1 with anti-reflecting layer are bonded together with polyvinyl alcohol-based adhesives and make and be inserted with polarizer between them as mentioned above, obtain polarizer thus.Here, carry out the bonding tri acetyl cellulose film side of protective film LR1 with anti-reflecting layer and the transparent support side of optical compensating gage CA3 of making and be positioned at the polarizer side.

With the optical anisotropic layer C5 side that optical anisotropic layer A3 is adhered to described polarizer, obtain polarizer PCA3F by acrylic based binders thus.And, on the optical anisotropic layer A3 of optical compensating gage, also apply acrylic based binders.At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides all prepares with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical anisotropic layer A3 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TFY80UL, by Fuji Photo Film Co., Ltd. makes) with commercially available acquisition substitutes the protective film LR1 among the polarizer PCA3F, structure polarizer PCA3R.

The structure of [Comparative Examples 4] polarizer PCA4

Make up polarizer PCA4F and PCA4R in the mode identical with embodiment 13; be tri acetyl cellulose film (the FUJITACK TFY80UL of the cellulose acetate film CTA2 of polarizer PCA1 among the embodiment 13 with commercially available acquisition; by FUJI PHOTO FILMCO., LTD makes) substitute.

The structure of [Comparative Examples 5] polarizer PCA5

Make up polarizer PCA5F and PCA5R in the mode identical with embodiment 14; be tri acetyl cellulose film (the FUJITACK TFY80UL of the cellulose acetate film CTA2 of polarizer PCA2 among the embodiment 14 with commercially available acquisition; by FUJI PHOTO FILMCO., LTD makes) replace.

The structure of [Comparative Examples 6] polarizer PCA6

(structure of optical anisotropic layer C7)

Under 140 ℃ temperature, the ARTONZF14 of commercially available acquisition is also stretched 14% in the horizontal direction at longitudinal stretching 13% with successively biaxial-oriented machine, thereby make up film C7 (optical anisotropic layer).Film thickness after stretching is 78 μ m.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(structure of optical anisotropic layer A4)

In the above on the surface of the optical anisotropic layer C7 of Gou Jianing, use the solid-state corona treatment of 6KVA type (can obtain) to carry out Corona discharge Treatment from Pillar Inc., and on described surface, with the solution of the aforementioned polyimide of #5 metal thread bar spreader continuously coating in N-Methyl pyrrolidone/butyl cellosolve, transport the web-like transparent supporting body simultaneously.It 140 ℃ of heating 3 minutes, is formed the alignment film that thickness is 0.5 μ m thus.

When design of transportation has the web-like transparent supporting body of alignment film, carry out friction treatment continuously at vertical (transporting direction).With the aforementioned rod shaped liquid crystal molecule (N26) of 100 weight portions, (ILGACURE 907 for the Photoepolymerizationinitiater initiater of 1 weight portion, by Nippon Ciba-Geigy Co., Ltd. make), photopolymerization sensitizer (KAYACURE DETX with 0.3 weight portion, by Nippon Kayaku Co., Ltd. make) be dissolved in the methylene chloride of 900 weight portions, make coating fluid.Use #2 metal thread bar spreader with this coating fluid continuously coating to alignment film.Coating 110 ℃ the heating 2 minutes, and with ultraviolet light with 500mJ/cm ²Thereby irradiation makes rod shaped liquid crystal molecule polymerization, stationary arrangement state thus.Therefore, form optical anisotropic layer, and make up optical anisotropic layer A4.Rod shaped liquid crystal molecule is through arrange making vertical vertical than the direction of major axis and optical compensating gage.Therefore, make up optical compensating gage CA6.

On the glass substrate that makes separately, film thickness was that alignment film layer and the film thickness of 0.5 μ m are the rod shaped liquid crystal layer of 0.3 μ m after formation was dry, obtained containing the optical compensating layer A4G of rod shaped liquid crystal molecule thus.Measure Re ₍₄₅₀₎, Re ₍₅₉₀₎, Re ₍₆₅₀₎, Rth ₍₄₅₀₎, Rth ₍₅₉₀₎And Rth ₍₆₅₀₎The results are shown in table 18.

