CN101151558B

CN101151558B - Optical compensation film, polarizing plate and liquid crystal display device

Info

Publication number: CN101151558B
Application number: CN2006800095452A
Authority: CN
Inventors: 伊藤洋士; 中村亮
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2005-03-22
Filing date: 2006-03-22
Publication date: 2010-12-08
Anticipated expiration: 2026-03-22
Also published as: CN101151558A; JP2006267171A

Abstract

An optical compensation film is provided and has a cellulose acylate film coated with an optically anisotropic layer containing a liquid crystalline compound, cellulose having a glucose unit, a hydroxyl group of the glucose unit being substituted with an acyl group having at least two carbon atoms. The cellulose acylate film satisfies relationships specified in the specification.

Description

Optical compensation films, polaroid and LCD

Technical field

The present invention relates to a kind of optical compensation films, and polaroid and the LCD of respectively using this optical compensation films.

Background technology

LCD is because it has various advantages, the possibility height that can under low-voltage and low energy consumption, operate and reduce size and profile for example, and be widely used in the multiple application that comprises PC, mobile unit monitor and TV.Although for this LCD, according to the liquid crystal liquid crystal property molecule how in liquid crystal cell orientation various patterns have been proposed, main pattern so far is the TN pattern, wherein the alignment state of liquid crystal liquid crystal property molecule is to twist about 90 ° from the downside substrate side group plate that makes progress.

Usually, LCD is made of liquid crystal cell, optical compensation films and the polarizer.Optical compensation films is used for the chromatic dispersion of image and the expansion at visual angle, and with birefringence stretched film or the hyaline membrane that scribbles liquid crystal as optical compensation films.For example; Jap.P. No.2587398 discloses a kind of technology; its by the discoid liquid crystal of coating on the tri acetyl cellulose film, force liquid crystal to become alignment state and fixed orientation attitude to form optical compensation films, and this optical compensation films be applied to the brilliant unit of TN-mode liquid crystal go up to enlarge the visual angle.Yet the LCD that is used for TV for imagination is equipped with giant-screen and can watches from each angle has strict requirement for the visual angle correlativity, even if thereby above-mentioned technology can not satisfy this requirement.In this case, the pattern of having studied is different from the LCD of TN pattern, as IPS (switching in the face) pattern, OCB (optical compensation curved) pattern and VA (homeotropic alignment) pattern.Especially, obtained public attention in the LCD of IPS pattern in TV uses, because the change of the gradual change character that it is caused by the visual angle is little.

Cellulose acylate film has a feature, they on optical isotropy than other polymer film height (length of delay is low).Therefore, common rule is that cellulose acetate membrane is used for the optically anisotropic application of needs, as polaroid.

Otherwise the used optical compensation films (phase shift films) of LCD needs optical anisotropy (length of delay height).Especially, when cellulose acylate film is used for the IPS-mode LCD, need their Re value to be 20nm～150nm, the Re/Rth ratio is 1.5～7.

Up to now, the general rule of optical material technical field is, use synthetic polymer membranes when needing polymer film to have under the situation of optical anisotropy (length of delay height), and use cellulose acetate membrane when needing polymer film to have under the situation of optical isotropy (length of delay is low).

EP-A-911656 discloses the cellulose acetate membrane with high retardation value, though it has violated the rule that is generally believed so far, also being applicable to needs optically anisotropic application.In this patent, in order to obtain high retardation value under the situation of using cellulose acetate, adding has the compound, the particularly compound of 1,3,5-triazines ring of at least two aromatic rings, and carries out stretch processing.

Although cellulose acetate is the material that is difficult to stretch usually, and be known that and be difficult to increase its double refractive inde, but in the patent documentation of citation, additive molecule is orientated simultaneously, thereby making to increase double refractive inde and obtain high retardation value become possibility by stretch processing.

This film also can be used as the diaphragm of polaroid, so its advantage is to be suitable for providing thin LCD with lower price.

JP-A-2002-71957 discloses a kind of blooming; its contain have 2～4 carbon atoms acyl group as substituent cellulose esters; and at the degree of substitution of acetyl group as the degree of substitution of A, propiono or bytyry during as B; satisfy relation: 2.0≤A+B≤3.0; and A＜2.4; and the refractive index of measuring at quick shaft direction as Nx, with 590 nm light when the refractive index of measuring at slow-axis direction with 590 nm light is during as Ny, further satisfies to concern: 0.0005≤Nx-Ny≤0.0050.

In the IPS pattern, as improving the black a kind of method that shows the attitude visual angle of color harmony, after deliberation between liquid crystal layer and polaroid configuration have the optical compensation material of birefringent characteristic.For example, disclose by the birefringent medium that will have optical axis and be configured between substrate and the polaroid, can obtain when when vergence direction is observed, white attitude or the medium tone of showing shows the painted improvement of attitude, wherein said optical axis right angle intersection and the effect (referring to JP-A-9-80424) that the delay of liquid crystal layer increases and reduces when having the compensating for tilt attitude respectively.In addition; proposed to use the method for optical compensation films; described film have negative intrinsic birefringence and comprise styrene polymer or discoid liquid crystal compounds (referring to JP-A-10-54982; JP-A-11-202323 and JP-A-9-292522); use has the optical axis in the film of positive birefringence and the face and has the film of positive birefringence and the combination of the optical axis of embrane method line direction; method (referring to JP-A-11-133408) as optical compensation films; use has the method (referring to JP-A-11-305217) of the biaxial optical compensate film of half-wavelength delay; and use and to have the diaphragm of the negative film that postpones, and on this film surface, provide method (referring to JP-A-10-307291) with the optical compensating layer that is just postponing as polaroid.

In JP-A-9-211444 and JP-A-11-316378, the optical compensation films with the layer that is made of liquid crystal compounds is used on the polaroid, is used for the ocb mode liquid crystal display, thereby obtains wide visual angle.

Disclosed method can make effectively that low-cost production approaches LCD in the above-mentioned document.Yet in recent years, the use of LCD under various environment is increasing, and the optical compensation performance of using above-mentioned technology to change cellulose ester membrane under these environment becomes problem.More specifically, its problem is that these cellulose ester membranes are influenced by environmental change, humidity effect especially, and particularly when they are stacked on the liquid crystal cell, thereby their Re length of delay and Rth retardation variation make the optical compensation performance change.Therefore, need address this problem.

Summary of the invention

A purpose of illustrative of the present invention, non-limiting embodiments provides a kind of optical compensation films that uses cellulose acylate film, it shows the characteristic of interior delay of excellent face and thickness direction retardation, and has reduced the delay that depends on the ambient humidity variation; Another purpose of illustrative of the present invention, non-limiting embodiments provides a kind of polaroid that uses this optical compensation films.

The further purpose of illustrative of the present invention, non-limiting embodiments provides a kind of LCD that viewing angle characteristic changes that reduces.

The embodiment of these purposes below the present invention realizes.

(1-1) a kind of optical compensation films with cellulose acylate film; described cellulose acylate film is coated with the optical anisotropic layer that contains the rod shaped liquid crystal compound; wherein said cellulose acylate film comprises the cellulose with glucose unit; the acyl group that the hydroxyl of described glucose unit is had at least two carbon atoms replaces, and described cellulose acylate film satisfies relation (I) and (II):

(I)：2.0≤DS2+DS3+DS6≤3.0

(II)：DS6/(DS2+DS3+DS6)≥0.315

Wherein DS2 represents the degree of substitution of acyl group to glucose unit 2-position hydroxyl, and DS3 represents the degree of substitution of acyl group to glucose unit 3-position hydroxyl, and DS6 represents the degree of substitution of acyl group to glucose unit 6-position hydroxyl.

(1-2) as (1-1) described optical compensation films; its Re of wherein said cellulose acylate film (550) value is 20nm～150nm; Rth (550)/Re (550) ratio is 1.5～7; its Re of described optical anisotropic layer (550) value that contains described rod shaped liquid crystal compound is 0nm～10nm, Rth (550) value for-80nm～-400nm.

[in above-mentioned (1-2), wherein Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm.]

(1-3) as (1-1) or (1-2) described optical compensation films; wherein under 25 ℃-10%RH and 25 °-80%RH condition; difference DELTA Re (Re10%RH-Re80%RH) between the length of delay Re (550) of described cellulose acylate film is 12nm or following; under 25 ℃-10%RH and 25 °-80%RH condition, the difference DELTA Rth (Rth10%RH-Rth80%RH) between the length of delay Rth (550) of described cellulose acylate film is 32nm or following.

[in above-mentioned (1-3), wherein Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm.]

(1-4) a kind of polaroid, it has each described optical compensation films and polarizer as (1-1)～(1-3).

(1-5) a kind of LCD, it has liquid crystal cell and as (1-1)～(1-3) each described optical compensation films or as (1-4) described polaroid.

(1-6), wherein use the IPS pattern as (1-5) described LCD.

In the present invention, following pattern also is preferred.

(1-7) as (1-1)～(1-3) each described optical compensation films, the acyl group in the wherein said cellulose acylate film is an acetyl group.

(1-8) as (1-1)～(1-3) each described optical compensation films, wherein said cellulose acylate film contains at least a delay expression agent (retardation developer) that comprises bar-shaped or discoid compound.

(1-9) as (1-1)～(1-3) each described optical compensation films, wherein said cellulose acylate film contains at least a adjuvant that is selected from plastifier, ultraviolet light absorber or separation promoter.

(1-10) as (1-1)～(1-3) each described optical compensation films, its thickness of wherein said cellulose acylate film is 40 μ m～180 μ m.

(1-11) as (1-1)～(1-3) each described optical compensation films, the content of wherein said adjuvant in described cellulose acylate film accounts for 10～30% of cellulose acylate film quality.

(1-12) as (1-1)～(1-3) each described optical compensation films, wherein said cellulose acylate film balance water content under 25 ℃ of temperature and the humidity 80%RH be 3.4% or below.

(1-13) as (1-1)～(1-3) each described optical compensation films, wherein at 60 ℃, under the following 24 hours condition of 95%RH, the moisture content perviousness of described cellulose acylate film is 400g/m ²24hr-2,300g/m ²24 hr (being scaled film thickness 80 μ m calculates).

(1-14) as (1-1)～(1-3) each described optical compensation films, wherein said cellulose acylate film left standstill 48 hours under the condition of 80 ℃ and 90%RH, and mass change is 0～5%.

(1-15) as (1-1)～(1-3) each described optical compensation films, wherein said cellulose acylate film leaves standstill the change in size that caused in 24 hours all in the scope 0%～5% leaving standstill under the condition of 60 ℃ and 95%RH under the change in size that caused in 24 hours and the cellulose acylate film condition at 90 ℃ and 5%RH.

(1-16) as (1-1)～(1-3) each described optical compensation films, the glass transition temperature Tg of wherein said cellulose acylate film is 80 ℃～180 ℃.

(1-17) as (1-1)～(1-3) each described optical compensation films, the elastic modulus of wherein said cellulose acylate film is 1,500MPa～5,000MPa.

(1-18) as (1-1)～(1-3) each described optical compensation films, the photoelastic coefficient of wherein said cellulose acylate film is 50 * 10 ^-13Cm ²/ dyne or following.

(1-19) as (1-1)～(1-3) each described optical compensation films, the mist degree of wherein said cellulose acylate film is 0.01%～2%.

(1-20) as (1-1)～(1-3) each described optical compensation films, the mean diameter that wherein said cellulose acylate film contains secondary is fine particles of silica of 0.2 μ m～1.5 μ m.

(1-21) as (1-4) described polaroid, when it is measured, have further that at least one is selected from veneer transmissivity TT, parallel transmissivity PT, the factor of transmissivity CT or degree of polarization P of intersecting satisfies the following formula (a) and (b) respectively under 25 ℃ and 60%RH condition, (c) or (d):

(a)40.0≤TT≤45.0

(b)30.0≤PT≤40.0

(c)CT≤2.0

(d)95.0≤P。

(1-22) as (1-4) described polaroid, when the intersection transmissivity under the wavelength X is expressed as CT (λ), described polaroid about intersect transmissivity further satisfy following formula (e), (f) and (g) at least one:

(e)CT(380)≤2.0

(f)CT(410)≤0.1

(g)CT(700)≤0.5。

(1-23) as (1-4) described polaroid, when described polaroid after leaving standstill 500 hours under 60 ℃ and the 95%RH condition, further have and intersect the variation delta P of the variation delta CT of transmissivity or degree of polarization at least and satisfy following formula (j) or (k):

(j)-6.0≤ΔCT≤6.0

(k)-10.0≤ΔP≤0.0

(wherein variable quantity is defined as test back measured value and deducts the preceding resulting value of measured value of test).

(1-24) as (1-4) described polaroid, on surface relative with liquid crystal cell, that will place diaphragm, further provide the one deck at least that is selected from hard conating, antiglare layer or the anti-reflecting layer.

(1-25) as (1-4) described polaroid, it is packaged in the damp proof bag that interior humidity is adjusted to 25 ℃ of following 43%RH～65%RH.

(1-26) as (1-4) described polaroid, it is packaged in interior humidity and is adjusted to and is stacked on ambient humidity on the liquid crystal board with described polaroid and differs in 15%RH or the following damp proof bag.

Above-mentioned purpose can also the embodiment below the present invention realize.

(2-1) a kind of optical compensation films with cellulose acylate film; described cellulose acylate film is coated with the optical anisotropic layer that contains liquid crystal compounds; wherein said cellulose acylate film comprises the cellulose with glucose unit; the acyl group that the hydroxyl of described glucose unit is had at least two carbon atoms replaces, and described cellulose acylate film satisfies relation (I) and (II):

(I)：2.0≤DS2+DS3+DS6≤3.0

(II)：DS6/(DS2+DS3+DS6)≥0.315

(2-2) as (2-1) described optical compensation films, wherein said cellulose acylate film contains at least a delay that comprises bar-shaped or discoid compound expresses agent.

(2-3) as (2-1) or (2-2) described optical compensation films; wherein under 25 ℃-10%RH and 25 °-80%RH condition; difference DELTA Re (Re10%RH-Re80%RH) between the length of delay Re (550) of described cellulose acylate film is 12nm or following; under 25 ℃-10%RH and 25 °-80%RH condition, the difference DELTA Rth (Rth10%RH-Rth80%RH) between the length of delay Rth (550) of described cellulose acylate film is 32nm or following.

[in above-mentioned (2-3), Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm.]

(2-4) as (2-1)～(2-3) each described polaroid, wherein said liquid crystal compounds is discoid liquid crystal compounds.

(2-5) a kind of polaroid, it has each described optical compensation films and polarizer as (2-1)～(2-4).

(2-6) a kind of LCD, it has liquid crystal cell and as (2-1)～(2-4) each described optical compensation films or as (2-5) described polaroid.

(2-7), wherein use ocb mode as (2-6) described LCD.

In the present invention, following pattern also is preferred.

(2-8) as (2-1)～(2-4) each described optical compensation films, the acyl group in the wherein said cellulose acylate film is an acetyl group.

(2-9) as (2-1)～(2-4) each described optical compensation films, wherein said cellulose acylate film contains at least a adjuvant that is selected from plastifier, ultraviolet light absorber or separation promoter.

(2-10) as (2-1)～(2-4) each described optical compensation films, the thickness of wherein said cellulose acylate film is 40 μ m～180 μ m.

(2-11) as (2-1)～(2-4) each described optical compensation films, the content of wherein said adjuvant in described cellulose acylate film accounts for 10～30% of described cellulose acylate film quality.

(2-12) as (2-1)～(2-4) each described optical compensation films, wherein said cellulose acylate film balance water content under 25 ℃ of temperature and humidity 80%RH is below 3.4%.

(2-13) as (2-1)～(2-4) each described optical compensation films, wherein under 24 hours condition under the 60 ℃-95%RH, the moisture content perviousness of described cellulose acylate film is 400g/m ²24hr～2,300g/m ²24hr (being scaled film thickness 80 μ m calculates).

(2-14) as (2-1)～(2-4) each described optical compensation films, wherein said cellulose acylate film is after leaving standstill 48 hours under the condition of 80 ℃ and 90%RH, and mass change is 0～5%.

(2-15) as (2-1)～(2-4) each described optical compensation films; wherein said cellulose acylate film leaves standstill the change in size due to 24 hours under 60 ℃ and 95%RH; and under 90 ℃ and 5%RH, leave standstill change in size due to 24 hours, all in 0%～5% scope.

(2-16) as (2-1)～(2-4) each described optical compensation films, the glass transition temperature Tg of wherein said cellulose acylate film is 80 ℃～180 ℃.

(2-17) as (2-1)～(2-4) each described optical compensation films, the elastic modulus of wherein said cellulose acylate film is 1,500MPa～5,000MPa.

(2-18) as (2-1)～(2-4) each described optical compensation films, the photoelastic coefficient of wherein said cellulose acylate film is 50 * 10 ^-13Cm ²/ dyne or following.

(2-19) as (2-1)～(2-4) each described optical compensation films, the mist degree of wherein said cellulose acylate film is 0.01%～2%.

(2-20) as (2-1)～(2-4) each described optical compensation films, the mean diameter that wherein said cellulose acylate film contains secondary is fine particles of silica of 0.2 μ m～1.5 μ m.

(2-21) as (2-1)～(2-16) each described optical compensation films, wherein said liquid crystal compounds is discoid liquid crystal compounds.

(2-22) as (2-5) described polaroid, when under 25 ℃ and 60%RH condition, measuring, further have at least one factor that is selected from veneer transmissivity TT, parallel transmissivity PT, intersects transmissivity CT or degree of polarization P and satisfy following formula (a) and (b), (c) or (d) respectively:

(a)40.0≤TT≤45.0

(b)30.0≤PT≤40.0

(c)CT≤2.0

(d)95.0≤P。

(2-23) as (2-5) described polaroid, when the intersection transmissivity of measuring under wavelength X is expressed as CT (λ), described polaroid about intersect transmissivity also satisfy following formula (e), (f) and (g) at least one:

(e)CT(3?80)≤2.0

(f)CT(410)≤0.1

(g)CT(700)≤0.5。

(2-24) as (2-5) described polaroid, when described polaroid after leaving standstill 500 hours under 60 ℃ and the 95%RH condition, also have and intersect the variation delta P of the variation delta CT of transmissivity and degree of polarization at least and satisfy following formula (j) or (k):

(j)-6.0≤ΔCT≤6.0

(k)-10.0≤ΔP≤0.0

(2-25) as (2-5) described polaroid, on surface relative with liquid crystal cell, that will place diaphragm, also provide the one deck at least that is selected from hard conating, antiglare layer or the anti-reflecting layer.

(2-26) as (2-5) described polaroid, it is packaged in the damp proof bag that interior humidity is adjusted to 25 ℃ of following 43%RH～65%RH.

(2-27) as (2-5) described polaroid, it is packaged in interior humidity and is adjusted to and is stacked on ambient humidity on the liquid crystal board with described polaroid and differs in 15%RH or the following damp proof bag.

According to the present invention; a kind of optical compensation films may be provided; the cellulose acylate film of its use shows in the excellent face and the lag characteristic of thickness direction, and reduces the delay variation with ambient humidity, and a kind of polaroid that uses this optical compensation films also is provided.

In addition, the present invention can provide a kind of LCD that viewing angle characteristic changes that reduces.

Description of drawings

Fig. 1 is the synoptic diagram of a pixel region example in the LCD of the present invention

Fig. 2 is the synoptic diagram of LCD example of the present invention.

Fig. 3 is the synoptic diagram of another example of LCD of the present invention.

Specifying of invention

Describe exemplary of the present invention below in detail.

(cellulose acylate)

Describe the cellulose acylate that the present invention preferably uses below in detail.By β-1, the 4-key constitutes cellulosic each glucose unit and has free hydroxyl in its 2-position, 3-position and 6-position.Cellulose acylate is these hydroxylic moieties or the polymkeric substance that all obtained by the acyl group esterification.Acyl substituted degree DS2, DS3 and DS6 refer to the hydroxy esterification rate (under the situation of 100% esterification, degree of substitution is 1) of 2-position, 3-position and 6-position respectively.