(structure of polarizer PCA6)

The protective film LR1 that the tri acetyl cellulose film (FUJITACK TFY80UL) of commercially available acquisition and preparation embodiment 1 are obtained with anti-reflecting layer concentration be in the sodium hydrate aqueous solution of 1.5mol/L in 55 ℃ of immersions, wash with water then so that NaOH is fully rinsed out.Then, described film is to soak 1 minute and soaked so that fully rinse out dilute sulfuric acid aqueous solution in water in 35 ℃ in the dilute sulfuric acid aqueous solution of 0.005mol/L in concentration.At last, at 120 ℃ that sample is fully dry.

The tri acetyl cellulose film (FUJITACK TFY80UL) of the commercially available acquisition of saponification as mentioned above and protective film LR1 with anti-reflecting layer be bonded together with polyvinyl alcohol-based adhesives make and be inserted with polarizer between them.Here, carry out bonding feasible tri acetyl cellulose film side and be positioned at the polarizer side with protective film LR1 of anti-reflecting layer.

By acrylic based binders the optical anisotropic layer C7 side of optical compensating gage CA6 is adhered to the tri acetyl cellulose film of the commercially available acquisition of above-mentioned polarizer, obtains polarizer PCA6F thus.And, on the optical anisotropic layer A4 of optical compensating gage CA6, also apply acrylic based binders.

At this moment, each rolls up the vertically parallel to each other of film, and owing to the protective film of polarizer and polarizer both sides makes with web-like, so they are bonded together continuously.In addition, as shown in Figure 1, the slow axis of optical compensating layer A4 is parallel with the axis of homology of polarizer.

In addition, the tri acetyl cellulose film (FUJITACK-TFY80UL, by Fuji Photo Film Co., Ltd. makes) with commercially available acquisition substitutes the protective film LR1 among the polarizer PCA6F, structure polarizer PCA6R.

[embodiment 16] are installed on the VA plate

With polarizer PAC 1F-9F and the PCA1F-6F punching on the viewable side (face side) that makes up among embodiment 7-12, Comparative Examples 1-3, embodiment 13-15 and the Comparative Examples 4-6, make the absorption axes of 26 inches wide polarizers be positioned at the longer sides side.In addition, polarizer PAC1R-9R and PCA1R-6R punching with on the backlight side (back side) make the absorption axes of 26 inches wide polarizers be positioned at than short brink.

The polarizer of VA type liquid crystal TV (KDL-L26HVX, by Sony Co., Ltd. makes) and the inboard and the outside of retardation plate are peeled, and the polarizer after the punching is bonding on it as mentioned above, makes liquid crystal indicator 1-15 shown in table 19 thus.After the bonding polarizer, with them at 50 ℃ and 5kg/cm ²Under keep 20 minutes, and bonding.At this moment, they make the absorption axes of viewable side polarizer be in the direction with plate level through arrangement, and the absorption axes of backlight side polarizer is in the direction vertical with plate, and binder side is the liquid crystal cell side.

Use the analyzer (EZ-Contrast 160D is made by ELDIM SA) that makes up as mentioned above, the brightness measuring that shows by dark state and white calculate the visual angle (contrast than 20 or bigger scope in).The azimuth direction of 45 ° angle is shown in table 19.

In addition, on the u ' v ' of dark state chromatic diagram, carry out colour examining, and by determination of colority value (u ' 0 of plate normal direction (0 ° polar angle), v ' 0), with rotating in a counter-clockwise direction 45 ° orientation (45 ° position angles) slave plate normal direction from the screen level direction to colourity (u ' 60 of the direction (60 ° polar angles) of 60 ° of plate surface tilt, v ' 60), defined as following equation, calculate color alteration index Δ Cu ' v '.The results are shown in table 19.Table 19 shows, by the present invention, obtains the liquid crystal indicator that viewing angle properties is improved and the look change improves when optical angle (optic angle) is reverse from the front under dark state.

ΔCu′v′＝((u′0-v′60) ²-(v′0-v′60) ²) ^0.5

Table 19

Industrial applicibility

According to the present invention; has the cellulose acylate film of the little optical anisotropy (Re, Rth) that is lower than certain level as the protective film of polarizer by use; a kind of VA type liquid crystal indicator is provided, and it has corner point and the excellent display characteristic of excellent viewing angle characteristic, reduction.