The total degree of substitution of acyl group, or DS2+DS3+DS6 are preferably 2.00～3.00, and more preferably 2.22～2.90, preferred especially 2.40～2.82.In addition, DS6/ (DS2+DS3+DS6) preferred 0.315 or more than, more preferably 0.322 or more than, preferred especially 0.324～0.340.Here; the DS2 representative is to the degree of substitution (hereinafter being also referred to as " 2-position acyl substituted degree ") of glucose unit 2-position hydroxyl; DS3 representative is to the degree of substitution (hereinafter being also referred to as " 3-position acyl substituted degree ") of glucose unit 3-position hydroxyl and the DS6 representative degree of substitution (hereinafter being also referred to as " 6-position acyl substituted degree ") to glucose unit 6-position hydroxyl.

The acyl group that uses in the cellulose acylate of the present invention can only be a kind of acyl group, or is made of two or more acyl groups.When using two or more acyl groups, wherein a kind of preferably acetyl group.When the total degree of substitution of acetyl group of 2-position, 3-position and 6-position hydroxyl is expressed as DSA, and the total degree of substitution of acyl group outside the acetyl group of 2-position, 3-position and 6-position hydroxyl is when being expressed as DSB, and the value of DSA+DSB is preferably 2.2～2.86, and preferred especially 2.40～2.80.In addition, the DSB value be 1.50 or more than, preferred especially 1.7 or more than.In addition, at least 28% of the DSB value is degree of substitution to 6-position hydroxyl.In addition, in the DSB value to the ratio of 6-position hydroxyl degree of substitution be preferably 30% or more than, more preferably 31% or more than, preferred especially 32% or more than.Selectively, may use the DSA+DSB of 6-position value be 0.75 or more than, preferred 0.80 or more than, preferred especially 0.85 or above cellulose acylate film.These cellulose acylate films make and may prepare the good solution with suitable solubleness, particularly when using no chlorine organic solvent.In addition, can use the low and high solution of filtration efficiency of these film preparation viscosity.

In the acyl group of cellulose acylate of the present invention, each group has at least 2 carbon atoms, can be aliphatic group or aromatic group, is not particularly limited.Cellulose acylate can be cellulosic alkyl-carbonyl ester or alkenyl carbonyl ester, perhaps cellulosic aryl carbonyl ester or aryl-and the alkyl-carbonyl ester, each can also have substituting group.The suitable example of such acyl group comprises acetyl group, propiono, bytyry; valeryl, caproyl, caprylyl; capryl, dodecane acyl group, tridecane acyl group; tetradecane acyl group, hexadecane acyl group, octadecanoyl; isobutyryl, uncle's bytyry, cyclohexane carbonyl; oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl.In these groups, acetyl group, propiono, bytyry, dodecane acyl group, octadecanoyl, uncle's bytyry, oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl are more preferred than other, and acetyl group, propiono and bytyry are particularly advantageous.

(method of synthetic cellulose acylate)

The ultimate principle of cellulose acylate synthetic method is documented in people's such as Migita WoodChemistry, in the 180-190 page or leaf (Kyoritsu Shuppan Co., Ltd., 1968).Representative synthetic method is to use the liquid phase esterification process of carboxylic acid anhydrides, acetate and sulfuric acid catalyst.Particularly,, be added to then in the carboxylation potpourri of cooling in advance and carry out esterification with the plain parent material of an amount of acetate pretreatment of fiber such as velveteen and wood pulp, thus synthetic cellulose acylate completely (in the 2-position, the degree of substitution summation of 3-position and 6-position be about 3).Above-mentioned carboxylation potpourri contain usually acetate as solvent, carboxylic acid anhydrides as esterifying agent and sulfuric acid as catalyzer.Its stoichiometry of normally used carboxylic acid anhydrides is above the total amount of the water that exists in cellulose that reacts with it and the system.After acylation reaction is finished, add neutralizing agent () aqueous solution for example, the carbonate of calcium, magnesium, iron, aluminium or zinc, acetate or oxide, with excess carboxylic acid acid anhydride remaining in the hydrolyzation system, and in and the partial esterification catalyzer.Then; exist down at a small amount of acetylization reaction catalyzer (usually, residual sulfuric acid), the complete cellulose acylate that obtains is remained under 50～90 ℃; carry out saponification and aging, cellulose acylate becomes the cellulose acylate with required acyl substituted degree and degree of polymerization thereby make completely.When obtaining required cellulose acylate; with above-mentioned neutralizing agent fully in and remaining catalyzer in the system; perhaps do not neutralize cellulose acylate solution is added in water or the dilute sulfuric acid and (perhaps water or dilute sulfuric acid are poured in the cellulose acylate solution); the plain acylate of defibre; wash then and stabilization processes, thereby obtain cellulose acylate.

In cellulose acylate film of the present invention, the component of polymer that preferably constitutes film consists essentially of above-mentioned cellulose acylate.Term " basically " meaning is the component of polymer of 55 quality % or more (preferred 70 quality % or more, more preferably 80 quality % or more).Parent material as film is made preferably uses the cellulose acylate particle.Preferred 90 quality % or more used particle size are 0.5～5mm.In addition, preferred 50 quality % or more used particle size are 1～4mm.The cellulose acylate particle preferably has the shape of the sphere of approaching as far as possible.

The viscometric degree of polymerization of the cellulose acylate that the present invention uses is 200～700, and is preferred 250～550, more preferably 250～400, preferred especially 250～350.Average degree of polymerization can be according to people's such as Uda limiting viscosity (limiting viscosity) method (Kazuo Uda and Hideo Saito, Seni-Gakkai Shi (The Journal of the Society of Fiber Science andTechnology, Japan) 18 (1), 105-120,1962)) measure.In addition, this has detailed further record in JP-A-9-95538.

When cellulose acylate is removed low molecular weight compositions, it is big that its mean molecular weight (degree of polymerization) becomes.Yet its viscosity becomes and is lower than conventional cellulose acylate, and therefore, it is useful removing low molecular weight compositions.The cellulose acylate that contains a small amount of low molecular weight compositions can obtain by remove low molecular weight compositions from the synthetic cellulose acylate of conventional method.Removing low molecular weight compositions can be by carrying out with the organic solvent washing cellulose acylate that is fit to.When manufacturing contained the cellulose acylate of a small amount of low molecular weight compositions, the sulfuric acid catalysis dosage in the acylation reaction preferably was adjusted to 0.5～25 mass parts, in the cellulose of 100 mass parts.When being adjusted to the amount of sulfuric acid catalyst in the above-mentioned scope, the also cellulose acylate of preferred (even molecular weight distribution) can synthetic molecular weight distributes.When being used to make cellulose acylate film of the present invention, the cellulose acylate water cut is preferably 2 quality % or still less, more preferably water cut 1 quality % or still less, special preferred water content 0.7 quality % or still less.Usually, cellulose acylate contains water, and its water cut is known as 2.5～5 quality %.In order in the present invention cellulose acylate to be adjusted to this water cut, need carry out drying, its method is not particularly limited, as long as can obtain required water cut.

The parent material cotton of these cellulose acylates that the present invention uses and synthetic method write up are at JIII Journal of Technical Disclosure No.2001-1745; in 7～12 pages (publish May 15 calendar year 2001, Japan Institute of Invention and Innovation).

(adjuvant)

In each manufacturing step; according to its purposes; can be (for example with various adjuvants; plastifier, ultraviolet light absorber, rotten inhibitor; postpone (optical anisotropy) and express agent; fine particle, release agent and infrared absorbent) be added in the cellulose acylate solution of the present invention, these adjuvants can be solid or oily product.In other words, its fusing point and boiling point are not particularly limited.For example, 20 ℃ of fusing points or lower and fusing point are higher than 20 ℃ ultraviolet light absorber and can be mixed with each other, and perhaps plastifier can similarly mix, and these contents for example are documented among the JP-A-2001-151901.The example of release agent comprises the ethyl ester of citric acid.In addition, the infrared ray absorbing dyestuff for example is documented among the JP-A-2001-194522.These adjuvants can add in any time in the dope preparation process, and the step of adding adjuvant can be used as the final step adding of dope preparation process.In addition, the various quantity of material that added are not particularly limited, as long as can bring into play its effect.When cellulose acylate film formed multilayer, the kind of the adjuvant of adding can be different in each layer with its amount.This for example is documented among the JP-A-2001-151902, and is hitherto known technology.Preferably by selecting the kind and the addition thereof of these adjuvants, the glass transition temperature (Tg) of cellulose acylate film is adjusted to 70～145 ℃ and will use the elastic modulus of stretching testing machine measurement to be adjusted to 1,500～3,000MPa.

In addition, preferably use write up, since the material of 16 pages (publish May 15 calendar year 2001, Japan Institute of Invention and Innovation) at JIII Journal of Technical Disclosure No.2001-1745.

(plastifier)

Film preferably of the present invention contains plastifier.The compound that is used as plastifier in this film is not particularly limited, but it is hydrophobic that they preferably have more than cellulose acylate, its example comprises phosphate, as Triphenyl phosphate, lindol, tricresyl phosphate base diphenyl, octyl diphenyl phosphate, di(2-ethylhexyl)phosphate phenylbiphenylyl ester, tricresyl phosphate octyl group ester and tricresyl phosphate butyl ester; Phthalic ester, phthalic acid diethyl ester for example, phthalic acid dimethoxy-ethyl ester, phthalic acid dimethyl esters, phthalic acid dioctyl ester, phthalic acid dibutyl ester and phthalic acid two-2-ethylhexyl; Ethyl glycolate, as glyceryl triacetate, tributyrin, butyl phthalyl butyl alcohol acid esters, ethyl phthalyl ethyl hexanol acid esters, methyl phthalyl ethyl hexanol acid esters and butyl phthalyl butyl alcohol acid esters.Need, these plastifier can use separately or use with its two or more composition.

(postponing to express agent)

For expressing length of delay in the present invention, suitable is to have the compound of at least two aromatic rings as postponing to express agent.By the polymkeric substance of per 100 mass parts, postpone to express preferred 0.05～20 mass parts of agent consumption, more preferably 0.1～10 mass parts, further preferred 0.2～5 mass parts, preferred especially 0.5～2 mass parts.Can be used in combination two or more and postpone to express agent.

Used delay is expressed agent and is preferably had absorption maximum at the wavelength zone of 250～400nm, and does not preferably absorb basically at visible region.

Used in this manual term " aromatic ring " not only comprises the aromatic hydrocarbon ring, and comprises aromatic heterocycle.

The aromatic hydrocarbon ring is 6-unit's ring (that is phenyl ring) especially preferably.

Aromatic heterocycle is unsaturated heterocycle normally, and they are 5-, 6-or 7-unit ring preferably, more preferably 5-or 6-unit ring.Aromatic heterocycle respectively has most two keys usually.Wherein contained heteroatoms is nitrogen, oxygen and sulphur atom, particularly nitrogen-atoms preferably.The example of aromatic heterocycle comprises furan nucleus, thiphene ring, pyrrole ring ， oxazole ring ， isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazoles ring, furazan ring, triazole ring, pyranoid ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazines ring.

The aromatic ring that is fit to is a phenyl ring, furan nucleus, thiphene ring, pyrrole ring ， oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazines ring.In these rings, the 1,3,5-triazines ring is particularly preferred.More specifically, can advantageously use disclosed compound in JP-A-2001-166144.

Aromatic ring quantity that postpone to express agent preferably 2～20, more preferably 2～12, more more preferably 2～8, preferred especially 2～6.

Bonding relation between two aromatic rings is divided into the situation that (a) ring forms condensed ring, and (b) ring is with the situation of singly-bound Direct Bonding, or (c) ring with the situation (because of two rings are aromatic rings, so can not form the spiral shell key) of linking group bonding.The bonding relation can be any in (a)～(c).

The example of condensed ring in the situation (a) (two or more aromatic rings form) comprises the indenes ring, naphthalene nucleus, azulenes, fluorenes ring, phenanthrene ring, anthracene nucleus, acenaphthylene ring, inferior cyclohexyl biphenyl, the naphtho-naphthalene nucleus, pyrene ring, indole ring, iso-indoles ring, the coumarone ring, benzothiophene ring, indolizine ring, benzoxazole ring, the benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, the indazole ring, chromene ring, quinoline ring, isoquinoline ring, the quinolizine ring, quinazoline ring, cinnolines ring, quinoxaline ring, the phthalazines ring, pteridine ring, carbazole ring, acridine ring, the phenanthridines ring, xanthene ring, azophenlyene ring, the phenothiazine ring, phenoxthine ring ， phenoxazine ring and thianthrene ring.In these rings, than other preferably naphthalene nucleus, azulenes, indole ring, benzoxazole ring, benzoxazole ring, benzimidazole ring, benzotriazole ring and quinoline ring.

Singly-bound in the situation (b) is the carbon-carbon bond between two aromatic rings preferably.Two aromatic rings can pass through two or more singly bounds, form cycloaliphatic ring or nonaromatic heterocycles between them.

Linking group in the preferable case (c) also is connected to the carbon atom of two aromatic rings.Linking group is alkylidene preferably, alkenylene, alkynylene ,-CO-,-O-,-NH-, two or more combination of-S-or its.As follows by the example that makes up the linking group that above-mentioned two or more group forms.In addition, following each linking group can about upset.

c1：-CO-O-

c2：-CO-NH-

C3:-alkylidene-O-

c4：-NH-CO-NH-

c5：-NH-CO-O-

c6：-O-CO-O-

C7:-O-alkylidene-O-

The c8:-CO-alkenylene-

C9:-CO-alkenylene-NH-

C10:-CO-alkenylene-O-

C11:-alkenylene-CO-O-alkylidene-O-CO-alkylidene-

C12:-O-alkylidene-CO-O-alkylidene-O-CO-alkylidene-O-

C13:-O-CO-alkylidene-CO-O-

The c14:-NH-CO-alkenylene-

The c15:-O-CO-alkenylene-

Aromatic ring and linking group can have substituting group.

Described substituent example comprises halogen atom (F, Cl, Br; I), hydroxyl, carboxyl; cyano group, amino, nitro; sulfo group, carbamyl, sulfamoyl; urea groups, alkyl, thiazolinyl; alkynyl, aliphatic acyl radical, aliphatics acyloxy; alkoxy, alkoxy carbonyl, alkoxycarbonyl amino; alkylthio group, alkyl sulphonyl, aliphatics acylamino-; the aliphatics sulfonamido, the amino that aliphatics replaces, the carbamyl that aliphatics replaces; the sulfamoyl that aliphatics replaces, urea groups and nonaromatic heterocycles base that aliphatics replaces.

Carbon number in the alkyl is preferably 1～8.Alkyl group than naphthenic base more preferably, straight chained alkyl is particularly preferred.These alkyl can also have substituting group (for example, hydroxyl, carboxyl, alkoxy, the amino of alkyl-replacement).The example of such alkyl (alkyl that comprises replacement) comprises methyl, ethyl, normal-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxy ethyl and 2-diethylamino ethyl.

Carbon number in the thiazolinyl is preferably 2～8.Alkenyl than cycloalkenyl group more preferably, straight-chain alkenyl is particularly preferred.These thiazolinyls can also have substituting group.The example of such thiazolinyl comprises vinyl, allyl and 1-hexenyl.

Carbon number in the alkynyl is preferably 2～8.Alkynyl group than cycloalkynyl radical more preferably, straight-chain alkynyl is particularly preferred.These alkynyls can also have substituting group.The example of such alkynyl comprises ethinyl, 1-butynyl and 1-hexin base.

Carbon number in the aliphatic acyl radical is preferably 1～10.The example of such aliphatic acyl radical comprises acetyl group, propiono and bytyry.

Carbon number in the aliphatics acyloxy is preferably 1～10.The example of such aliphatics acyloxy comprises acetoxyl group.

Carbon number in the alkoxy is preferably 1～8.Such alkoxy can also have substituting group (for example, alkoxy).The example of alkoxy (alkoxy that comprises replacement) comprises methoxyl, ethoxy, butoxy and methoxy ethoxy.

Carbon number in the alkoxy carbonyl is preferably 2～10.The example of such alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.

Carbon number in the alkoxycarbonyl amino is preferably 2～10.The example of such alkoxycarbonyl amino comprises the amino and ethoxy carbonyl amino of methoxycarbonyl.

Carbon number in the alkylthio group is preferably 1～12.The example of such alkylthio group comprises methyl mercapto, ethylmercapto group and hot sulfenyl.

Carbon number in the alkyl sulphonyl is preferably 1～8.The example of such alkyl sulphonyl comprises methane sulfonyl and ethane sulfonyl.

Carbon number in the aliphatics acylamino-is preferably 1～10.The example of such acylamino-comprises acetylamino.

Carbon number in the aliphatics sulfonamido is preferably 1～8.The example of such aliphatics sulfonamido comprises sulfonyl methane amino, butane sulfonamido and normal octane sulfonamido.

Carbon number in the amino that aliphatics replaces is preferably 1～10.The example of the amino that such aliphatics replaces comprises dimethylamino, diethylamino and 2-carboxy ethyl amino.

Carbon number in the carbamyl that aliphatics replaces is preferably 2～10.The example of the carbamyl that such aliphatics replaces comprises methylamino formoxyl and diethylamino formoxyl.

Carbon number in the sulfamoyl that aliphatics replaces is preferably 1～8.The example of the sulfamoyl that such aliphatics replaces comprises methyl sulfamoyl and diethyl amino sulfonyl.

Carbon number in the urea groups that aliphatics replaces is preferably 2～10.The example of the urea groups that such aliphatics replaces comprises the methyl urea groups.

The example of nonaromatic heterocycles base comprises piperidyl and morpholinyl.

The molecular weight of postpone expressing agent preferably 300～800.

In the present invention, preferably bar-shaped or discoid compound is expressed agent as postponing, and except the compound with 1,3,5-triazines ring, uses the bar-shaped compound advantageous particularly with straight-chain molecular structure.Term " straight-chain molecular structure " refers to that the stable molecular structure of the thermokinetics of bar-shaped compound is a straight chain.The stable structure of thermokinetics can be determined by crystal structure analysis or Molecular Orbital Calculation.For example, use Molecular Orbital Calculation software program (for example, the WinMOPAC2000 that Fujitsu produces) can carry out Molecular Orbital Calculation, thereby can measure the molecular structure in the time of the heat that is used to form target compound can being minimized.Statement " molecular structure is a straight chain " refers to that main chain forms 140 ° or above angle in the stable structure of thermokinetics.

As the bar-shaped compound with at least two aromatic rings, those of following formula (1) representative are fit to:

Formula (1): Ar ¹-L ¹-Ar ²

In following formula (1), Ar ¹And Ar ²Each represents aromatic group independently.

Term used herein " aromatic group " is intended to comprise aryl (aromatic hydrocarbyl), the aryl of replacement, the heterocyclic radical that aromatic heterocycle and aromatic series replace.

The heterocyclic radical that the aryl of aryl or replacement replaces than aromatic heterocycle and aromatic series more preferably.The normally undersaturated ring of heterocycle in the aromatic heterocycle, they are 5-, 6-or 7-unit ring preferably, more preferably 5-or 6-unit ring.Each has maximum two keys usually heteroaromatic.Wherein contained heteroatoms is nitrogen, oxygen or sulphur atom preferably, more preferably nitrogen or sulphur atom.The example of aromatic ring comprises phenyl ring in the aromatic group, furan nucleus, thiphene ring, pyrrole ring ， oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring or pyrazine ring.In these rings, phenyl ring than other more preferably.