According to the present invention, a kind of liquid crystal indicator also is provided, a kind of VA type liquid crystal indicator particularly has the aberration of improvement during with positive face tilt when the visual angle under dark state.

Claims

1, a kind of liquid crystal indicator, it comprises: liquid crystal board, in described liquid crystal board, between upper substrate and infrabasal plate, be inserted with the liquid crystal of band negative dielectric anisotropic, described liquid crystal is vertical orientated from the teeth outwards, being oriented in when not applying voltage of described liquid crystal is almost vertical, level almost when applying predetermined voltage, and when applying than the little voltage of described predetermined voltage, tilt; Be placed on first polarizer and second polarizer of described liquid crystal board both sides, the absorption axes of wherein said polarizer is perpendicular to one another; Be placed on first retardation films between described liquid crystal board and described first polarizer; And be placed on second retardation films between described liquid crystal board and described second polarizer; wherein said polarizer comprises polarization film and described polarization film is sandwiched in therebetween a pair of protective film, and wherein at least one described protective film is the cellulose acylate film that satisfies following relational expression:

0≤Re ₍₆₃₀₎≤ 10 Hes | Rth ₍₆₃₀₎|≤25.

2, liquid crystal indicator as claimed in claim 1, wherein said first retardation films satisfies:

50≤Re ₍₅₈₉₎≤ 100 and 30≤Rth ₍₅₈₉₎≤ 80 and

Described second retardation films satisfies:

Re ₍₅₈₉₎≤ 20 and 100≤Rth ₍₅₈₉₎|≤300.

3, liquid crystal indicator as claimed in claim 1, wherein said cellulose acylate film satisfies:

0≤Re ₍₆₃₀₎≤ 5 Hes | Rth ₍₆₃₀₎|≤10.

4, liquid crystal indicator as claimed in claim 1, wherein said cellulose acylate film satisfies:

0≤Re ₍₆₃₀₎≤ 3 Hes | Rth ₍₆₃₀₎|≤5.

5, as each liquid crystal indicator of claim 1-4, wherein said cellulose acylate film contains the compound of the delay Rth of at least a reduction film thickness direction, and the amount of described compound satisfies following formula (I) and (II):

(I)(Rth(A)-Rth(0))/A≤-1.0，

(II)0.01≤A≤30，

6, as each liquid crystal indicator of claim 1-4, wherein said cellulose acylate film is that the cellulose acylate of 2.85-3.00 is made by the acyl substituted degree, and described cellulose acylate contains at least a reduction Re _(λ)And Rth _(λ)Compound, with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

7, as each liquid crystal indicator of claim 1-4, wherein said cellulose acylate film contains at least a this film of reduction | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎| compound, with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

8, as each liquid crystal indicator of claim 1-4, the thickness of wherein said cellulose acylate film is 10-120 μ m.

9, a kind of liquid crystal indicator, it comprises:a pair of substrate that faces with each other and place, and be inserted in nematic liquid crystal material between the described a pair of substrate, at least one in the described substrate has electrode; And described liquid crystal indicator has liquid crystal cell; This liquid crystal cell has liquid crystal layer; In described liquid crystal layer; The surperficial near normal ground of the liquid crystal molecule of described nematic liquid crystal material and described a pair of substrate is arranged under dark state; Through installing so that described liquid crystal cell inserts in the first polarization film and the second polarization film therebetween; Be installed in respectively between described liquid crystal layer and described the first polarization film and the optical compensating film between described liquid crystal layer and described the second polarization film

(I)200≤Δn _(λ)xd≤1000，

(II)Rth _sum(λ)/λ＝AxΔn _(λ)x d/λ+B，

(III) Re _{Sum (λ)}/ λ=Cx λ/{ Δ n _(λ)Xd}+D and

(IV)0.488≤A≤0.56，

B＝-0.0567，

-0.041≤C≤0.016 and

D=0.0939; And

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(X) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

The axis of homology of the polarization film that more close described optical compensating film is placed in slow axis and described first polarization film and described second polarization film in 10, the liquid crystal indicator as claimed in claim 9, the face of wherein said optical compensating film is substantially parallel.

11, as the liquid crystal indicator of claim 9 or 10, wherein, satisfy following formula (I)-(IV) with respect to differing 50nm or at least two bigger wavelength.

12, as the liquid crystal indicator of claim 9 or 10, wherein, satisfy following formula (I)-(IV) with respect to 450nm, 550nm and these three wavelength of 650nm.

13, a kind of liquid crystal indicator, it comprises: a pair of substrate that faces with each other and place, and be inserted in nematic liquid crystal material between the described a pair of substrate, at least one in the described substrate has electrode; And described liquid crystal indicator has liquid crystal cell; this liquid crystal cell has liquid crystal layer; in described liquid crystal layer; the surperficial near normal ground of the liquid crystal molecule of described nematic liquid crystal material and described a pair of substrate is arranged under dark state; make described liquid crystal cell be sandwiched in first polarization film and second polarization film therebetween through installation; be installed in the optical compensating film between described liquid crystal layer and one of described first polarization film and described second polarization film; and be installed in the cellulose acylate film between at least one in described liquid crystal layer and described first polarization film and described second polarization film

(V)200≤Δn _(λ)xd≤1000，

(VI)Rth _sum(λ)/λ＝ExΔn _(λ)xd/λ，

(VII) R _{Esum (λ)}/ λ=Fx λ/{ Δ n _(λ)Xd}+G and

(VIII)0.726≤E≤0.958，

0.0207≤F≤0.0716 and

G=0.032; And

(IX) 0≤Re _{2 (630)}≤ 10 Hes | Rth _{2 (630)}|≤25 and

(X) | Re _{2 (400)}-Re _{2 (700)}|≤10 Hes

|Rth ₂₍₄₀₀₎-Rth ₂₍₇₀₀₎|≤35。

14, as the liquid crystal indicator of claim 13, the axis of homology of the polarization film that more close described optical compensating film is placed in slow axis and described first polarization film and described second polarization film in the face of wherein said optical compensating film is substantially parallel.

15, as the liquid crystal indicator of claim 13 or 14; angle between the axis of homology of the polarization film that more close described cellulose acylate film is installed in slow axis and described first polarization film and described second polarization film in the face of wherein said cellulose acylate film; between-10 ° to 10 °, perhaps between 80 ° to 110 °.

16, as the liquid crystal indicator of claim 13 or 14, wherein, satisfy following formula (V)-(VIII) with respect to differing 50nm or at least two bigger wavelength.

17, as the liquid crystal indicator of claim 13 or 14, wherein, satisfy following formula (V)-(VIII) with respect to 450nm, 550nm and these three wavelength of 650nm.

18, a kind of optical compensating gage, it has the transparent supporting body that satisfies following formula (1) and (2) successively, be installed on the described transparent supporting body and satisfy the optical anisotropic layer A of following formula (3) and be installed on the optical anisotropic layer C that described optical anisotropic layer A went up and satisfied following formula (4):

(1) 0≤Re ₍₅₉₀₎≤ 10 Hes | Rth ₍₅₉₀₎|≤25,

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200,

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400

19, a kind of optical compensating gage, it has the transparent supporting body that satisfies following formula (1) and (2) successively, be installed on the described transparent supporting body and satisfy the optical anisotropic layer C of following formula (4) and be installed on the optical anisotropic layer A that described optical anisotropic layer C went up and satisfied following formula (3):

(1) 0≤Re ₍₅₉₀₎≤ 10 Hes | Rth ₍₅₉₀₎|≤25,

(3) 10≤Re ₍₅₉₀₎≤ 150 and 0≤Rth ₍₅₉₀₎≤ 200,

(4) 0≤Re ₍₅₉₀₎≤ 10 and 40≤Rth ₍₅₉₀₎≤ 400

20, as the optical compensating gage of claim 18 or 19, wherein said transparent supporting body contains at least a reduction Rth _(λ)Compound, its content satisfies following formula (5) and (6):

(5) (Rth _(λ)(A)-Rth _(λ)(0))/A≤-1.0 and

(6)0.01≤A≤30

21, as the optical compensating gage of claim 18 or 19, wherein said transparent supporting body contains at least a reduction | Re ₍₄₀₀₎-Re ₍₇₀₀₎| and | Rth ₍₄₀₀₎-Rth ₍₇₀₀₎| compound, with respect to the solids content of the raw polymer of described supporter, the amount of described compound is 0.01-30 weight %.