Substituent example in the heterocyclic radical that aryl that replaces and aromatic series replace comprises halogen atom (F, Cl, Br; I), hydroxyl, carboxyl; cyano group, amino, alkyl amino are (for example; methylamino, ethylamino, butyl amino; dimethylamino), nitro, sulfo group; carbamyl, alkyl-carbamoyl (for example, N-methylamino formoxyl; N-ethylamino formoxyl, N, N-formyl-dimethylamino); sulfamoyl, alkylsulfamoyl group (for example, N-methyl sulfamoyl; N-ethyl sulfamoyl, N, N-dimethylamino sulfonyl); urea groups, alkyl urea groups (for example, N-methyl urea groups; N, N-dimethyl urea groups, N; N, N '-trimethyl urea groups), alkyl is (for example; methyl, ethyl, propyl group; butyl, amyl group, heptyl; octyl group, isopropyl, sec-butyl; tertiary pentyl, cyclohexyl, cyclopentyl); thiazolinyl (for example, vinyl, allyl; hexenyl), alkynyl (for example, ethinyl; butynyl), acyl group (for example, formoxyl; acetyl group, bytyry, caproyl (hexannoyl); lauroyl), acyloxy (for example, acetoxyl group; butyryl acyloxy, hexylyloxy, bay acyloxy); alkoxy (for example, methoxyl, ethoxy; propoxyl group, butoxy, amoxy; heptan the oxygen base, octyloxy), aryloxy group (for example; phenoxy group), alkoxy carbonyl (for example, methoxycarbonyl; ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl; pentyloxy carbonyl, heptan oxygen base carbonyl), aryloxycarbonyl is (for example; phenyloxycarbonyl); alkoxycarbonyl amino (for example, butoxy carbonyl amino, hexyloxy carbonyl amino); alkylthio group (for example; methyl mercapto, ethylmercapto group, rosickyite base; butylthio; penta sulfenyl, heptan sulfenyl, hot sulfenyl); arylthio (for example; thiophenyl), alkyl sulphonyl (for example, methyl sulphonyl; ethylsulfonyl; the sulfonyl propyl base, butyl sulfonyl, amyl group sulfonyl; the heptyl sulfonyl; the octyl group sulfonyl), acylamino-(for example, acetylamino; the butyl acylamino-; the hexyl acylamino-, the lauryl acylamino-) and the non-aromatic heterocyclic radical is (for example; morpholinyl, pyrazinyl).

In these substituting groups, than other preferably halogen atom, cyano group, carboxyl, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acylamino-, alkoxy carbonyl, alkoxy, alkylthio group and alkyl.

Moieties in alkyl amino, alkoxy carbonyl, alkoxy and alkylthio group and alkyl can also have substituting group.The substituent example of moieties and alkyl comprises halogen atom, hydroxyl, carboxyl, cyano group, amino; alkyl amino, nitro, sulfo group, carbamyl, alkyl-carbamoyl; sulfamoyl, alkylsulfamoyl group, urea groups, alkyl urea groups, thiazolinyl; alkynyl, acyl group, acyloxy, alkoxy; aryloxy group, alkoxy carbonyl, aryloxycarbonyl, alkoxycarbonyl amino; alkylthio group, arylthio, alkyl sulphonyl, acylamino-and non-aromatic heterocyclic radical.In these substituting groups, than other preferably halogen atom, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acyl amino, alkoxy carbonyl and alkoxy.

In formula (1), L ¹Be to be selected from alkylidene, alkenylene, alkynylene ,-O-, the divalent linker of-CO-or its two or more combinations.Alkylidene can have ring structure.As the ring alkylidene, cyclohexylene, particularly 1, the 4-cyclohexylene is suitable for.About the open chain alkylidene, straight-chain alkyl-sub-than branched alkylidene more preferably.

Carbon number in such alkylidene is preferably 1～20, and more preferably 1～15, preferred again 1～10, more more preferably 1～8, preferred especially 1～6.

Have the alkenylene of open-chain structure and alkynylene ratio and have the ring structure person is preferred, have the alkenylene of linear chain structure and alkynylene ratio and have the branched structure person is preferred.It is suitable that carbon number in described alkenylene and described alkynylene respectively is 2～10, preferred 2～8, and more preferably 2～6, preferred again 2～4,2-(ethenylidene or ethynylene) especially preferably.

Preferred 6～20 of carbon number in the described aryl, more preferably 6～16, more preferably 6～12 again.

Ar ¹And Ar ²Pass L ¹Formed angle is preferably at least 140 ° when facing with each other state.

As bar-shaped compound, the compound of following formula (2) representative is more suitable for:

Formula (2):

Ar ¹-L ²-X-L ³-Ar ²

In following formula (2), Ar ¹And Ar ²Be aromatic group independently.As Ar ¹And Ar ²Definition and the example of aromatic group with identical to described in the formula (1) those.

In formula (2), L ²And L ³Each representative is selected from alkylidene ,-O-, the divalent linker of-CO-and its two or more combinations.

About alkylidene, the alkylidene with open-chain structure is more preferred than the alkylidene with ring structure, and straight-chain alkyl-sub-than branched alkylidene more preferably.

Carbon number in the described alkylidene is preferably has 1～10, and more preferably 1～8, more preferably 1～6 again, preferred especially 1～4.Yet optimal number is 1 or 2 (corresponding to methylene or ethylidene).

L ²And L ³Each is only to be-O-CO-or-CO-O-.

In formula (2), X is 1,4-cyclohexylene, ethenylidene or ethynylene.

The example of the compound of formula (1) representative is as follows.

Exemplary compounds (1)～(34), (41) and (42) respectively have two unsymmetrical carbons in 1-position and 4-position.Yet,,, but geometric isomeride (trans-and cis-) is only arranged separately so these compounds all do not have optical isomer (optical activity) because exemplary compounds (1), (4)～(34), (41) and (42) have symmetrical meso-form molecular structure.The exemplary compounds (1) of trans (1-trans) and cis (1-cis) is as follows.

As mentioned above, the bar-shaped compound of the present invention's use preferably has linear chain structure.Therefore, trans-compound is more preferred than cis-compound.

Exemplary compounds (2) and (3) all have optical isomer (four isomeride altogether) except geometric isomeride.About geometric isomeride, as mentioned above, trans-ratios of the isomers cis-isomeride is more preferably.Yet,, comment on some good more nonsensical than other as for optical isomer.Therefore they can be any of dextrorotation (D), left-handed (L) or racemic form.

In exemplary compounds (43)～(45), though the ethenylidene key of center can for trans-and cis-, because above-mentioned identical, preferably trans-.

Other compounds suitable for use are as follows.

Can mix use in the ultra-violet absorption spectrum that solution state shows maximum absorption wavelength (λ max) less than two or more bar-shaped compounds of 250nm.

Bar-shaped compound can be by synthetic with reference to record method in the literature.The example of described document comprises Mol.Cryst.Liq.Cryst., Vol.53,229 pages (1979), ibid., Vol.89,93 pages (1982), and ibid., Vol.145,111 pages (1987), and ibid., Vol.170,43 pages (1989), J.Am.Chem.Soc., Vol.113,1349 pages (1991), ibid., Vol.118,5346 pages (1996), and ibid., Vol.92,1582 pages (1970), J.Org.Chem., Vol.40,420 pages (1975) and Tetrahedron, Vol.48, No.16,3437 pages (1992).

The addition that postpones the expression agent is preferably 0.1～30 quality % of used amount of polymers, more preferably 0.5～20 quality %.

By the cellulose acylate of per 100 mass parts, above-mentioned aromatics preferable amount is 0.01～20 mass parts, more preferably 0.05～15 mass parts, preferred especially 0.1～10 mass parts.Can mix and use above-mentioned two or more aromatics.

Describe the organic solvent of dissolving cellulos acylate below in detail.

(chloro solvent)

When preparation cellulose acylate solution of the present invention, the chloro organic solvent is preferably used as primary solvent.In the present invention, be not particularly limited the kind of chloro organic solvent, as long as can realize that the dissolving cellulos acylate is to carry out fluid casting or film formed purpose.These chloro organic solvents are methylene chloride or chloroform preferably, preferred especially methylene chloride.In addition, be not particularly limited for the organic solvent that mixes outside the chloro organic solvent.In this case, the methylene chloride of use must account at least 50 quality %.The following describes the non-chloro organic solvent that mixes use with the chloro organic solvent.In other words, non-chloro organic solvent preferably is selected from the ester that all has 3～12 carbon atoms, ketone, ether, the solvent of hydrocarbon.Ester, ketone, ether and hydrocarbon can have ring structure.Have any two or more esters, ketone and ether functional group (that is, and-O-,-CO-and-COO-) compound also can be used as solvent.For example, solvent can have another kind of functional group simultaneously, as alcoholic extract hydroxyl group.When solvent had two or more functional groups, the carbon number of solvent can be in the scope to compound defined with any functional group.Example with ester of 3～12 carbon atoms comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.Example with ketone of 3～12 carbon atoms comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexane.Example with ether of 3～12 carbon atoms comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-diox, 1,3-dioxolane, tetrahydrofuran, anisole and phenetol.Representative examples of organic with two or more functional groups comprises the 2-ethoxy ethyl acetate, 2-methyl cellosolve and butoxy ethanol.

The alcohol that is used in combination with the chloro organic solvent is straight chain, side chain or ring-type preferably, preferred especially saturated aliphatic hydrocarbon.The hydroxyl of alcohol can be a primary hydroxyl to any of tert-hydroxyl.The example of alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-methyl-2-butanols and cyclohexanol.In addition, fluorine-based alcohol also is suitable as alcohol.Its example comprises the 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3,3-tetrafluoro-1-propyl alcohol.In addition, hydrocarbon can be straight chain, side chain or ring-type.Can use aromatic hydrocarbon or aliphatic hydrocarbon.Aliphatic hydrocarbon can be saturated or undersaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.

The combination that the present invention is preferably used as the chloro organic solvent of primary solvent includes but not limited to following:

Methylene chloride/ethanol/butanols (75/10/5/5/5, mass parts),

Methylene chloride/acetone/methanol/propyl alcohol (80/10/5/5, mass parts),

Methylene chloride/butanols/cyclohexane (75/10/5/5/5, mass parts),

Methylene chloride/methyl ethyl ketone/methyl alcohol/butanols (80/10/5/5, mass parts),

Methylene chloride/acetone/methyl ethyl ketone/ethanol/isopropyl alcohol (75/8/5/5/7, mass parts),

Methylene chloride/cyclopentanone/methanol/isopropanol (80/7/5/8, mass parts),

Methylene chloride/methyl acetate/butanols (80/10/10, mass parts),

Methylene chloride/cyclohexanone/methyl alcohol/hexane (70/20/5/5, mass parts),

Methylene chloride/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts),

Methylene chloride/1,3-dioxolanes/methanol/ethanol (70/20/5/5, mass parts),

Methylene chloride/diox/acetone/methanol/ethanol (60/20/10/5/5, mass parts),

Methylene chloride/acetone/cyclopentanone/ethanol/isobutyl alcohol/cyclohexane (65/10/10/5/5/5, mass parts),

Methylene chloride/methyl ethyl ketone/acetone/methanol/ethanol (70/10/10/5/5, mass parts),

Methylene chloride/acetone/ethyl/acetic acid esters/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts),

Methylene chloride/methyl acetoacetate/methanol/ethanol (65/20/10/5, mass parts) and

Methylene chloride/cyclopentanone/ethanol/butanols (65/20/10/5, mass parts).

(non-chloro solvent)

Then, the following describes the non-chloro organic solvent that when preparation cellulose acylate solution of the present invention, preferably uses.In the present invention, be not particularly limited non-chloro organic solvent, as long as can realize that the dissolving cellulos acylate is to carry out fluid casting or film formed purpose.Non-chloro organic solvent preferably is selected from the solvent of the ester, ketone and the ether that all have 3～12 carbon atoms.Ester, ketone, ether and hydrocarbon can have ring structure.Have any two or more esters, ketone and ether functional group (that is, and-O-,-CO-and-COO-) compound also can be used as primary solvent.For example, solvent can have another kind of functional group, as alcoholic extract hydroxyl group.When solvent had two or more functional groups, the carbon number of solvent can be in the scope to compound defined with any functional group.Example with ester of 3～12 carbon atoms comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.Example with ketone of 3～12 carbon atoms comprises acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexane.Example with ether of 3～12 carbon atoms comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-diox, 1,3-dioxolanes, tetrahydrofuran, anisole and phenetol.Representative examples of organic with two or more functional groups comprises the 2-ethoxy ethyl acetate, 2-methyl cellosolve and butoxy ethanol.

The used non-chloro organic solvent of above-mentioned cellulose acylate is selected from above-mentioned each side, but below preferred the use.That is, for the cellulose acylate that the present invention uses, preferred solvent is the mixed solvent that is made of three kinds or more kinds of solvent that differs from one another.First solvent is selected from methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, at least a in dioxolanes ， diox or its mixed solution.Second solvent is selected from ketone and the acetoacetic ester with 4～7 carbon atoms.The 3rd solvent is selected from the pure and mild hydrocarbon that respectively has 1～10 carbon atom, preferably has the alcohol of 1～8 carbon atom.When first solvent is the mixed solution of two or more solvents, can not use second solvent.First solvent is more preferably methyl acetate, acetone, and methyl formate, ethyl formate or its potpourri, second solvent is methyl ethyl ketone preferably, cyclopentanone, cyclohexanone or methyl acetoacetate or its mixed liquor.

Alcohol as the 3rd solvent can be straight chain, side chain or ring-type, preferred especially saturated aliphatic hydrocarbon.The hydroxyl of alcohol can be a primary hydroxyl to any of tert-hydroxyl.The example of alcohol comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-methyl-2-butanols and cyclohexanol.In addition, fluorine-based alcohol can be as alcohol.Its example comprises the 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3,3-tetrafluoro-1-propyl alcohol.In addition, hydrocarbon can be straight chain, side chain or ring-type.Can use aromatic hydrocarbon or aliphatic hydrocarbon.Aliphatic hydrocarbon can be saturated or undersaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.These pure and mild hydrocarbon as the 3rd solvent can use separately, or use with its two or more potpourri, thereby are not particularly limited.The preferred object lesson of the 3rd solvent comprises alcohol as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols and cyclohexanol; And hydrocarbon, as cyclohexane and hexane.Special particular methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol and 1-butanols.

Preferably, the mixed solvent of above-mentioned three kinds of solvents formation contains first solvent that accounts for 20～95 quality %, second solvent of 2～60 quality % and the 3rd solvent of 2～30 quality %.More preferably, mixed solvent contains first solvent that accounts for 30～90 quality %, second solvent of 3～50 quality % and alcohol or the 3rd solvent of 3～25 quality %.Particularly preferably be, mixed solvent contains first solvent that accounts for 30～90 quality %, second solvent of 3～30 quality % and alcohol or the 3rd solvent of 3～15 quality %.When first solvent is a mixed solution and when not using second solvent, preferably, mixed solvent contains first solvent that accounts for 20～90 quality % and the 3rd solvent of 5～30 quality %.More preferably, mixed solvent contains first solvent that accounts for 30～86 quality % and the 3rd solvent of 7～25 quality %.Used above-mentioned non-chloro organic solvent is documented in JIII Journal of Technical Disclosure No.2001-1745 in more detail among the present invention, in 12～16 pages (publish May 15 calendar year 2001, Japan Institute of Invention and Innovation).The preferred compositions of used non-chloro organic solvent includes but not limited to following among the present invention:

Methyl acetate/acetone/methanol/ethanol/butanols (75/10/5/5/5, mass parts),

Methyl acetate/acetone/methanol/ethanol/propanol (75/10/5/5/5, mass parts),

Methyl acetate/acetone/methanol/butanols/cyclohexane (75/10/5/5/5, mass parts),

Methyl acetate/acetone/butanols (81/8/7/4, mass parts),

Methyl acetate/acetone/butanols (82/10/4/4, mass parts),

Methyl acetate/acetone/butanols (80/10/4/6, mass parts),

Methyl acetate/methyl ethyl ketone/methyl alcohol/butanols (80/10/5/5, mass parts),

Methyl acetate/acetone/methyl ethyl ketone/ethanol/isopropyl alcohol (75/8/5/5/7, mass parts),

Methyl acetate/cyclopentanone/methanol/isopropanol (80/7/5/8, mass parts),

Methyl acetate/acetone (85/10/5, mass parts),

Methyl acetate/cyclopentanone/acetone/methanol/butanols (60/15/14/5/6, mass parts),

Methyl acetate/cyclohexanone/methyl alcohol/hexane (70/20/5/5, mass parts),

Methyl acetate/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts),

Methyl acetate/1,3-dioxolanes/methanol/ethanol (70/20/5/5, mass parts),

Methyl acetate/dioxolanes/acetone/methanol/ethanol (60/20/10/5/5, mass parts),

Methyl acetate/acetone/cyclopentanone/ethanol/isobutyl alcohol/cyclohexane (65/10/10/5/5/5, mass parts),

Methyl formate/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, mass parts),

Methyl formate/acetone/ethyl acetate/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts),

Acetone/methyl acetoacetate/methanol/ethanol (65/20/10/5, mass parts),

Acetone/cyclopentanone/ethanol/butanols (65/20/10/5, mass parts),

Acetone/1,3-dioxolanes/ethanol/butanols (65/20/10/5, mass parts) and

1,3-dioxolanes/cyclohexanone/methyl ethyl ketone/methyl alcohol/butanols (55/20/10/5/5/5, mass parts).

In addition, can also use the cellulose acylate solution for preparing by following method:

From methyl acetate/acetone/butanols (81/8/7/4, mass parts) preparation cellulose acylate solution, filter and concentrate, and then add 2 mass parts butanols;

From methyl acetate/acetone/butanols (84/10/4/2, mass parts) preparation cellulose acylate solution, filter and concentrate, and then add 4 mass parts butanols; With

From methyl acetate/acetone (84/10/6, mass parts) preparation cellulose acylate solution, filter and concentrate, and then add 5 mass parts butanols.

(characteristic of cellulose acylate solution)

The cellulose acylate solution that the present invention uses is characterized in that cellulose acylate meltage in organic solvent is 10～30 quality %, more preferably 13～27 quality %, preferred especially 15～25 quality %.About the cellulose acylate concentration adjustment being arrived the method for these concentration; can be adjusted to prescribed concentration in dissolution phase; or at first be prepared into low concentration (for example, 9～14 quality %) solution, in enriching stage described later, be adjusted to the highly concentrated solution of appointment then.In addition, can prepare high concentration cellulose acylate solution in advance, add various adjuvants to it then, thereby preparation has the cellulose acylate solution of the low concentration of appointment.Even during in using these methods any, do not have special problem, as long as can obtain the concentration of cellulose acylate solution of the present invention yet.

In the present invention, when use the organic solvent identical with solution composition with the cellulose acylate solution dilution when concentration is 0.1～5 quality %, in the solution that obtains, the associated molecule amount of cellulose acylate preferably 150,000～15,000,000.More preferably, its associated molecule amount is 180,000～9,000,000.The associated molecule amount can be measured by the static light scattering method.The dissolving cellulos acylate, the inertia square radius of measuring simultaneously preferably becomes 10～200nm, more preferably 20～200nm at that time.In addition, the dissolving cellulos acylate makes second viral (virial) coefficient preferably become-2 * 10 ^-4～4 * 10 ^-4, more preferably-2 * 10 ^-4～2 * 10 ^-4The following describes the definition of associated molecule amount used among the present invention, inertia square radius and second virial coefficient.These are measured by the static light scattering method according to following program.For making measuring appliance convenient, measure and in rare zone, carry out.But these measured values have reflected the dope behavior in area with high mercury of the present invention.At first, cellulose acylate is dissolved in the solvent that dope uses, and prepares the solution of 0.1 quality %, 0.2 quality %, 0.3 quality % or 0.4 quality %.For preventing to absorb moisture content, cellulose acylate in advance 120 ℃ dry 2 hours down, under 25 ℃ and 10%RH, weigh then.Dissolving is carried out according to the method (conventional dissolving method, hot-cold lysis method or high-temperature digestion method) of dissolving dope.Then, these solution and filtrate solvent are crossed 0.2 μ m Teflon filtrator.Use light scattering measurement device (Ltd. makes for DLS-700, Otsuka Electronics Co.) down at 25 ℃, measure the static light scattering of filtering solution with 10 ° of strides from 30 ° to 140 °.The data that obtain with the analysis of Berry drawing.Because essential refractive index during this is analyzed, the solvent index that uses the Abbe refractometer to measure is by differential refractometer (DRM-1021, Otsuka Electronics Co., Ltd. manufacturing) solvent and the solution that uses light scattering measurement to use is measured its concentration gradient (dn/dc).