22, as the optical compensating gage of claim 18 or 19, wherein said transparent supporting body is formed by cellulose acylate film.

23, as the optical compensating gage of claim 22, wherein said cellulose acylate film is that the cellulose acylate of 2.85-3.00 is made by the acyl substituted degree, and described cellulose acylate film contains at least a reduction Re _(λ)And Rth _(λ)Compound, with respect to the solids content of described cellulose acylate, the amount of described compound is 0.01-30 weight %.

24, as the optical compensating gage of claim 18 or 19, the film thickness of wherein said transparent supporting body is 10-120 μ m.

25, as the optical compensating gage of claim 18 or 19, wherein said optical anisotropic layer A is made by the thin polymer film that stretches.

26, as the optical compensating gage of claim 18 or 19, wherein said optical anisotropic layer A is formed by liquid-crystal compounds.

27, as the optical compensating gage of claim 18 or 19, wherein said optical anisotropic layer C is made by the thin polymer film that stretches.

28, as the optical compensating gage of claim 18 or 19, wherein said optical anisotropic layer C is formed by liquid-crystal compounds.

29, as the optical compensating gage of claim 18 or 19, wherein said optical anisotropic layer C is formed by non-liquid-crystal compounds.

30, as the optical compensating gage of claim 18 or 19, the Re of wherein said optical anisotropic layer A _(λ)Wavelength dependency satisfy following formula (7) and (8):

(7) Re ₍₄₅₀₎/ Re ₍₅₅₀₎=0.60-0.98 and

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.00-1.60。

31, as the optical compensating gage of claim 18 or 19, the Rth of wherein said optical anisotropic layer C _(λ)Wavelength dependency satisfy following formula (9) and (10):

(9) Rth ₍₄₅₀₎/ Rth ₍₅₅₀₎=1.02-1.60 and

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.60-1.00。

32, as the optical compensating gage of claim 18 or 19, the Re of wherein said optical anisotropic layer A _(λ)Wavelength dependency satisfy following formula (7) and (8), and the Rth of described optical anisotropic layer C _(λ)Wavelength dependency satisfy following formula (9) and (10):

(7)Re ₍₄₅₀₎/Re ₍₅₅₀₎＝0.60-0.98，

(8)Re ₍₆₅₀₎/Re ₍₅₅₀₎＝1.00-1.60，

(9) Rth ₍₄₅₀₎/ Rth ₍₅₅₀₎=1.02-1.60 and

(10)Rth ₍₆₅₀₎/Rth ₍₅₅₀₎＝0.60-1.00。

33, a kind of polarizer has protective film in the both sides of described polarizer, and wherein at least one described protective film is the optical compensating gage as claim 18 or 19, and links to each other with described polarizer in the face of a side of described transparent supporting body.

34, as the polarizer of claim 33, wherein said protective film contains and is selected from least a in plastifier, ultraviolet light absorber, short release agent, dyestuff, matting agent and the electrically conductive particles.

35, as the polarizer of claim 33, wherein on the surface of at least one protective film, provide the one deck at least that is selected from hard conating, anti-glare layer, anti-reflecting layer, stain-proofing layer and the antistatic layer.

36, a kind of liquid crystal indicator, it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides, and wherein at least one described polarizer is the polarizer as claim 33.

37, a kind of liquid crystal indicator; it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides; wherein said polarizer comprises polarizer and a pair of this polarizer is sandwiched in therebetween protective film, and at least one described protective film is the optical compensating gage as claim 18.

38, a kind of liquid crystal indicator; it has liquid crystal cell and a pair of polarizer that is installed on these liquid crystal cell both sides; wherein said polarizer comprises polarizer and a pair of this polarizer is sandwiched in therebetween protective film, and at least one described protective film is the optical compensating gage as claim 19.

39, as the liquid crystal indicator of claim 36, wherein said liquid crystal cell is vertically aligned element.