(dope preparation)

In preparation cellulose acylate solution of the present invention (dope), its dissolving method is not particularly limited.Dope can at room temperature prepare, or uses hot-cold lysis method, high-temperature digestion method or its combined preparation.About these, the preparation method of cellulose acylate solution is documented in, for example JP-A-5-163301; JP-A-61-106628, JP-A-58-127737, JP-A-9-95544; JP-A-10-95854, JP-A-10-45950, JP-A-2000-53784; JP-A-11-322946, JP-A-11-322947, JP-A-2-276830; JP-A-2000-273239, JP-A-11-71463, JP-A-4-259511; JP-A-2000-273184 is among JP-A-11-323017 and the JP-A-11-302388.The said method of dissolving cellulos acylate also is applicable to the present invention in organic solvent, so long as within the scope of the invention.These detailed content, be non-chloro dicyandiamide solution especially, be documented in JIII Journal of Technical Disclosure No.2001-1745, in 22～25 pages (publish May 15 calendar year 2001, Japan Institute ofInvention and Innovation).In addition; cellulose acylate strong solution used among the present invention concentrates usually and filters; its details also is documented in JIII Journal of Technical Disclosure No.2001-1745; in 25 pages (publish May 15 calendar year 2001, Japan Institute of Invention and Innovation).During high-temperature digestion, cellulose acylate almost always is dissolved under the temperature that is equal to or higher than used organic solvent boiling point.In this case, dissolved under pressure.

In the cellulose acylate solution that the present invention uses, the viscosity of solution and dynamic energy storage elastic modulus are preferably within the specific limits.Use has the flow graph (CLS500) (making by TA Instruments Inc.) of diameter 4cm/2 ° steel pricker, measures the 1mL sample solution.About measuring condition, in 40 ℃～-10 ℃ scopes with 2 ℃/min speed change shake the step/intensification, the energy storage elastic modulus G under the static non-Newtonian viscosity n* (Pas) under measuring 40 ℃ and-5 ℃ ' (Pa).The temperature of sample solution is remained under the measurement initial temperature in advance, become constant, begin then to measure up to solution temperature.In the present invention, 40 ℃ of following viscosity are preferably 1～400Pas, and 15 ℃ of following dynamic energy storage elastic modulus are preferably 500Pa or bigger.More preferably, 40 ℃ of following viscosity are 10～200Pas, and 15 ℃ of following dynamic energy storage elastic modulus are 100～1,000,000Pa.In addition, higher dynamic energy storage elastic modulus under the preferred low temperature.For example, when the temperature of fluid casting supporter is-5 ℃, the dynamic energy storage elastic modulus under-5 ℃ preferably 10,000～1,000,000Pa, when the temperature of supporter is-50 ℃, the dynamic energy storage elastic modulus under-50 ℃ preferably 10,000～5,000,000Pa.

As mentioned above, cellulose acylate solution is characterised in that it obtains with the high concentration dope, and does not need method for concentration just can obtain having the cellulose acylate solution of high concentration and excellent stability.For making dissolving easier, cellulose acylate can be dissolved into low concentration after, the solution of Xing Chenging concentrates with method for concentration then.Though method for concentration is not particularly limited, but obtain the method for highly concentrated solution when being to use evaporating solvent for example, it comprises the steps: to introduce low concentration solution between right cylinder and rotational trajectory, described rotational trajectory is formed by the excircle of the blade of the rotation of the circumferencial direction in right cylinder, and between right cylinder and solution, apply the temperature difference (for example, JP-A-4-259511); Or the low concentration solution of heating is blown into container from nozzle, carry out the flash distillation of solvent, until the solution that comes out from nozzle bump chamber wall, when container takes out highly concentrated solution, removing solvent vapo(u)r, and (for example, United States Patent (USP) 2 to take out the method for highly concentrated solution, 541,012,2,858,229,4,414, the method of record in 341 and 4,504,355).

Before the fluid casting, preferred filter medium such as metal gauze (gauze) or the flannel that is fit to that uses removes by filter undissolved material and foreign matter in the solution, as dust and impurity.Be the plain acylate solution of filter fiber, using absolute filtering accuracy is the filtrator of 0.1～100 μ m, and preferably using absolute filtering accuracy is the filtrator of 0.5～25 μ m.The thickness of filtrator is 0.1～10mm preferably, more preferably 0.2～2mm.In this case, preferably at filter pressure 16kgf/cm or littler, more preferably 12kgf/cm or littler, more preferably 10kgf/cm or littler again, preferred especially 2kgf/cm or littler under filter.About filter medium, use conventional well known materials, as glass fibre, cellulose fibre, filter paper and fluororesin (for example, tetrafluoroethylene resin).Especially, preferably use pottery and metal.Just the viscosity of the cellulose acylate solution before film forms can be any, as long as it may carry out when film forms in the scope of fluid casting.Usually, preparation cellulose acylate solution makes its viscosity be preferably 10～2,000Pas, more preferably 30～1,000Pas, more preferably 40～500Pas again.The temperature of this moment is not particularly limited, as long as temperature is the fluid temperature in when casting.But preferably-5～70 ℃, more preferably-5～55 ℃.

(film formation)

The following describes the method for using cellulose acylate solution to make film.About making the method and apparatus of cellulose acylate film of the present invention, use conventional casting membrane of solution formation method and the solution-cast membrane formation device that is used to make the cellulosic triacetate film.In a single day the dope (cellulose acylate solution) of preparation is stored in and stores in the still in dissolution equipment (jar), finally regulates with regard to removing bubble contained in the dope.By for example compression type quantitative gear pump, the quantitative supply fluid of high precision is supplied to the compression type mould with dope from the dope floss hole to control its revolution.The lid (slit) of dope from the compression type mould evenly cast on the metal support of the fluid cast part of ceaselessly moving, half-dried dope film (being also referred to as net) is peeled off from metal support at the pick-up point place, has changeed a circle nearly in pick-up point place metal support.With the two ends that clip is clamped the net that obtains, use the stenter transmission network in the time of the width of maintenance net, and dry.Then,, finish drying, be put into and batch predetermined length on the coiling machine with the roller group transmission network of dryer.Stenter can change according to purpose with the combination of being furnished with the dryer of roller group.In the film solutions employed cast membrane formation method of making electronic console, not only solution-cast membrane formation device, and spreader also often joins the surface treatment of film, to provide such as bottom (subbing), antistatic layer, anti-halation layer and protective seam.Each manufacturing step of following simple declaration, but the invention is not restricted to this.

At first, when making cellulose acylate film with the solvent cast method, the cellulose acylate solution (dope) of preparation casts in drum barrel or is with, and forms film from its evaporating solvent.Preferably before the fluid casting, regulate dope concentration, make that solids content is 5～40 quality %.The surface of drum barrel or band preferably is polished to the mirror-smooth state.Dope preferably casts in surface temperature to be 30 ℃ or lower drum barrel or to be with.Especially, the metal support temperature preferably-10～20 ℃.In addition, in the present invention, can use to be documented in JP-A-2000-301555 JP-A-2000-301558, JP-A-07-032391, JP-A-03-193316, JP-A-05-086212, JP-A-62-037113, JP-A-02-276607, JP-A-55-014201, the method among JP-A-02-111511 and the JP-A-02-208650.

(multi-layered fluid casting)

Be used as on the smooth zone or drum barrel of metal support, cellulose acylate solution can be cast into individual layer, maybe can become two-layer multiple cellulose acylate solution-cast or multilayer.Under the situation of the multiple cellulose acylate solution of casting, a plurality of corresponding casting dies that can be provided with at interval from the direct of travel in metal support, casting contains the solution of cellulose acylate in succession, and lamination they, thereby the preparation film.For example, can be suitable for and be documented in JP-A-61-158414, the method among JP-A-1-122419 and the JP-A-11-198285.In addition, the cellulose acylate solution by two casting dies of casting can form film; this can be with for example being documented in JP-B-60-27562, JP-A-61-94724, JP-A-61-947245; JP-A-61-104813, the method among JP-A-61-158413 and the JP-A-6-134933 is carried out.In addition; can use the cellulose acylate film casing process that is documented among the JP-A-56-162617; wherein the mobile of high-viscosity cellulose acylate solution is enclosed in the low-viscosity cellulose acylate solution, and extrudes high viscosity and low-viscosity cellulose acylate solution simultaneously.In addition, also preferred embodiment as putting down in writing among JP-A-61-94724 and the JP-A-61-94725 will be included in the external solution as the pure composition of relatively poor solvent, and it is measured greater than its amount in internal solution.Selectively, use two casting dies, peel off the film that forms on the metal support of first casting die, and carry out the casting second time, thereby make film in film one side that contacts with the metallic support surface.This method for example is documented among the JP-B-44-20235.Cellulose acylate solution to be cast can be identical or different, is not particularly limited.For making a plurality of cellulose acylate layers have function, can extrude the cellulose acylate solution of corresponding function respectively from different casting dies.In addition, cellulose acylate solution also can be cast simultaneously with other functional layers (for example, adhesive phase, dye coating, antistatic layer, anti-halation layer, UV absorption layer and polarizing layer).

In the individual layer solution known to the routine, must extrude and have high concentration and full-bodied cellulose acylate solution, to obtain required film thickness.In this case, the poor stability of cellulose acylate solution, thus produce solid matter, it is relatively poor to produce spot problem and planarity, and this brings problem in many cases.As the method for head it off,, thereby high viscosity solution is extruded on metal support simultaneously from the casting die multiple cellulose acylate solution of casting.Not only can make the film that planarity is improved and had excellent surface quality, and, improve the film manufacturing speed by using concentrated cellulose acylate solution can realize reducing drying load.

Under casting situation altogether, internal layer and outer field thickness are not particularly limited.Yet outer field thickness preferably accounts for 1～50% of integral membrane thickness, more preferably 2～30%.Under the situation that is total at least three layers of casting, the layer that contacts with metal support is defined by outer film thickness with the overall film thickness of the layer that contacts with air.Under the situation of casting altogether, also may cast altogether has the above-mentioned adjuvant such as the plastifier of variable concentrations, the cellulose acylate solution of ultraviolet light absorber or matting agent, thus make cellulose acylate film with rhythmo structure.For example, can make cellulose acylate film with skin/core/surface structure.For example, the amount that matting agent is added in the top layer can be bigger than sandwich layer, or only be added in the top layer.The amount that plastifier and ultraviolet light absorber are added in the sandwich layer can be bigger than the top layer, or only be added in the sandwich layer.In addition, the kind of plastifier and ultraviolet light absorber also can change in sandwich layer and top layer.For example, low volatility plastifier and/or ultraviolet light absorber may be added in the top layer, and the ultraviolet light absorber that will have excellent plastic plastifier or have an excellent ultraviolet-absorbing is added in the sandwich layer.In addition, embodiment preferred is that release agent only is added in the top layer on metallic support side.In addition, for coming the cool metal supporter by cooling drum barrel method, make solution gelization, also preferably will be added in the top layer as the alcohol of relatively poor solvent, addition is greater than sandwich layer.The Tg of top layer and sandwich layer can be different, and the Tg of sandwich layer preferably is lower than the Tg on top layer.In addition, during casting, the viscosity that contains the solution of cellulose acylate can be different between top layer and sandwich layer.The viscosity on top layer preferably is lower than the viscosity of sandwich layer, but the viscosity of sandwich layer can be lower than the viscosity on top layer.

(fluid casting)

Method as cast-solution, the dope of evenly extruding preparation from the pressurizing mold method on the metal support is arranged, in case the doctor blade method of just using scraper to regulate film thickness on the metal support of casting in is arranged, or the contrary roll-coater method of using contrary rotation roller to regulate film thickness.Wherein, it is preferred using the method for pressurizing mold.Pressurizing mold comprises clothes hanger type and " T " pattern tool, preferably uses any.Except said method, can use hitherto known casting cellulosic triacetate solution to form the whole bag of tricks of film.By various conditions being set, considering the boiling point difference etc. between the solvent for use, can obtain the similar effect of in each document, putting down in writing.As making used continuous metal supporter in the cellulose acylate film of the present invention, use with chrome-plated surface and bright finished drum barrel, or surface finish and become the stainless steel band (being also referred to as belt) of minute surface.About making pressurizing mold used in the cellulose acylate film of the present invention, one or two or more moulds can be set above metal support.Mould preferably one or two.Be provided with under the situation of two or more moulds, the available various ratios of the dope amount of casting are assigned in each mould, maybe can dope be supplied to mould with each ratio by a plurality of accurate quantitative gear pumps.The temperature of the cellulose acylate solution of fluid casting usefulness preferably-10～55 ℃, more preferably 25～50 ℃.In this case, the institute in steps in temperature can be identical, or in each step can the difference.When temperature not simultaneously, only need the casting before temperature be assigned temperature.

(drying)

As making in the cellulose acylate film, the method for dry dope on metal support has usually from the method for the surface side-blown hot-air of metal support (drum barrel or band), i.e. the face side of the net on the metal support; Blow the method for hot-air from the dorsal part of drum barrel or band; With the liquid heat transfer method, make relative back side contact drum barrel or the band of the liquid of control temperature from the dope mould surface, and by heating drum barrel or the band of conducting heat, thereby the control surface temperature.Yet back side liquid heat transfer method is preferred.Metal support surface temperature before the fluid casting can be any temperature, as long as this temperature is equal to or less than the boiling point of dope with solvent.Yet for quickening drying or reduce the flowability of solution on metal support, temperature preferably is set to the temperature than low 1～10 ℃ of the maximum boiling point of solvent for use.Above-mentioned do not have dry situation about just peeling off after not being suitable for casting dope cooling.

(stretch processing)

In cellulose acylate film of the present invention, can be by the stretch processing control lag.In addition,, be documented in for example JP-A-62-115035 in the method for the positive stretched film of Width, JP-A-4-152125, JP-A-4-284211 is among JP-A-4-298310 and the JP-A-11-48271.Be length of delay in the face of the plain acylate film of increased fiber, the film of manufacturing is stretched.

The stretching of film is carried out at normal temperatures or under heating condition.The heating-up temperature preferably glass transition temperature than film is low.The stretching of film can be only at vertical or horizontal uniaxial tension, or can be simultaneously or successively biaxial-oriented.The draw ratio of carrying out is 1～200%, and is preferred 1～100%, and special preferred proportion is 1～50%.About the birefringence of blooming, the refractive index of suitable Width is greater than the refractive index of length direction.Therefore, preferred film is bigger at the level of stretch of Width.In addition, stretch processing can be carried out in the film forming process, or carries out after forming whole film with the form that net is rolled into volume.In the previous case, stretch processing can be carried out when the film that forms still contain residual solvent, and the film that forms therein amount of residual solvent be under 2～30% the state, can successfully stretch.

The thickness of the cellulose acylate film of finishing (dry back) though change according to final application target, is generally 5～500 μ m, preferred 20～300 μ m, preferred especially 40～180 μ m.Especially in the VA LCD time, film thickness 40～110 μ m suit.When selectively, being fit to that also film thickness is adjusted to 110～180 μ m.In this scope, water becomes and is difficult to pass through film.Thereby the film with this thickness suits, and under 60 ℃ and 90%RH condition, in endurancings in 500 hours of polaroid, can provide advantage.This is because it is believed that because the size and the film thickness of optical characteristics is proportional, and moisture content perviousness and the inversely proportional reduction of thickness, so the moisture content perviousness is more little, the film thickness of production is big more.

The gap of the concentration by regulating solids contained in the dope, the slit of die cover, the pressure of extruding from mould, the speed of metal support etc., can controlling diaphragm thickness to obtain desired thickness.The width of the cellulose acylate film that obtains like this is preferably 0.5～3m, more preferably 0.6～2.5m, more preferably 0.8～2.2m again.The film length that batches preferably 100～10,000m/ roller, more preferably 500～7,000m/ roller, more more preferably 1,000～6,000m/ roller.When take-up, preferably at least one end embossing of film.Its width is 3～50mm, preferred 5～30mm.It highly is 0.5～500 μ m, preferred 1～200 μ m.This can be side pressurization or both sides pressurization.In addition, the Re value changes within preferred ± 5nm in whole width, more preferably ± 3nm within.In addition, the Rth value changes within preferred ± 10nm, more preferably ± 5nm within.Re value and Rth value are changing in the preferred variation range at Width longitudinally.For keeping clear, suitable mist degree is controlled to be 0.01%～2%.For reducing mist degree, need the particle matting agent to disperse well, thereby reduce the number of particles of aggegation, and only be used in the top layer, thereby reduce addition.

(optical characteristics of cellulose acylate film)

The Re value of the cellulose acylate film that the present invention uses is preferably 20nm～150nm.In order to reduce the light leak of IPS mode LCD vergence direction effectively, the Re value is very preferred for 40nm～115nm, and 60nm～95nm is preferred.In addition, the Rth/Re ratio is adjusted to 1.5～7.In order to reduce the light leak of IPS mode LCD vergence direction effectively, the Rth/Re ratio is 2.0～5.5th, and is very preferred, 2.5～4.5th, and preferred.

For the ocb mode liquid crystal display, about the optical characteristics of cellulose acylate film of the present invention, preferably Re length of delay and Rth length of delay satisfy following relation (V) and (VI) respectively;

(V)：20nm≤Re(550)≤100nm

(VI)：70nm≤Rth(550)≤350nm

(wherein Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm).

Up to the present, preferably Re length of delay and Rth length of delay satisfy following relation (VI) and (VIII) respectively.

(V)：30nm≤Re(550)≤70nm

(VI)：150nm≤Rth(550)≤250nm

Because the light that makes wavelength X nm is at the direction bump film of normal to the film surface, Re (λ) value is measured with KOBRA 21ADH (Oji Scientific Instruments manufacturing).In addition, three length of delays that Rth (λ) value is measured based on three different directions calculate, be length of delay Re (λ), in face slow axis as sloping shaft and the light that makes wavelength X nm from respect to normal to the length of delay of measuring under the direction of film tilts the condition of+40 ° of directions bumps and in face slow axis as sloping shaft and the light that makes wavelength X nm from respect to normal to the length of delay of measuring under the direction of film tilts the condition of-40 ° of directions bumps, and input is assumed to mean refractive index value 1.48 and film thickness.

In this manual, unless refer else, λ is 550nm.

Owing to quality and size change along with humidity and high temperature changes following time lapse, comprise that the optical characteristic value of Re and Rth changes.Re and Rth value change more little, and film is suitable for using more.For reducing the changes in optical properties that humidity causes; use has the cellulose acylate of high acyl substituted degree in the 6-position; in addition, use hydrophobic additive to reduce (comprise plastifier, postpone to express agent and ultraviolet light absorber) moisture content perviousness and equilibrium water part content of film.At 60 ℃, 95%RH and the moisture content perviousness of measuring under the condition in 24 hours that is fit to are 400g/m ²～2,300g/m ²About the balance water content, the fit value of under 25 ℃ and 80%RH, measuring be 3.4% or below.About becoming the changes in optical properties amount that 80%RH causes 25 ℃ of following humidity from 10%RH, preferably the Re variable quantity is 12nm or following, and the Rth variable quantity is 32nm or following.Using the suitable amount of adjuvant is 10%～30 quality % of used cellulose acylate amount, preferred 12%～25 quality %, preferred especially 14.5%～20 quality %.When because of the adjuvant evaporation that adds or decompose when making film quality and change in size, optical characteristics changes.Therefore, preferably after 80 ℃ and 90%RH descended 48 hours, the mass change amount of the film that causes be 5% or below.Similarly, after 60 ℃ and 95%RH descended 24 hours, the change in size amount preferred 5% of the film that causes or below.In addition, after 90 ℃ and 5%RH descended 24 hours, the change in size amount preferred 5% of the film that causes or below.Even when a small amount of change in size and a small amount of mass change, as long as the photoelasticity modulus of film is little, the change of optical property quantitative change gets littler.Therefore, preferably the photoelastic coefficient of film is 50 * 10 ^-13Cm ²/ dyne or following.The glass transition temperature Tg of cellulose acylate film is preferably 80 ℃～180 ℃.The elastic modulus of cellulose acylate film is preferably 1,500MPa～5,000MPa.In addition, preferably the cellulose acylate film mean diameter that contains secondary is fine particles of silica of 0.2 μ m～1.5 μ m.

(optical anisotropic layer)

Optical anisotropic layer is made by liquid crystal compounds.Optical anisotropic layer can be formed directly on the transparent support surface.Also can allow on transparent supporting body, to form oriented layer, on oriented layer, form optical anisotropic layer then.Selectively,, transfer on the transparent supporting body then forming optical anisotropic layer by liquid crystal compounds on the substrate separately, thus the preparation optical compensation films.Be transferred the transparent supporting body of optical anisotropic layer on it, pressure-bonding coat can be provided in advance.

The preferred example of liquid crystal compounds comprises bar-shaped or discoid liquid crystal compounds.Bar-shaped or discoid liquid crystal compounds can be a high molecule liquid crystal.When forming optical anisotropic layer, polymerization or the crosslinked liquid crystal liquid crystal property that loses can be because of taking place in liquid crystal compounds.

＜rod shaped liquid crystal compound 〉

The example of rod shaped liquid crystal compound comprises the phenyl pyrimidine of azomethine, azoxy, cyanobiphenyl, cyanobenzene ester, benzoic ether, cyclohexane-carboxylic acid phenyl ester, cyano-phenyl cyclohexane, cyano group-replacement, phenyl pyrimidine, Ben Ji diox, tolane and the thiazolinyl cyclohexyl benzene formonitrile HCN of alkoxy-replacement.In addition, the rod shaped liquid crystal compound also comprises metal complex.In addition, also can use the liquid crystal polymer that in repetitive, contains corresponding to the molecular structure of rod shaped liquid crystal compound.In other words, the rod shaped liquid crystal compound can combine with polymkeric substance and form liquid-crystalline polymer.

The record of rod shaped liquid crystal compound can be for example Kikan Kagaku Sosetsu(Quarterly Review of Chemistry), Vol 22 (exercise question " Ekisho no Kagaku " (Chemistry of Liquid Crystals), the 4th, 7 and 11 chapters, The Chemical Society ofJapan(1994) and Ekisho Debaisu Handobukku(Handbook of LiquidCrystal Devices), the 3rd chapter, The 142-th Committee of Japan Society for thePromotion of Science.

Preferred its birefraction of rod shaped liquid crystal compound is 0.001～0.7.

In order to fix their alignment state, the rod shaped liquid crystal compound has polymerisable group and suits.Preferably undersaturated polymerizable groups of polymerizable groups or epoxy radicals, more preferably undersaturated polymerisable group, the preferred especially undersaturated polymerizable groups of ethylenic.

When cambium layer, the molecule of the rod shaped liquid crystal compound that preferred the present invention uses forms perpendicular direction orientation and is fixed on alignment state.Statement used herein " perpendicular " refers to that the angle that the surperficial and used rod shaped liquid crystal compound direction of film forms is 70 °～90 °.

These rod shaped liquid crystal molecules can tilted alignment, or the mode that can the pitch angle gradually changes is orientated (mixing orientation).At tilted alignment and mix in the orientation preferred 70 °～90 ° of average slope angle, more preferably 80 °～90 °, preferred especially 85 °～90 °.

The optical anisotropic layer that the rod shaped liquid crystal compound constitutes, can form by on the vertical alignment layer that forms on the supporter, applying the coating solution layer, cause the vertical orientated attitude in the layer, fixing then this vertical orientated attitude, described coating solution contain the rod shaped liquid crystal compound and the aftermentioned adjuvant (comprising polymerization initiator and air interface vertical-tropism agent) when needing.Also can form optical anisotropic layer by transferring on the cellulose acylate film by the layer that the rod shaped liquid crystal compound constitutes.For the optical characteristics that obtains to expect, not only can form optical anisotropic layer, and can form by the lamination of two-layer or more multi-layered component layer by one deck component layer.Selectively, can form optical anisotropic layer, the feasible optical characteristics that satisfies expection together by the layering product and the phase shift films of supporter.

The used solvent of preparation coating solution is suitable for organic solvent.Representative examples of organic comprises that acid amides (for example, N, dinethylformamide), sulfoxide (for example, dimethyl sulfoxide (DMSO)), heterogeneous ring compound (for example, pyridine), hydrocarbon are (for example, benzene and hexane), alkyl halide (for example, chloroform and methylene chloride), ester (for example, methyl acetate and butyl acetate), ketone (for example, acetone and methyl ethyl ketone) and ether (for example, tetrahydrofuran and 1, the 2-dimethoxy-ethane).In these solvents, alkyl halide and ketone are better than other.Two or more organic solvents can be used in combination.Can use known method (for example, extrusion coated, direct intaglio plate coating, contrary intaglio plate coating and pattern rubbing method) to use coating solution.

The liquid crystal compounds molecule of preferred fixed vertical orientation makes it remain on alignment state.What be fit to is to fix the liquid crystal compounds molecule by the polyreaction that is incorporated into polymerizable groups (P) wherein.Polyreaction comprises heat polymerization that uses thermal polymerization and the photopolymerization reaction that uses Photoepolymerizationinitiater initiater.Here, photopolymerization reaction is more preferred than heat polymerization.The example of Photoepolymerizationinitiater initiater used herein comprises that the alpha-carbonyl compound (is disclosed in U.S. Patent No. 2,367,661 and 2,357,670), acyloin ether (is disclosed in U.S. Patent No. 2,448,828), the aromatic series acyloin compound (being disclosed in U.S. Patent No. 2,722,512) of α-hydrocarbon-replacement, the multinuclear naphtoquinone compounds (is disclosed in U.S. Patent No. 3,046,127 and 2,951,758), the combination of triarylimidazoles dimer and right-aminophenyl ketone (is disclosed in U.S. Patent No. 3,549,367), acridine and compound phenazine (are disclosed in JP-A-60-105667 and U.S. Patent No. 4,239,850) with the oxadiazole compound (is disclosed in U.S. Patent No. 4,212,970).

The consumption of Photoepolymerizationinitiater initiater is preferably 0.01～20 quality % of coating solution solid content, more preferably 0.5～5 quality %.Be the bar-shaped liquid crystal liquid crystal property molecule of polymerization, the suitable ultraviolet ray that is to use is shone.Irradiation energy is preferably 20mJ/cm ²～50J/cm ², more preferably 100～800mJ/cm ²For quickening photopolymerization reaction, can under heating, carry out rayed.The thickness that comprises first delay zone of optical anisotropic layer is preferably 0.1～10 μ m, more preferably 0.5～5 μ m, preferred especially 1～5 μ m.

(vertical alignment layer)

For making liquid crystal compounds vertical orientated, importantly reduce the surface energy of alignment films in the alignment films side.More specifically, reduce the surface energy of alignment films by means of the functional group of polymkeric substance, thereby make liquid-crystal compounds be in the setting attitude.As reduce alignment layer surface can functional group, the hydrocarbyl group that fluorine atom and each group contain 10 or above carbon atom is effective.For fluorine atom or hydrocarbyl group are existed on the surface of alignment films, what be fit to is side chain rather than the main chain of fluorine atom or hydrocarbyl group being introduced polymkeric substance.Fluorine atom ratio in the fluoropolymer is preferably 0.05%～80 quality %, more preferably 0.1%～70 quality %, more preferably 0.5%～65 quality % again, preferred especially 1%～60 quality %.Hydrocarbyl group is the combination of aliphatic group, aromatic group or these groups.Aliphatic group can be any in ring-type, side chain and the linear chain structure.Aliphatic group is alkyl (comprising naphthenic base) or thiazolinyl (comprising cycloalkenyl group) preferably.Hydrocarbyl group can have the substituting group that water is not had strong affinity, as halogen atom.Carbon number in each hydrocarbyl group is preferably 10～100, and more preferably 10～60, preferred especially 10～40.Preferably the main chain of polymkeric substance has polyimide structures or polyvinyl alcohol structures.

Polyimide is synthetic by the condensation reaction between tetrabasic carboxylic acid and the diamines usually.By increasing the kind of used tetrabasic carboxylic acid or diamines, can synthesize polyimide with the multipolymer equivalent.Fluorine atom or hydrocarbyl group may reside in the repetitive of the repetitive in repetitive, diamines source of tetracarboxylic acid acid source or this two provenance.In that hydrocarbyl group is introduced under the situation of polyimide, particularly preferably be, in the main chain of polyimide or side chain, form the steroid structure.Steride structure that exists in the side chain and the hydrocarbyl group equivalent that contains 10 or above carbon atom have the function that makes liquid crystal compounds vertical orientated.Term used herein " steroid structure " finger ring penta ring hydrogen phenanthrene ring structure or in the scope of aliphatics ring the ring structure (as long as this modification does not form aromatic ring) of part key modification Cheng Shuanjian.

As making the vertical orientated another kind of method of liquid crystal compounds, can advantageously use the method for mixed organic acid and high polymer, as polyvinyl alcohol (PVA), modified polyethylene alcohol or polyimide.The organic acid example that is suitable for mixing comprises carboxylic acid, sulfonic acid and amino acid.

Can use the acid alignment agent in the aftermentioned air interface alignment agent.In addition, also can favourable use quaternary ammonium salt.Their combined amount is preferably 0.1%～20 quality % of used high polymer amount, more preferably 0.5%～10 quality %.

Preferably, the saponification degree of employed polyvinyl alcohol (PVA) is 70～100%, particularly 80～100%, and the degree of polymerization is 100～5,000.

Under the situation that makes rod shaped liquid crystal compound orientation, preferably, alignment films constitutes by have the polymkeric substance of hydrophobic group as functional group in side chain.The type of functional group can be selected according to liquid crystal liquid crystal property molecule type and required alignment state.For example, the modification group of modified polyethylene alcohol can be introduced by copolymerization sex change, chain transfer sex change or block polymerization sex change.The example of modification group comprises that hydrophilic radical (for example, hydroxy-acid group, sulfonic acid group, phosphonyl group, amino, ammonium group, amide group, thiol group), (for example have alkyl that the alkyl, fluorine of 10～100 carbon atoms replace, sulfide group, polymerisable group, undersaturated polymerizable groups, epoxide group and aziridinyl) and alkoxysilyl (for example, trialkoxysilyl, dialkoxy silicyl and monoalkoxy silicyl).The example of described modified polyethylene alcoholic compound comprise be documented in JP-A-2000-155216[0022]～[0145] section and JP-A-2002-62426[0018]～[0022] section in those.

Has the polymkeric substance that has crosslinkable functional group in the side chain that makes the liquid crystal molecular orientation function when forming alignment films when using side chain to contain the polymkeric substance of the crosslinking functionality that combines with main chain or using, and when using the composition contain polyfunctional monomer to form phase shift films thereon, may make the polyfunctional monomer copolymerization in the phase shift films that forms on polymkeric substance in the alignment films and the alignment films.Consequently, not only between polyfunctional monomer, and between the polymer molecule of alignment films, in addition, between the polymkeric substance of polyfunctional monomer and alignment films, all form covalent bond, thereby securely alignment films and phase shift films are combined.Therefore, use polymkeric substance to form alignment films and obviously improved the optical compensation film strength with crosslinking functionality.Wherein, the crosslinking functionality of the polymkeric substance in the preferred orientation film contains polymerisable group, as polyfunctional monomer.The example of polymer-based group is included in JP-A-2000-155216[0080]～[0100] section in the record those.

Except above-mentioned crosslinking functionality, the polymkeric substance in the alignment films also can be crosslinked with crosslinking chemical.Wherein the example of operable crosslinking chemical comprise aldehyde, N-methylol compound, dioxane derivatives, can be by compound, active vinyl-compound, active halogen compound, isoxazole and the dialdehyde starch of activated carboxyl effect.Can be used in combination two or more crosslinking chemicals.Comprise as the example of the compound of crosslinking chemical and to be disclosed in JP-A-2002-62426[0023]～compound in [0024] section.In these compounds, the aldehyde of high response, particularly glutaraldehyde, preferred than other.

The crosslinking chemical addition is preferably 0.1～20 quality % of polymer loading, more preferably 0.5～15 quality %.The preferred 1.0 quality % or following of unreacted crosslinking chemical ratio of remnants, more preferably 0.5 quality % or following in the alignment films.By similar above-mentioned control, even when the alignment films of LCD is used for a long time, even or long-time when placing alignment films in high temperature and high humidity atmosphere, also can realize enough permanance, net can not appear.

Alignment films forms by the composition that coating one deck on transparent supporting body contains the composition that is used to form oriented layer basically, described composition comprises above-mentioned polymkeric substance and crosslinking chemical, heat drying layer (causing cross-linking reaction wherein), and make drying layer accept friction treatment.As mentioned above, on being applied to transparent supporting body after, can carry out cross-linking reaction at any time.When water-soluble polymers such as polyvinyl alcohol (PVA) form material as oriented layer, preferably make water and have the solvent that the potpourri of the organic solvent (for example, methyl alcohol) of froth breaking effect is used as coating composition.The mass ratio of water/methyl alcohol is preferably 0: 100～and 99: 1, more preferably 0: 100～91: 9.By regulating mixing ratio in above-mentioned scope, can prevent to form bubble, thereby can significantly be reduced in alignment films and the further defective in the retardation layer surface.

The example that is suitable for the coating process of alignment films comprises spin coating method, dip coated method, curtain coating method, extrusion coating method, bar coating method and method of roll coating.In these coating processes, particularly preferably be the bar coating method.Dried film thickness is preferably 0.1～10 μ m.Heat drying can carry out under 20～100 ℃ temperature range.For forming full cross-linked key, suitable heating-up temperature is 60～100 ℃, particularly 80～100 ℃.Drying can be carried out 1 minute～36 hours continuously, but be 1～30 minute drying time that is fit to.In addition, suit pH regulator to the value that is suitable for most used crosslinking chemical.When the crosslinking chemical that uses was glutaraldehyde, pH preferably was adjusted to 4.5～5.5, and particularly 5.

Alignment films preferably is located on the transparent supporting body.Cross-linked polymer film is after this by the way, and alignment films comes into operation.Vertical orientated for the rod shaped liquid crystal compound, what be fit to is that alignment films is not carried out friction treatment.Selectively, make the liquid crystal compounds molecular orientation and they are fixed on alignment state by using alignment films, thereby form phase shift films, then phase shift films is transferred to separately on the polymer film (or transparent supporting body).Needing under the situation of friction treatment,, be fit to improve in advance the degree of crosslinking of alignment films for preventing dust.The value that remaining cross-linked dosage (Ma) and the ratio (Ma/Mb ratio) that is added to the cross-linked dosage (Mb) in the coating solution obtain after will deducting crosslinking Treatment with 1, promptly be worth (1-(Ma/Mb)), when being defined as degree of crosslinking, degree of crosslinking is preferably 50%～100%, more preferably 65%～100%, preferred especially 75%～100%.

(air interface vertical-tropism agent)

Usually, liquid crystal compounds has the performance that along inclined direction is orientated in the air interface side.Therefore,, need the liquid crystal compounds molecule on the control air interface side for realizing even vertical orientated attitude, thus vertical orientated.For this reason, what be fit to is, can be in air interface side uneven distribution and effect, make and the liquid crystal compounds molecule to be included in the liquid crystal coating solution at the compound of vertical direction orientation by its excluded volume effect or antistatic property, be used to form phase shift films then.

As described air interface alignment agent, can use disclosed compound in JP-A-2002-20363 and JP-A-2002-129162.In addition, be documented in Japanese patent application No.2002-212100[0072]～[0075] section, Japanese patent application No.2002-262239[0037]～[0039] section, Japanese patent application No.2003-91752[0071]～[0078] section, Japanese patent application No.2003-119959[0052]～[0054], [0065]～[0066] and [0092]～[0094] section, Japanese patent application No.2003-330303[0028]～[0030] section and Japanese patent application No.2004-003804[0087]～[0090] section in item also be applicable to the present invention in due course.In addition, mixing these compounds in the liquid crystal coating solution can improve the coating suitability and control the inhomogeneous and repellency of generation in the coating layer.

The ratio of used air interface alignment agent is preferably 0.05%～5 quality % in the liquid crystal coating solution.When using the air interface alignment agent of fluorochemicals type, its ratio is preferably 1 quality % or following.

＜discoid liquid crystal compounds 〉

Discoid liquid crystal compounds comprises the research report that is documented in people such as C.Destrade, Mol.Cryst., Vol.71, the benzene derivative in 111 pages (1981); Be documented in people's such as C.Destrade research report, MoI.Cryst., Vol.122,141 pages (1985) and Physics lett.A, Vol.78, three polyindenes (truxene) derivant in 82 pages (1990); Be documented in people's such as B.Kohne research report, Angew.Chem., Vol.96, the cyclohexane derivant in 70 pages (1984); With the research report that is documented in people such as J.M.Lehn, J.Chem.Commun., people's such as 1794 pages (1985) and J.Zhang research report, J.Am.Chem.Soc., Vol.116, big ring of aza-crown in 2655 pages (1994) or the big ring of phenylacetylene.

Usually, discoid liquid crystal compounds has and makes side chain (as the benzoyloxy of straight chained alkyl, alkoxy or replacement) and parent nucleus in the radial structure that is connected of minute subcenter.Preferably each individual molecule of discoid liquid crystal compounds or molecule self-assembly have rotational symmetry, and discoid liquid crystal compounds is to provide the compound of determining orientation.

When forming optical anisotropic layer by discoid liquid crystal compounds, the final compound that exists does not need to show liquid crystal liquid crystal property in the optical anisotropic layer.For example, when the discoid liquid crystal compounds of micromolecule has can be with the group of heat or light reaction the time, compound is exposed to heat or light, changes into macromolecular compound by polyreaction or cross-linking reaction, thereby forms optical anisotropic layer.Common rule is that discoid liquid crystal compounds loses its liquid crystal liquid crystal property because of changing into macromolecular compound.The discoid liquid crystal compounds of favourable use is disclosed among the JP-A-8-50206.Polymerization about discoid liquid crystal compounds is documented among the JP-A-8-27284.

For by polymerization fixed disc shape liquid crystal compounds, must make as substituent polymerisable group to combine with the disc centre of discoid liquid crystal compounds.Yet,, be difficult in polyreaction, keep the alignment state of disc centre so if polymerisable group directly combines with disc centre.When introducing linking group between disc centre and polymerisable group is exactly this situation.What therefore, have that the discoid liquid crystal compounds of polymerisable group is suitable for is the compound of following formula representative.

D(-L-Q) _n

Wherein, D is a disc centre, and L is a divalent linker, and Q is polymerisable group, and n is 4～12 integer.

The example of disc centre (D) illustrates hereinafter.In each example, LQ (or QL) refers to the combination of divalent linker (L) and polymerisable group (Q) below.

In above-mentioned formula, divalent linker (L) preferably be selected from alkylidene, alkenylene, arlydene ,-CO-,-NH-,-O-,-divalent linker of two or more combinations of S-or these groups.More preferably, divalent linker (L) be selected from alkylidene, arlydene ,-CO-,-NH-,-O-or-divalent linker that at least two divalent linkers of S-combine.In the described divalent linker, particularly preferably be selected from alkylidene, arlydene ,-CO-or-divalent linker that is combined to form of at least two divalent linkers of O-is as divalent linker (L).The suitable carbon number that comprises in each alkylidene is 1～12, is 2～12 in each alkenylene, is 6～10 in each arlydene.

The example of divalent linker (L) is as follows.Each linking group left side combines with disc centre (D), and the right side combines with polymerisable group (Q).AL represents alkylidene or alkenylene, and AR represents arlydene.In addition, alkylidene, alkenylene and arlydene can have substituting group (for example, alkyl).

L1：-AL-CO-O-AL-

L2：-AL-CO-O-AL-O-

L3：-AL-CO-O-AL-O-AL-

L4：-AL-CO-O-AL-O-CO-

L5：-CO-AR-O-AL-

L6：-CO-AR-O-AL-O-

L7：-CO-AR-O-AL-O-CO-

L8：-CO-NH-AL-

L9：-NH-AL-O-

L10：-NH-AL-O-CO-

L11：-O-AL-

L12：-O-AL-O-

L13：-O-AL-O-CO-

L14：-O-AL-O-CO-NH-AL-

L15：-O-AL-S-AL-

L16：-O-CO-AR-O-AL-CO-

L17：-O-CO-AR-O-AL-O-CO-

L18：-O-CO-AR-O-AL-O-AL-O-CO-

L19：-O-CO-AR-O-AL-O-AL-O-AL-O-CO-

L20：-S-AL-

L21：-S-AL-O-

L22：-S-AL-O-CO-

L23：-S-AL-S-AL-

L24：-S-AR-AL-

In above-mentioned formula, polymerisable group (Q) can be according to the type selecting of used polyreaction.Particularly, preferably undersaturated polymerizable groups of polymerisable group (Q) or epoxy radicals, more preferably undersaturated polymerizable groups, the preferred especially undersaturated polymerizable groups of ethylenic.

In above-mentioned formula, n is 4～12 integer.Concrete numerical value is selected according to the kind of used disc centre (D).A plurality of L-Q combinations can be identical or different, but preferably identical.

About the orientation of liquid crystal compounds molecule, preferably, in optical anisotropic layer, the mean direction of molecule axis of symmetry forms 43 °～47 ° angle with respect to length direction.

In mixing orientation, the angle before the molecule axis of symmetry of liquid crystal compounds molecule and the supporting body surface is along with the distance of distance supporting body surface increases along the increase of optical anisotropic layer depth direction or reduces.Yet preferably, angle increases along with distance and reduces.Angle can various state variation, for example increase continuously state, continuously reduce state, intermittently the increase state, intermittently reduce state, comprise the state that increases continuously and reduce continuously, and comprise the state that intermittently that increase and reduce changes.Intermittently change and comprise that pitch angle wherein is in zone that the mid point of thickness direction does not change.

As long as angle is the state that increases or reduce on the whole, can comprise the zone that does not have angle to change so, but preferably, angle is continuous variable condition.

Usually, by suitably selecting the material of liquid crystal compounds or alignment films, or, can control the mean direction of the molecule axis of symmetry of liquid crystal compounds molecule by suitably selecting the friction treatment method.The slow axis of the slow axis of transparent supporting body and optical anisotropic layer can be by carrying out the slow-axis direction that friction treatment is regulated optical anisotropic layer in the direction that is different from the transparent supporting body slow axis neither under the also uneven situation of orthogonal in optical compensation films.

Usually, by suitable selection liquid crystal compounds or the additive types used with liquid crystal compounds, can control the direction of molecule axis of symmetry of the liquid crystal compounds molecule of optical anisotropic layer face side (air side).Can comprise plastifier, surfactant, polymerisable monomer and polymkeric substance with the examples of additives that liquid crystal compounds uses.Similar to the above, by the classification and the above-mentioned additive types of suitable selection liquid crystal compounds, also can control the intensity of variation of the direction of orientation of molecule axis of symmetry.When the option table surface-active agent, preferably guarantee to coordinate mutually with its surface tension control effect to coating solution.

About the plastifier, surfactant and the polymerisable monomer that use with liquid crystal compounds, preferably they are compatible with discoid liquid crystal compounds, can change the pitch angle of liquid crystal compounds, or can not hinder orientation.In these adjuvants, preferably use polymerisable monomer (compound that for example, contains vinyl, ethyleneoxy, acryloyl group and methacryl).In liquid crystal compounds, the addition of described compound is preferably 1～50 quality %, more preferably 5～30 quality %.In addition, when in adjuvant, mixing monomer, can strengthen bonding between alignment films and the optical anisotropic layer with 4 or more a plurality of polymerisable functional groups.

When discoid liquid crystal compounds is used as liquid crystal compounds, preferably will has certain compatibility, also the polymkeric substance of the tilt angle varied of discoid liquid crystal compounds is added in the optical anisotropic layer with discoid liquid crystal compounds.

As the polymkeric substance that adds, cellulose esters and cellulose ether are fit to, and cellulose esters is more preferred than cellulose ether.The example of cellulose esters comprises cellulose acetate, cellulose acetate propionic ester and cellulose acetate butyric ester.The example of cellulose ether is a hydroxy propyl cellulose.Regulate the addition of described polymkeric substance, make it not hinder the orientation of discoid liquid crystal compounds molecule.Particularly, in discoid liquid crystal compounds, preferred 0.1～10 quality % of the addition of polymkeric substance, more preferably 0.1～8 quality %, more preferably 0.1～5 quality % again.

In the discoid liquid crystal compounds, discoid nematic liquid crystal phase-solid phase inversion temperature is preferably 70 ℃～300 ℃, more preferably 70 ℃～170 ℃.

The preferred 0.1 μ m of the thickness of optical anisotropic layer～20 μ m, more preferably 0.5 μ m～15 μ m, more preferably 1 μ m～10 μ m again.

(alignment films)

Preferably between transparent supporting body and optical anisotropic layer, alignment films is set.

The layer that alignment films preferably is made of crosslinked polymkeric substance.For forming described layer, can use crosslinkable polymkeric substance.For example, make polymkeric substance, form crosslinked by using up or heat or change pH and react to each other with crosslinking functionality.Selectively, can be by using the crosslinking chemical cross-linked polymer.Used crosslinking chemical is the high response compound, and the linking group that is derived from crosslinking chemical is incorporated between the polymkeric substance, forms crosslinked between polymkeric substance.

The alignment films that is made of crosslinked polymkeric substance contains the coating solution of the potpourri of crosslinkable polymkeric substance or polymkeric substance and crosslinking chemical usually by coating on transparent supporting body, make coating layer carry out light or thermal treatment or pH regulator then and form.

For in the process of friction orientation film, preventing dust, be suitable for increasing in advance the degree of crosslinking of alignment films.The value that remaining cross-linked dosage (Ma) and the ratio (Ma/Mb ratio) that is added to the cross-linked dosage (Mb) in the coating solution obtain after will deducting crosslinking Treatment with 1, promptly be worth (1-(Ma/Mb)), when being defined as degree of crosslinking, degree of crosslinking is preferably 50%～100%, more preferably 65%～100%, preferred especially 75%～100%.

The example of used polymkeric substance comprises polymethylmethacrylate in alignment films, polyacrylic acid, polymethylacrylic acid, polystyrene, poly maleimide, polyvinyl alcohol (PVA), modified polyethylene alcohol, poly-(N hydroxymethyl acrylamide), polyvinyl toluene, the tygon of chlorosulfonation, NC Nitroncellulose, Polyvinylchloride, the polyolefin of chlorination, polyester, polyimide, polyvinyl acetate, tygon, carboxymethyl cellulose, gelatin, polypropylene, the multipolymer of any two kinds monomer is (as acrylic acid-methacrylic acid copolymer in polycarbonate and the above-mentioned polymkeric substance of formation, styrene-maleimide copolymer, styrene-ethylene base toluene multipolymer, vinyl acetate-vinyl chloride copolymer and vinyl-vinyl acetate copolymer).Silane coupling agent also can be used as polymkeric substance.As the polymkeric substance that alignment films is used, water-soluble polymers is fit to.

In these polymkeric substance, poly-(N hydroxymethyl acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol (PVA) and modified polyethylene alcohol are better than other, gelatin, polyvinyl alcohol (PVA) and modified polyethylene alcohol are particularly preferred, and polyvinyl alcohol (PVA) and modified polyethylene alcohol are best suited for.

The saponification degree of polyvinyl alcohol (PVA) and modified polyethylene alcohol is preferably 70～100%, and more preferably 80～100%, more more preferably 85%～95%.The degree of polymerization of polyvinyl alcohol (PVA) and modified polyethylene alcohol is preferably 100～3, and 000.

In modified polyethylene alcohol, can pass through modification by copolymerization, chain transfer modification and block polymerization modification and introduce the modification group.The example of the modification group of introducing by copolymerization comprises-COONa ,-Si (OX) ₃(wherein X is hydrogen atom or alkyl) ,-N (CH ₃) ₃Cl ,-C ₉H ₁₉, COO ,-SO ₃Na and-C ₁₂H ₂₅The example of the modification group of introducing by chain transfer comprises-COONa ,-SH and-C ₁₂H ₂₅The example of the modification group of introducing by block polymerization comprises-COOH ,-CONH ₂,-COOR (wherein R is an alkyl) and C ₆H ₅In addition, alkylthio group also is the modification group that is fit to.

Modified polyethylene alcohol is documented among the JP-A-8-338913.

When hydrophilic polymer such as polyvinyl alcohol (PVA) are used in the alignment films,, preferably control water content number percent from the viewpoint of film thickness.Water content number percent is preferably 0.4%～2.5%, and more preferably 0.6%～1.6%.Can use the commercially available moisture content number percent measuring equipment that utilizes Karl Fischer technology, measure water content number percent.

The thickness of alignment films is preferably 10 μ m or following.

Other compositions in the＜retardation layer 〉

Plastifier, surfactant, polymerisable monomer can use with above-mentioned liquid crystal compounds, thereby can improve the orientation of homogeneity, layer intensity and the liquid crystal compounds of coating.Preferably, these compositions and liquid crystal compounds have excellent compatibility, and do not disturb the orientation of liquid crystal compounds.

The example of polymerisable monomer comprises the compound of polymerisable compound of free radical or cationic polymerizable.The polymerisable monomer of preferably multifunctional free radical, can advantageously use can with the above-mentioned monomer that contains the liquid-crystal compounds copolymerization of polymerizable groups.Particularly, at JP-A-2002-296423[0018]～[0020] section in disclosed compound be fit to.By discoid liquid crystal liquid crystal property molecule, the addition of described compound is generally 1～50 quality %, preferred 5～30 quality %.

The example of surfactant comprises the known so far compound as surfactant, but preferred especially fluorochemicals.More specifically, for example, can advantageously use at JP-A-2002-330725[0028]～[0056] section in disclosed compound and at Japanese patent application No.2003-295212[0069]～[0126] section in the record compound.

Preferably, can increase the viscosity of coating solution with the polymkeric substance that liquid crystal compounds uses.The example of described polymkeric substance comprises cellulose esters, and the example of suitable cellulose esters is included in JP-A-2000-155216[0178] section in those disclosed.In order not disturb the orientation of liquid-crystal compounds, suitable is that the polymer ratio that is added in the liquid crystal liquid crystal property molecule is 0.1～10 quality %, preferred 0.1～8 quality %.

In addition, preferred its Re value of optical anisotropic layer is 0nm～10nm, its Rth value is-and 80nm～-400nm.

(manufacturing of optical compensation films)

Optical compensation films is made web-like usually.Preferably make the optical compensation films of web-like by carrying out following steps (1)～(4) continuously:

(1) on the length of the transparent supporting body that length direction is carried, form the step of alignment films, comprise coating one deck resin solution, dry this layer with carry out friction treatment and make resin bed become alignment films, or lamination is coated with preformed alignment films;

(2) coating solution that will contain liquid crystal compounds is applied to the step on the alignment layer surface;

(3) make the step of liquid crystal compounds molecular orientation, by in the coating solution drying that is coated with or afterwards, to its heating, and fixed orientation attitude forms optical anisotropic layer under the temperature of the transition temperature that is not less than liquid crystal compounds; And

(4) batch the step of laminar product length with optical anisotropic layer.

In step (3), preferably, under being not less than the temperature of transition temperature, make in the liquid crystal liquid crystal property molecular orientation, blow to the lip-deep film-surface wind speed of liquid crystal compounds from the direction that is different from the friction treatment direction and satisfy following mathematical expression:

0＜V＜5.0×10 ^-3×η

Wherein V blows to the lip-deep film-surface wind speed of liquid crystal compounds (m/sec), and η is the viscosity (cp) of optical anisotropic layer under the liquid crystal compounds orientation temperature.

The most suitable scope of V is 0～2.5 * 10 ^-3* η.

According to step (1)～(4), can be continuously and as one man make optical compensation films, the molecule axis of symmetry of liquid crystal compounds molecule slow axis (length direction of transparent supporting body) in the mean direction (mean direction of molecule axis of symmetry in the optical anisotropic layer) of the lip-deep rectangular projection of transparent supporting body is different from the face of transparent supporting body wherein, in addition, the mean direction of molecule axis of symmetry and the angle between the frictional direction are-2 °～+ 2 °, preferably-1 °～+ 1 °, or 0 ° basically.In other words, the manufacture method that comprises step (1)～(4) is suitable for large-scale production.

When optical compensation films was used for the ocb mode liquid crystal display, preferably, the angle that slow axis (length direction of transparent supporting body) forms in the mean direction of molecule axis of symmetry and the face of transparent supporting body was essentially 45 °.

In step (2), the polymerisable liquid crystal compound with crosslinkable functional group is as liquid crystal compounds, in step (3), because coating layer is continuously by rayed, solidify coating layer by polymerization polymerizable liquid-crvstalline compound, thereby the fixed orientation attitude is carried out step (4) subsequently.

In step (2) before, can remove the step of dust to the friction treatment surface of transparent supporting body or alignment films.

In step (4) before, can check step,, check the optical anisotropic layer that forms in the step (3) by its optical characteristics of continuous coverage.

Step (1)～(4) write up is in JP-A-9-73081.

From handling the suitability and the viewpoint in net life-span, the preferred 100mm～500mm of diameter of used friction roller, more preferably 200mm～400mm in the step (1).Require the friction roller width wideer than the film width of carrying thus, the width of friction roller is preferably (film width) * 2 ^1/2Or more than.From preventing the viewpoint of dust, the revolution of friction roller preferably is arranged on low value.According to the sensitivity of liquid crystal compounds for orientation, the preferred 100rpm of revolution～1,000rpm, more preferably 250rpm～850rpm.

Even when being arranged on low value, also can keep the orientation of liquid crystal compounds, preferably heating transparent supporting body or alignment films in friction treatment for revolution at friction roller.What be fit to is that heating-up temperature is set, and makes the surface temperature of transparent supporting body or alignment films in the scope of (glass transition temperature of material-50 ℃)～(glass transition temperature of material+50 ℃).When using the alignment films of polyvinyl alcohol (PVA) manufacturing, suitable is the ambient humidity of controlling in the friction treatment.Relative humidity under 25 ℃ is preferably 25%～70%, and more preferably 30%～60%, preferred especially 35%～55%.

From the productivity of liquid crystal and the viewpoint of orientation, the transporting velocity of transparent supporting body is preferably 10m/min～100m/min, more preferably 15m/min～80m/min.For carrying, can utilize the existing various device that is used for transport membrane.Carrying method is not particularly limited.

Can be applied on the transparent supporting body by material such as polyvinyl alcohol (PVA) are dissolved in the coating solution for preparing in water or the organic solvent, dry then, to form alignment films.Forming alignment films can carry out before series of steps.Selectively, the continuous alignment films that forms on the length surface of while at transparent supporting body can carried.

In step (2), the coating solution that will contain liquid crystal compounds is applied on the alignment layer surface.The solvent of coating solution is preferably organic solvent.Described representative examples of organic comprises that acid amides (for example, N, dinethylformamide), sulfoxide (for example, dimethyl sulfoxide (DMSO)), heterogeneous ring compound are (for example, pyridine), hydrocarbon (for example, benzene and toluene), alkyl halide (for example, chloroform, methylene chloride and tetrachloroethane), ester (for example, methyl acetate and butyl acetate), ketone (for example, acetone and methyl ethyl ketone) and ether (for example, tetrahydrofuran and 1,2-dimethoxy-ethane).In these solvents, alkyl halide and ketone are better than other.Two or more organic solvents can be used in combination.

Be to form optical anisotropic layer highly uniformly, the surface tension of suitable is coating solution is 25mN/m or following, preferred 22mN/m or following.

Be to obtain low surface tension, preferably surfactant is added in the coating solution that optical anisotropic layer uses.Surfactant is fluorochemical surfactant preferably, and the more preferably surfactant of fluoropolymer type preferably includes the surfactant of the polymkeric substance with fluorine aliphatic group especially.Fluoropolymer can be the multipolymer that is made of fluorine-containing repetitive and other repetitives (for example, be derived from polyoxy alkylidene (methyl) acrylate those).

The quality mean molecular weight of fluoropolymer is preferred 3,000～100,000, and more preferably 6,000～80,000.The addition of fluoropolymer is preferably and contains 0.005%～8 quality % of liquid crystal compounds as solids in the coating solution of principal ingredient, more preferably 0.01%～1 quality %, preferred especially 0.05%～0.5 quality %.

Can use known method (as metal wire rod rubbing method, extrusion coated method, direct intaglio plate rubbing method, contrary intaglio plate coating process and die head rubbing method (die coating)) that coating solution is applied on the alignment layer surface.Can suitably determine the coating weight of coating solution based on the thickness of optical anisotropic layer.

In step (3), in the coating solution drying that is coated with or afterwards, under the temperature of the transition temperature that is not less than the liquid crystal compounds molecule, make the liquid crystal compounds molecular orientation, and the fixed orientation attitude forms optical anisotropic layer.By heating in dry run or after dry, liquid crystal compounds becomes orientation as required.Consider boiling point and the transparent supporting body and the used material of alignment films of solvent for use in the coating solution, determine baking temperature.Can determine orientation temperature based on the transition temperature of used liquid crystal compounds liquid crystal phase-solid phase.When used liquid crystal compounds was discoid liquid crystal compounds, orientation temperature was preferably selected from 70 ℃～300 ℃, more preferably 70 ℃～170 ℃.

Mesomorphic viscosity is preferably 10cp～10,000cp, more preferably 100cp～1,000cp.When viscosity is too small, the influence that the liquid crystal liquid crystal property molecule is easy to be dried when orientation, thus be that continuous production need be very accurate to the speed/direction control of wind.On the other hand, when viscosity was high, the liquid crystal liquid crystal property molecular change must be low to the susceptibility of wind, but its orientation is slack-off, and productivity is significantly descended.

Can control the viscosity of liquid crystal layer by the molecular structure of liquid crystal compounds.By an amount of adjuvant (particularly cellulosic polymer) and the jelling agent of using in optical anisotropic layer, can regulate viscosity.

Heated airflow that can be by sending into predetermined temperature or pass the heating chamber that remains on predetermined temperature heats.

Fixed orientation liquid crystal compounds molecule forms optical anisotropic layer when remaining on alignment state.Can be by being cooled to the solid transformation temperature or passing through polyreaction immobile liquid crystallinity compound molecule.By polyreaction fixedly is preferred.Polyreaction comprises heat polymerization that uses thermal polymerization and the photopolymerization reaction that uses Photoepolymerizationinitiater initiater.Photopolymerization reaction is preferred.

The example of available here Photoepolymerizationinitiater initiater comprises that the alpha-carbonyl compound (is disclosed in U.S. Patent No. 2,367,661 and 2,357,670), acyloin ether (is disclosed in U.S. Patent No. 2,448,828), the aromatic series acyloin compound (being disclosed in U.S. Patent No. 2,722,512) of α-hydrocarbon-replacement, the multinuclear naphtoquinone compounds (is disclosed in U.S. Patent No. 3,046,127 and 2,951,758), the combination of triarylimidazoles dimer and right-aminophenyl ketone (is disclosed in U.S. Patent No. 3,549,367), acridine and compound phenazine (are disclosed in JP-A-60-105667 and U.S. Patent No. 4,239,850) with the oxadiazole compound (is disclosed in U.S. Patent No. 4,212,970).The consumption of Photoepolymerizationinitiater initiater is preferably 0.01～20 quality % of coating solution solid content, more preferably 0.5～5 quality %.

In the rayed that is used for promoting the polymerization of liquid crystal compounds molecule and fixes its alignment state, preferred use ultraviolet ray.Irradiation energy is preferably 20mJ/cm ²～50J/cm ², more preferably 100～800mJ/cm ²For quickening photopolymerization reaction, can under heating, carry out rayed.Transparent supporting body by using the coating solution coating that optical anisotropic layer uses along place the light source place up and down or about course pass through, carry out rayed.

Carrying out step (4) before, can on the optical anisotropic layer that step (3) forms, protective seam be set.For example, the diaphragm of making in advance can be stacked on the surface of the optical anisotropic layer of making along length continuously.

In step (4), the length that has the laminar product of optical anisotropic layer is rolled into volume.For example, the supporter with continuous conveying of optical anisotropic layer can twine around cylindrical core.

The optical compensation films that obtains in the step (4) is web-like, handles even therefore also be easy to when making a large amount of film.In addition, the film of gained can in statu quo be preserved and carry.

(polaroid)

Polaroid comprises the polarizer and places two transparent protective films of its both sides.Cellulose acylate film of the present invention can be used as a diaphragm.Another diaphragm can use common cellulose acetate membrane.The polarizer comprises the iodo polarizer, uses the dye-based polarizer and the polyenoid alkyl polarizer of two look dyestuffs.The iodo polarizer and the dye-based polarizer use the manufacturing of polyvinyl alcohol (PVA) basement membrane usually.When using cellulose acylate film of the present invention as the diaphragm of the polarizer, the manufacture method of polaroid is not particularly limited, can use the conventional method manufacturing.A kind of method of making polaroid is arranged; comprise the steps: the cellulose acylate film that alkali treatment obtains; connect in polarizer both sides, use the aqueous solution of fully saponified polyvinyl alcohol (PVA) to stretch then by dipping polyvinyl alcohol (PVA) film preparation in iodine solution.What can replace alkali treatment is to use the easily bonding method that is documented among JP-A-6-94915 and the JP-A-6-118232.Be used for the bonding agent that the treatment surface with diaphragm is stacked on the polarizer and comprise, for example, polyvinyl alcohol-based adhesives such as polyvinyl alcohol (PVA) and polyvinyl butyral and vinyl latex such as butyl acrylate.Polaroid generally includes the diaphragm on two surfaces of the polarizer and the protection polarizer, also comprises diaphragm that is stacked to a surface of polaroid and the independent film that is stacked to opposed surface.Diaphragm and independent film are used for protection polaroid when transportation polaroid or testing product.In this case, pile up the surface that diaphragm is protected polaroid, and be used on the offside on surface that polaroid piles up liquid crystal board.Separately film is used to cover the adhesive phase that piles up with liquid crystal board, and is used on the face side that polaroid piles up liquid crystal board.

Cellulose acylate film of the present invention preferably is stacked on the polarizer, makes that the axis of homology of the polarizer is consistent with the slow axis of cellulose acylate film of the present invention.Estimate the polaroid of making down in polaroid cross-polarized light attitude (cross nicol); disclose when the quadrature precision between the slow axis of cellulose acylate film of the present invention and the absorption axes of the polarizer (perpendicular to the axle of the axis of homology) during greater than 1 °; degree of polarization performance degradation under polaroid cross-polarized light attitude produces light leak.In this case, when making up, can not obtain enough blackness or contrast with liquid crystal cell.Therefore, preferred 1 ° or littler of the deviation between the principal refractive index nx direction of cellulose acylate film of the present invention and the axis of homology direction of polaroid, more preferably 0.5 ° or littler.

In polaroid of the present invention, preferably, 25 ℃ with 60%RH under veneer transmissivity (TT), parallel transmissivity (PT), intersect transmissivity (CT) and degree of polarization (P) and satisfy in the following formula (a)～(d) at least one:

40.0≤TT≤45.0 (a)

30.0≤PT≤40.0 (b)

CT≤2.0 (c)

95.0＜P (d)

Order according to veneer transmissivity (TT), parallel transmissivity (PT) and intersection transmissivity (CT), preferred is respectively 40.5≤TT≤45,32≤PT≤39.5 and CT≤1.5, and preferred again is respectively 41.0≤TT≤44.5,34≤PT≤39.0 and CT≤1.3.Degree of polarization P preferably 95.0% or bigger, and more preferably 96.0% or bigger, more more preferably 97.0% or bigger.

In polaroid of the present invention, when the intersection transmissivity under the wavelength X during as CT (λ), CT ₍₃₈₀₎, CT ₍₄₁₀₎And CT ₍₇₀₀₎Preferably satisfy at least one in the following formula (e)～(g):

CT ₍₃₈₀₎≤2.0 (e)

CT ₍₄₁₀₎≤1.0 (f)

CT ₍₇₀₀₎≤0.5 (g)。

CT more preferably ₍₃₈₀₎≤ 1.95, CT ₍₄₁₀₎≤ 0.9 and CT ₍₇₀₀₎≤ 0.49, CT more preferably again ₍₃₈₀₎≤ 1.90, CT ₍₄₁₀₎≤ 0.8 and CT ₍₇₀₀₎≤ 0.48.

In polaroid of the present invention, after leaving standstill 500 hours under the condition of polaroid at 60 ℃ and 95%RH, the variable quantity (Δ P) of the variable quantity (Δ CT) of transmissivity and degree of polarization of intersecting satisfy following formula (j) and (k) at least one:

-6.0≤ΔCT≤6.0 (j)

-10.0≤ΔP≤0.0 (k)。

Wherein variable quantity refers to deduct the preceding resulting value of measured value of test from testing the back measured value.

More preferably-5.8≤Δ CT≤5.8 and-9.5≤Δ P≤0.0, more more preferably-5.6≤Δ CT≤5.6 and-9.0≤Δ P≤0.0.

In polaroid of the present invention, when polaroid after leaving standstill 500 hours under 60 ℃ and the 90%RH, the variable quantity (Δ P) of the variable quantity (Δ CT) of transmissivity and degree of polarization of intersecting satisfy following formula (h) and (i) at least one:

-3.0≤ΔCT≤3.0 (h)

-5.0≤ΔP≤0.0 (i)。

In polaroid of the present invention, when polaroid after leaving standstill 500 hours under 80 ℃, the variable quantity (Δ P) of the variable quantity (Δ CT) of transmissivity and degree of polarization of intersecting satisfy following formula (l) and (m) at least one:

-3.0≤ΔCT≤3.0 (l)

-2.0≤ΔP≤0.0 (m)。

Use UV3 100PC (making) in 380～780nm scope, to measure veneer transmissivity (TT), the parallel transmissivity (PT) of polaroid and the transmissivity (CT) of intersecting, and use the mean value of measuring for 10 times (mean value under 400～700nm) as each TT, PT and CT by Shimadzu Corporation.Can be according to degree of polarization (%)=100 * [(parallel transmissivity-intersection transmissivity)/(parallel transmissivity+intersection transmissivity)] ^1/2Try to achieve degree of polarization (P).Carry out the polaroid endurancing with two kinds of patterns, the polaroid that (1) only has polaroid and (2) to pile up with bonding agent and glass.In the pattern when measuring independent polaroid, make up cellulose acylate film of the present invention, it is inserted between two polarizers, prepare two same sample, measure then.For the pattern of piling up glass, (about 5cm * 5cm) wherein is stacked on polaroid on glassly, makes cellulose acylate film of the present invention place glass side to prepare two samples.In measuring the veneer transmissivity, sample is arranged to its film side guides light source into, and measure.Measure two samples respectively, average as the veneer transmissivity.

(through the bag of anti-wet process)

In the present invention, " through the bag (damp proof bag) of anti-wet process " defined by the moisture content perviousness of measuring according to cup method (JIS-Z208).Consider bag influence of external environment humidity, preferably uses 40 ℃ with 90%RH under the moisture content perviousness be 30g/ (m ²My god) or littler material.Surpass 30g/ (m ²My god) time prevent that the influence of bag external environment humidity lost efficacy.The moisture content perviousness is 10g/ (m more preferably ²My god) or littler, 5g/ (m most preferably ²My god) or littler.

The bag of wet process of material prevent to(for) process is not particularly limited, as long as it satisfies above-mentioned moisture content perviousness, can use known materials (Hoso Zairyo Binran (Manual of PackagingMaterials), Japan Packaging Institute (1995), Hoso Zairyo no Kiso Chisiki (Basic Knowledge of Packaging Materials), Japan Packaging Institute (November calendar year 2001), Kinosei Hoso Nyumon (Introduction to Functional Packaging), 21st Century Packaging Research Institute (on February 28th, 2002, first edition, the first impression)).In the present invention, low, the in light weight and easy-to-handle material of moisture content perviousness is desirable, and the deposited film that preferred especially use obtains by cvd silicon oxide on plastic foil, aluminium oxide, stupalith etc., or the stack membrane of composite membrane such as plastic foil and aluminium foil.Thickness for aluminium foil is not particularly limited, as long as the thickness of paper tinsel makes the humidity in the bag not influenced by ambient humidity.Yet the thickness of paper tinsel is preferably several microns to the hundreds of micron, more preferably 10 μ m～500 μ m.The humidity of the bag of the anti-wet process that the present invention uses preferably one of meets the following conditions:

When polaroid is in packed state, requires 25 ℃ of temperature to pack interior humidity down and be adjusted to 43%RH～70%RH, preferred 45%RH～65%RH, more preferably 45%RH～63%RH.

Need regulate the interior humidity of bag of packing polaroid, the feasible ambient humidity that is stacked on the liquid crystal board with polaroid differs 15%RH or following.

(anti-reflecting layer)

Functional membrane such as anti-reflecting layer decision design are on the transparent protective film of the liquid crystal cell opposition side configuration of polaroid.Especially; in the present invention, be fit to the anti-reflecting layer of use, wherein light scattering layer and low-index layer are layered on the transparent protective film in this order at least; or using such anti-reflecting layer, wherein middle index layer, high refractive index layer and low-index layer are layered on the transparent protective film in this order.The following describes its preferred example.

The following describes the preferred example of anti-reflecting layer, wherein light scattering layer and low-index layer are arranged on the transparent protective film.

The delustring particle preferably is dispersed in the light scattering layer that the present invention uses, the material refractive index in the light scattering layer beyond the delustring particle preferably 1.50～2.00, the refractive index of low-index layer preferably 1.35～1.49.In the present invention, light scattering layer has antiglare properties and hard conating performance simultaneously, and can by single or multiple lift for example 2～4 layers constitute.

Anti-reflecting layer is preferably designed to rough shape, make that center line average roughness Ra is 0.08～0.40 μ m, 10-point mean roughness Rz is 10 times of Ra or bigger, average concavo-convex be 1～100 μ m apart from Sm, from the standard deviation of the deepest part projecting height of jog is 0.5 μ m or littler, with the center line is that the average concavo-convex standard deviation apart from Sm of benchmark is 20 μ m or littler, the pitch angle is that 0～5 ° face accounts for 10% or bigger, thereby obtains abundant antiglare properties and the uniform delustring texture of vision.For the reflected light color under the illuminant-C, work as a ^*Value is-2～2, b ^*Value is for-3～3, is 0.5～0.99 o'clock at the minimum value and the peaked ratio of 380～780nm scope internal reflection rate, and catoptrical color is preferably neutrality.In addition, by b with transmitted light under the illuminant-C ^*Value is adjusted to 0～3, thereby when being used for display, the white yellow hue that shows preferably descends.In addition, when by inserting 120 μ m * 40 μ m lattices between surface source of light and anti-reflective film, and the standard deviation of measuring the Luminance Distribution on the film is 20 or more hour, when film of the present invention is used for the high definition panel, preferably reduces flash of light.

As optical characteristics, the specular reflectance of the anti-reflecting layer that uses in the present invention is 2.5% or still less, transmissivity is 90% or bigger, and 60-degree gloss number is 70% or still less the time, can suppress outside reflection of light, and improve observability.Therefore, this anti-reflecting layer is preferred.Especially, specular reflectance is more preferably 1% or still less, and most preferably 0.5% or still less.The mist degree of anti-reflecting layer is 20～50%, internal haze/total haze value is 0.3～1, after forming low-index layer, haze value has descended 15% or still less from the haze value that equals light scattering layer, the sharpness that sees through image is to be 20～50% under the 0.5mm at the comb shape width, the ratio of the transmissivity of the light of vertical transmission/on 2 ° the direction of tilting from vertical direction is 1.5～5.0, can prevent the flash of light of high definition LCD panel or reduce the fuzzy of literal etc.Therefore, this is preferred.

(low-index layer)

The refractive index of the low-index layer of the anti-reflective film that the present invention uses is 1.20～1.49, preferred 1.30～1.44.From reducing the angle of reflectivity, the refractive index of low-index layer preferably meets following formula (IX):

(m/4)×0.7＜n1d1＜(m/4)×1.3 (IX)

Wherein m is a positive odd number, and n1 is the refractive index of low-index layer, and d1 is the thickness (nm) of low-index layer, and λ is a wavelength, and its value is 500～550nm.

The following describes the material of the low-index layer that forms the present invention's use.

The low-index layer that the present invention uses contains the fluoropolymer as the low-refraction bonding agent.Preferably by the fluoropolymer of heat or crosslinking by ionizing radiation, its dynamic friction coefficient is 0.03～0.20 to fluoropolymer, with water contact angle be 90～120 °, pure water landing angle is 70 ° or littler, and can be crosslinked by heat or ionizing ray.When the anti-reflective film of the present invention's use was connected in the image display, the peeling force of commercially available adhesive tape was preferably lower, can easily peel off the strip of paper used for sealing or the notepaper of adhesion.Peeling force is 500gf or littler preferably, more preferably 300gf or littler, most preferably 100gf or littler.The skin hardness of measuring by the microhardness instrument is high more, and is difficult more to the film scratch.The skin hardness of film is 0.3GPa or bigger preferably, more preferably 0.5GPa or bigger.

The fluoropolymer that uses in the low-index layer comprises and contains as constituent and the fluorine-containing monomer unit of cross-linking reaction is provided and constitutes the fluorinated copolymer of unit, and the silane compound that contains perfluoroalkyl (for example, (17 fluoro-1,1,2,2-tetrahydrochysene decyl) triethoxysilane) hydrolysate or dehydration condensation.

The object lesson of fluorine-containing monomer unit comprises fluoroolefins (for example, fluorothene, vinylidene fluoride, tetrafluoroethene, perfluoro capryl ethene, hexafluoropropylene, perfluor-2,2-dimethyl-1,3-dioxole), (methyl) acrylic acid alkyl derivative of partially or completely fluoridizing (for example, Biscoat6FM (Osaka Organic Chemical Industry, Ltd. produces), or M-2020 (DaikinIndustries, Ltd. produce)) and the vinyl ether fluoridized wholly or in part.Perfluoroolefine is preferred, and from the angle of refractive index, solubleness, transparency and utilizability, hexafluoropropylene is particularly preferred.

Provide the formation unit of cross-linking reaction to comprise, by being aggregated in the formation unit that the monomer that has self-crosslinking functional group in its molecule in advance obtains, as (methyl) acrylic acid glycidyl esters and glycidyl vinyl ether; Has carboxyl by polymerization, hydroxyl, the monomer of amino or sulfo group etc. (for example, (methyl) acrylic acid, (methyl) acrylic acid methylol ester, (methyl) acrylic acid hydroxyalkyl acrylate, the acrylic acid allyl ester, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid and crotonic acid) the formation unit that obtains; With by polymer reaction crosslinkable group is introduced the formation unit that above-mentioned formation unit (for example, can introduce crosslinkable group by making acryloyl chloride and hydroxyl reaction) obtains as (methyl) acryloyl group.

Except the above-mentioned fluorine-containing monomer unit that cross-linking reaction is provided with constitute the unit, from the transparency equal angles of solubleness solvent and film, no fluorine monomer also can be by suitable copolymerization.The monomeric unit that can use simultaneously is not particularly limited, and its example comprises alkene (for example, ethene, propylene, isoprene, vinyl chloride or vinylidene chloride), acrylate is (for example, methyl acrylate, methyl acrylate, acrylic acid ethyl ester or 2-ethylhexyl acrylate), methacrylate is (for example, methyl methacrylate, the methacrylic acid ethyl ester, methacrylic acid butyl ester or Ethylene glycol dimethacrylate), styrene derivative is (for example, styrene, divinylbenzene, vinyltoluene, or, α-Jia Jibenyixi), vinyl ether (for example, methyl vinyl ether, ethyl vinyl ether or cyclohexyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate base ester or cinnamic acid vinyl esters), acrylamide is (for example, N tert butyl acrylamide or N-cyclohexyl acrylamide), Methacrylamide and acrylic nitrile derivates.

Above-mentioned polymkeric substance can suitably mix and uses the rigidizer be documented among JP-A-10-25388 and the JP-A-10-147739.

(light scattering layer)

Form light scattering layer and be used to make film to have the light diffusing energy that produces because of surface scattering and/or scattering-in, and have the hard conating performance of improving the film mar resistance.Therefore, the light scattering layer of formation contain bonding agent that the hard conating performance is provided, provide light diffusing can the delustring particle and be used to improve refractive index when needed, prevent crosslinked contraction and the inorganic filler that increases intensity.

For the hard conating performance is provided, the thickness of light scattering layer is 1～10 μ m preferably, more preferably 1.2～6 μ m.Thickness is crossed when approaching, and the hard conating performance is insufficient.On the other hand, when thickness is blocked up, crispatura or the fragility variation, it is improper to cause processing.

The bonding agent of light scattering layer preferably has saturated hydrocarbon chain or polyether chain as the polymkeric substance of main chain, more preferably has the polymkeric substance of saturated hydrocarbon chain as main chain.In addition, binder polymer preferably has crosslinked structure.Has saturated hydrocarbon chain as the binder polymer of the main chain polymkeric substance of ethylenically unsaturated monomers preferably.Have saturated hydrocarbon chain as main chain and binder polymer, preferably have (being total to) polymkeric substance of the monomer of two or more ethylenic unsaturated groups with cross-linked structure.Be to improve refractive index, can be chosen in and contain aromatic ring in the molecule or at least one is selected from the monomer of the atom of halogen atom, sulphur atom, phosphorus atoms and nitrogen-atoms.

Monomer with two or more ethylenic unsaturated groups (for example comprises polyvalent alcohol and (methyl) acrylic acid ester, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid butanediol ester, two (methyl) acrylic acid hexanediol ester, diacrylate 1, the 4-cyclohexyl, four (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, four (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid pentaerythritol ester, tetramethyl

acrylic acid

1,2,3-cyclohexane ester, polyurethane polyureas acrylate or polyester polyacrylate); Its oxirane-modified product; Vinyl benzene and its derivant (for example, 1,4-divinylbenzene, 4-vinyl benzoic acid-2-acryloyl group ethyl ester or 1,4-divinyl cyclohexanone); Vinyl sulfone (for example, divinylsulfone); Acrylamide (for example, methylene-bisacrylamide) and Methacrylamide.Can mix two or more that use in the above-mentioned monomer.

The object lesson of high refractive index monomers comprises two (4-methacryl sulfur phenenyl) sulfide, vinyl naphthalene, and ethenylphenyl sulfide and 4-methacryloxy phenyl-4 '-the methoxyphenyl thioether.Can mix two or more that use in these monomers.

In the presence of optical free radical initiating agent or thermal free radical initiator,, can carry out the polymerization that these contain the monomer of ethylenic unsaturated group by with ionization radiation exposure or heating.

Therefore, preparation contains the coating solution of monomer, optical free radical initiating agent or thermal free radical initiator, delustring particle and inorganic filler with ethylenic unsaturated group, and is coated on the transparent supporting body.Then, use ionizing ray irradiation or heating, solidify the coating solution of coating, form anti-reflective film by polyreaction.About these optical free radical initiating agents etc., can use known materials.

Has polyethers as the polymkeric substance of main chain multi-functional epoxy compound's ring-opening polymerization polymer preferably.In the presence of optical free radical initiating agent or thermal free radical initiator,, can carry out multi-functional epoxy compound's ring-opening polymerization by with ionization radiation exposure or heating.Therefore, preparation contain have the multi-functional epoxy compound, the coating solution of optical free radical initiating agent or thermal free radical initiator, delustring particle and inorganic filler, and be coated on the transparent supporting body.Then, use ionizing ray irradiation or heating, solidify the coating solution of coating, thereby form anti-reflective film by polyreaction.

Replace having the monomer of two or more ethylenic unsaturated groups or except that it, crosslinking functionality is introduced polymkeric substance, and pass through the reaction of this crosslinking functionality, cross-linked structure is introduced in the binder polymer with monomer with crosslinking functionality.

The example of crosslinking functionality comprises isocyanate groups, epoxy radicals, aziridinyl ， oxazolinyl, aldehyde radical, carbonyl, diazanyl, carboxyl, methylol and active methylene group.Vinyl sulfonic acid, acid anhydrides, cyanacrylate derivant, melamine, etherificate methylol, ester, carbamate and metal alkoxide such as tetramethoxy-silicane also can be used as monomer, introduce cross-linked structure.Can also use the functional group that shows cross-linking properties because of decomposition reaction, as the blocked isocyanate group.That is, in the present invention, crosslinking functionality can be because of decomposition shows reactive group, but is not to show reactivity immediately.

By being coated with the back heating, the binder polymer that contains crosslinking functionality can form crosslinked structure.

For antiglare properties is provided, light scattering layer contains the delustring particle greater than filler grain, and its particle mean size is 1～10 μ m, preferred 1.5～7.0 μ m, for example inorganic compound particles or resin particle.

The concrete preferred example of above-mentioned delustring particle comprises for example inorganic compound particles, as silicon oxide particle and TiO ₂Particle; And resin particle, as the particle of acrylic resin, the resinoid particle of cross-linked acrylic acid, polystyrene particle, crosslinked styrene particle, melamine resin particle and benzoguanamine resin particle.Wherein, crosslinked styrene particle, crosslinked acrylic resin particle, crosslinked acryloyl group styrene resin particle and silicon oxide particle are preferred.

The shape of particle that is suitable for can be spherical or irregular shape.

In addition, can also mix two or more delustring particles that use different-grain diameter.Have the delustring particle of greater particle size that antiglare properties can be provided, and the delustring particle that has than small particle diameter can provide another kind of optical property.

In addition, the size distribution of above-mentioned delustring particle most preferably is a monodispersity, and each particle preferably has same particle size as far as possible.For example, when particle diameter ratio mean grain size big 20% or more particle were defined by corase particles, the ratio of corase particles preferably 1% or littler in all particles, and more preferably 0.1% or littler, more more preferably 0.01% or littler.After the normal synthetic reaction, the delustring particle that obtains having this size distribution by classification, and when increasing the classification number of times or strengthening its degree, can obtain having the delustring particle that more preferably distributes.

Above-mentioned delustring particle is included in the light scattering layer, makes that the amount of delustring particle is preferably 10～1,000mg/m in the light scattering layer that forms ², more preferably 100～700mg/m ²

Use the Coulter counting method to measure the size distribution of delustring particle, and the distribution that will measure is converted into the population distribution.

For improving the refractive index of light scattering layer, this layer preferably also contains inorganic filler except above-mentioned delustring particle, and it is selected from titanium, zirconium, and aluminium, indium, zinc, tin and antimony, mean grain size is 0.2 μ m or littler, preferred 0.1 μ m or littler, more preferably 0.06 μ m or littler.

On the contrary, use the high index of refraction particle to increase in the light scattering layer of delustring particle refringence therein, also preferred use monox, thus the refractive index of this layer can be remained on quite low level.Preferred particle diameter is identical with above-mentioned inorganic filler.

The object lesson of used inorganic filler comprises TiO in the light scattering layer ₂, ZrO ₂, Al ₂O ₃, In ₂O ₃, ZnO, SnO ₂, Sb ₂O ₃, ITO and SiO ₂From increasing the angle of refractive index, TiO ₂And ZrO ₂Be particularly preferred.Silane coupled processing or titanium coupling processing are also preferably passed through in the surface of inorganic filler, the preferred surface conditioning agent that uses have can with the functional group of adhesive reaction on the filling surface.

The addition of these inorganic fillers preferably the light scattering layer gross mass 10～90%, more preferably 20～80%, especially more preferably 30～75%.

Compare with wavelength, described filler has enough little particle diameter, thus can not cause scattering, and the filler dispersion in the binder polymer is as the optics homogeneous material.

The potpourri piece of bonding agent and inorganic filler in the light scattering layer preferably has refractive index 1.48～2.00, and more preferably 1.50～1.80.For regulating refractive index in above-mentioned scope, can compatibly select the kind and the amount ratio of bonding agent and inorganic filler.How to select them to learn by experiment in advance at an easy rate.

In light scattering layer, even for preventing crawling, uneven drying is even, point defect etc., and to guarantee surface uniformity, the coating composition that is used to form antiglare layer contains fluorochemical surfactant or contains the surfactant of silicones or its two.Especially, preferably use fluorochemical surfactant,, just can manifest the effect that improves surface imperfection,, uneven drying even point defect even as crawling because add surfactant in a small amount.Its objective is by when strengthening surface uniformity, high-speed coating is provided, thereby boosts productivity.

The following describes anti-reflecting layer, wherein middle index layer, high refractive index layer and low-index layer are layered on the transparent protective film in this order.

Designed anti-reflective film has on substrate the layer structure by the order of middle index layer, high refractive index layer and low-index layer (outermost layer), makes refractive index satisfy following relation:

The refractive index of the refractive index＞low-index layer of the refractive index＞transparent supporting body of the refractive index of high refractive index layer＞middle index layer.

In addition, between transparent supporting body and middle index layer, hard conating can be set.In addition, index layer hard conating, high refractive index layer and low-index layer during anti-reflecting layer can comprise.Its example is documented in JP-A-8-122504, JP-A-8-110401, and JP-A-10-300902 is among JP-A-2002-243906 and the JP-A-2000-111706.

In addition, each layer can be endowed other functions, its example comprise antifouling low-index layer and antistatic high refractive index layer (referring to, for example, JP-A-10-206603 and JP-A-2002-243906).

The mist degree of anti-reflective film preferably 5% or still less, more preferably 3% or still less.In addition, by the film strength measured according to the pencil hardness test of JIS K5400 preferably H or bigger, more preferably 2H or bigger, most preferably 3H or bigger.

(high refractive index layer and middle index layer)

The high refractive index layer of anti-reflective film is made of curable film and matrix binder, and the mean grain size that curable film contains high index of refraction at least is 100nm or littler mineral compound ultrafine particle.

The mineral compound ultrafine particle of high index of refraction comprises that refractive index is 1.65 or bigger, preferred 1.9 or bigger mineral compound.Its example comprises Ti, Zn, Sb, Sn, Zr, Ce, Ta, the oxide of La and In and contain the composite oxides of above-mentioned metallic atom.

The preparation ultrafine particle by handle with surface-treating agent particle surface (for example, silane coupling agent, referring to JP-A-11-295503, JP-A-11-153703 and JP-A-2000-9908; Anionic compound or organic metal coupling agent, referring to JP-A-2001-310432), form the high index of refraction particle as the core-shell structure of core (referring to, JP-A-2001-166104 etc.), with mix to use specific dispersant (referring to, JP-A-11-153703, United States Patent (USP) 6,210,858 and JP-A-2002-2776069).

The material that forms matrix comprises known thermoplastic resin and thermoset resin at present.

In addition, preferred at least a composition is selected from the composition that contains the polyfunctional compound, the group that it contains two or more free radicals at least and/or cationic polymerizable further preferably comprises the organometallics that contains hydrolyzable group or the composition of its partial condensate.Its example comprises and is documented in JP-A-2000-47004, JP-A-2001-315242, the composition among JP-A-2001-31871 and the JP-A-2001-296401.

In addition, further preferably from the hydrolytic condensate of metal alkoxide and colloidal metal oxide that obtains and the curable film that obtains from metal alkoxide compositions.These for example are documented among the JP-A-2001-293818.

The refractive index of high refractive index layer normally 1.70～2.20, the thickness of high refractive index layer is 5nm～10 μ m preferably, more preferably 10nm～1 μ m.

In the refractive index of index layer be adjusted to value between the refractive index of the refractive index of low-index layer and high refractive index layer.In the refractive index preferably 1.50～1.70 of index layer.In addition, its thickness is 5nm～10 μ m preferably, more preferably 10nm～1 μ m.

(low-index layer)

The low-index layer stacked above one another is on high refractive index layer.The refractive index of low-index layer is 1.20～1.55, preferred 1.30～1.50.

Low-index layer preferably constitutes the outermost layer with mar resistance and antifouling property.As the method for significantly improving mar resistance, it effectively gives surperficial sliding, can use the method for the rete of at present known introducing silicones or introducing fluorine.

The refractive index of fluorochemicals is preferably 1.35～1.50, and more preferably 1.36～1.47.In addition, fluorochemicals preferably contain 35～80 quality % fluorine atom compound and have crosslinked or polymerisable functional group.

Fluorochemicals comprise for example be documented in JP-A-9-222503[0018]～[0026] section, JP-A-11-38202[0019]～[0030] section, JP-A-2001-40284[0027]～[0028] section and JP-A-2000-284102 in compound.

Silicon resin compound is the compound with polysiloxane structure, preferably contains curable functional group or polymerisable functional group in its polymer chain, is used for forming crosslinked structure at film.Its example comprises reactive silicon resin (for example, Silaplane (Chisso Corporation manufacturing)) and the polysiloxane (JP-A-11-258403) that has silanol at two ends.

Crosslinked or polyreaction with fluorine-containing and/or siloxane polymer of crosslinked or polymerizable groups, the coating composition that preferably contains polymerization initiator, emulsion etc. by rayed or heating, form outermost layer, this is to carry out in its coating or afterwards.

In addition, the film that solidifies of sol-gel further preferably, it co-exists in down at catalyzer, and the silane coupling agent that solidifies organometallics such as silane coupling agent and contain specific fluorine-containing alkyl by condensation reaction obtains.

Its example comprises that the silane compound or its partial hydrolysis condensation product that contain Polyfluoroalkyl (are documented in JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, compound among JP-A-9-157582 and the JP-A-11-106704), with contain fluorine-containing long chain alkyl group or contain the silicyl (being documented in JP-A-2000-117902, the compound among JP-A-2001-48590 and the JP-A-2002-53804) of perfluoroalkyl ether group.

As above-mentioned adjuvant outside these, low-index layer (for example can contain filler, silicon dioxide (monox), average primary particle size is the low-refraction mineral compound of 1～150nm, as fluorine-containing particle (magnesium fluoride, calcium fluoride or barium fluoride) and be documented in JP-A-11-3820[0020]～[0038] section) in thin organic particle), silane coupling agent, slip agent, surfactant etc.

When low-index layer was in outermost lower floor position, it can form (for example, vacuum deposition method, sputtering method, ion plating, plasma CVD method) by gas phase process.Coating process is preferred, because make low-index layer marked downly.

The film thickness of low-index layer is 30～200nm preferably, more preferably 50～150nm, most preferably 60～120nm.

(layer outside the anti-reflecting layer)

In addition, hard conating can also be set, forward scattering layer, bottom, antistatic layer, following coating, protective seam etc.

(hard conating)

Hard conating is arranged on the surface of supporter, for the transparent protective film with anti-reflecting layer provides physical strength.Especially, it preferably is arranged between transparent supporting body and the above-mentioned high refractive index layer.Hard conating preferably forms by the cross-linking reaction or the polyreaction of light and/or heat solidifiable compound.Curable functional group is the functional group of photopolymerizable preferably, contains the organometallics of hydrolyzable functional group, and especially the organoalkoxysilane based compound is preferred.

The object lesson of these compounds comprises and high refractive index layer is exemplified similar compound.The concrete component composition of hard conating comprises and for example is documented in JP-A-2002-144913, those in the international open No.00/46617 pamphlet of JP-A-2000-9908 and PCT.

High refractive index layer also can serve as hard conating.In this case, preferably use, make it be contained in the hard conating and form hard conating the described technology fine dispersion of high refractive index layer particulate.

Hard conating also can serve as antiglare layer (aftermentioned), and antiglare layer contains the particle that mean grain size is 0.2～10 μ m, thereby antiglare properties is provided.

Can suitably design the thickness of hard conating according to purposes.The thickness of hard conating is 0.2～10 μ m preferably, more preferably 0.5～7 μ m.

In the pencil hardness test according to JIS K5400, the intensity of the hard conating of measurement is H or bigger preferably, more preferably 2H or bigger, most preferably 3H or bigger.In addition, in the Taber test according to JISK5400, the preferred wear extent of test pieces after test is as far as possible little.

(antistatic layer)

Providing under the situation of antistatic layer, preferably giving electric conductivity in specific insulation is 10 ^-8(Ω cm ^-3) or littler.By using hygroscopic material, water-soluble inorganic salt, certain surfactant, cationic polymer, anionic polymer or colloidal silica etc., can make specific insulation is 10 ^-8(Ω cm ^-3).Yet this depends on temperature and humidity to a great extent, thereby the problem that exists is can not guarantee sufficient electric conductivity under low humidity.Therefore, the material used of conductive layer metal oxide preferably.Some metal oxides are coloured, and such metal oxide is unfavorable, because when they were used as the material of conductive layer, whole film was coloured.The metal that forms colourless metallic oxide comprises Zn, Ti, and Sn, Al, In, Si, Mg, Ba, Mo, W and V, the preferred use contained these metal oxides as principal ingredient.Its object lesson comprises ZnO, TiO ₂, SnO ₂, Al ₂O ₃, In ₂O ₃, SiO ₂, MgO, BaO, MoO ₃, WO ₃, V ₂O ₅With its composite oxides, ZnO, TiO ₂And SnO ₂Be particularly preferred.As for containing heteroatomic example, ZnO adds Ai or In is effectively, for SnO ₂Add Sb, Nb or halogen atom and be effectively and for TiO ₂It is effective adding Nb or Ta.In addition, described in JP-B-59-6235, can also use a kind of material, wherein above-mentioned metal oxide and different crystalline metal particle or fibrous material (for example, titanium dioxide) adhesions.Volume resistance value and surface resistivity are the physical values that differs from one another, so they can not compare simply.Yet, for the electric conductivity of guaranteeing specific insulation is 10 ^-8(Ω cm ^-3) or littler, the surface resistivity of conductive layer is about 10 ^-10(Ω/square) or littler, more preferably 10 ^-8(Ω/square) or littler.When antistatic layer was arranged as outermost layer, the surface resistivity that needs to measure conductive layer was as value at this moment, and this value can be measured in forming the described stacked membrane process of this instructions.

(LCD)

Cellulose acylate film of the present invention, comprise the optical compensation films of cellulose acylate film and use the polaroid of optical compensation films, can be used for the liquid crystal cell and the LCD of various display modes.The various display modes that propose comprise TN (twisted-nematic) at present, IPS (switching in the face), FLC (ferroelectric liquid crystals), AFLC (anti ferroelectric liquid crystal), OCB (optical compensation curved), STN (supertwist is to row), VA (homeotropic alignment) and HAN (mix and arrange to row).In these patterns, preferably use IPS, OCB or TN pattern.

LCD shown in Fig. 2 has light polarizing film 8 and 20, the first delay zones, 10, the second delay zones 12,

substrate

13 and 17, and be clipped in liquid crystal layer 15 between these substrates.Light polarizing film 8 is clipped between diaphragm 7a and the 7b, and light polarizing film 20 is clipped between diaphragm 19a and the 19b.

In the LCD shown in Fig. 2, liquid crystal cell is by

substrate

13 and 17 and be clipped in liquid crystal layer therebetween 15 and constitute.In not having twist structured IPS type liquid crystal cell, when transmission mode, thickness of liquid crystal layer d (μ m) and refractive index anisotropy Δ n's is long-pending, and promptly the optimal value of Δ nd is 0.2～0.4 μ m.In this scope, white display brightness height, black display brightness is low, thereby obtains the display of good illumination, high-

contrast.Substrate

12 and 17 has the alignment films (not shown), it is formed on the respective side that contacts with liquid crystal layer 15, thereby the liquid crystal liquid crystal property molecule is near being parallel to substrate surface, in addition, when not applying the voltage attitude or applying the low-voltage attitude, the direction of liquid crystal molecular orientation can be controlled by the

direction

14 and 18 of friction treatment on alignment films respectively.In addition, voltage can be applied to the inside surface that electrode (Fig. 2 does not show) on the liquid crystal liquid crystal property molecule is formed on

substrate

13 or 17.

In Fig. 1, schematically show the liquid crystal liquid crystal property molecules align in the pixel area of liquid crystal layer 15.Fig. 1 is a synoptic diagram, be illustrated in the arrangement that has near liquid crystal liquid crystal property molecule in the zone of minimum area of a pixel that equals liquid crystal layer 15, together with the alignment films that on the inside surface of

substrate

13 and 17, forms scrape wiping direction 4, and be formed on

substrate

13 and 17 inside surfaces, voltage can be applied to the

electrode

2 and 3 on the liquid crystal liquid crystal property molecule.The anisotropic nematic liquid crystal that has a positive induction when use carries out activity when driving as the field effect liquid crystal, and the direction of liquid crystal molecular orientation is not 5a and 5b when applying the voltage attitude or applying the low-voltage attitude, at this moment, obtains black the demonstration.When applying voltage between

electrode

2 and 3, the liquid crystal liquid crystal property molecule is changed into 6a and 6b according to the voltage that applies respectively with its direction of orientation.Under this condition, carry out bright demonstration usually.

Turn back to the explanation of Fig. 2, the axis of homology 9 of configuration light polarizing film 8 and the axis of homology 21 of light polarizing film 20 are perpendicular to one another them.The slow-axis direction 16 of liquid crystal liquid crystal property molecule in the liquid crystal layer 16 when the slow axis 11 in first delay zone 10 (cellulose acylate film of the present invention) is parallel to the axis of homology 9 of light polarizing film 8 and deceives demonstration.

LCD shown in the arrangement plan 2 make light polarizing film 8 be clipped between two diaphragm 7a and the 7b, but diaphragm 7b can not have.In addition, light polarizing film 20 also is clipped between two diaphragm 19a and the 19b, but can not have near the diaphragm 19 on liquid crystal layer 15 sides.In the embodiment shown in Fig. 2, position with liquid crystal cell is a benchmark, first delay zone and second delay zone (rod shaped liquid crystal compound layer of the present invention) can be configured in liquid crystal cell and observe between the light polarizing film of side, or be configured in liquid crystal cell and between the light polarizing film at the display back side.According in each of these structures of implementing pattern of the present invention, the second delay zone position is more near liquid crystal cell.

Fig. 3 illustrates the another kind of pattern of the present invention of implementing.In the LCD shown in Fig. 3, second delay zone 12 places between the light polarizing film 8 and first delay zone 10.In the LCD shown in Fig. 3, diaphragm 7b and diaphragm 19a can not have.In the embodiment shown in Fig. 3, the slow axis 11 in first delay zone 10 during perpendicular to the axis of homology 9 of light polarizing film 8 and black the demonstration in the liquid crystal layer 15 slow-axis direction 16 of liquid crystal liquid crystal property molecule arrange.In addition, in the embodiment shown in Fig. 3, be benchmark with the position of liquid crystal cell, first delay zone and second delay zone can be configured in liquid crystal cell and observe between the light polarizing film of side, or be configured between the light polarizing film at the liquid crystal cell and the display back side.According in each of these structures of implementing pattern of the present invention, the first delay zone position is more near liquid crystal cell.

In addition, in Fig. 3, the embodiment of the transmission-mode display that is provided with upside polaroid and downside polaroid is shown, but embodiment of the present invention can be the reflection-mode display that only is provided with a polaroid.In this case, the light path in the liquid crystal cell doubles, thereby optimum Δ nd value becomes and is 1/2 of above-mentioned value.Liquid crystal cell of the present invention is not limited to those of IPS pattern, and any LCD can be suitable for, as long as their liquid crystal liquid crystal property molecule is arranged essentially parallel to the surface orientation of above-mentioned a pair of substrate when black the demonstration.The example of this display comprises ferroelectric liquid Crystal, Antiferroelectric liquid crystal display and ECB-mode LCD.

The structure of LCD of the present invention is not limited to Fig. 1～shown in Figure 3, can comprise other elements.For example, color filter can place between liquid crystal layer and the light polarizing film.In addition, the surface of the diaphragm on the light polarizing film can be carried out anti-reflex treated and hard conating is arranged.In addition, can use the composed component of giving electric conductivity.Using under the situation of display as transmission-type, backlightly can be arranged on the display back side as light source cold cathode or thermic cathode fluorimetric pipe, light emitting diode, field emission apparatus or el light emitting device.In this case, position backlight can each upside or downside in Fig. 2 and Fig. 3.In addition, can liquid crystal layer and backlight between place reflective polaroid, diffuser plate, prismatic lens and optical waveguide.Selectively, as mentioned above, LCD of the present invention can be a reflection-type.In this case, only have a polaroid to place and observe on the side, reflectance coating places on the inside surface of the back side of liquid crystal cell or liquid crystal cell bottom side substrate.Certainly, can use above-mentioned light source on observation liquid crystal cell side, to provide preceding light.

LCD of the present invention comprises through image observation escope, image projection escope and light modulation type display.The embodiment of active matrix liquid crystal display that the present invention is used for 3-or 2-terminal semiconductor devices such as TFT or MIM is effective especially.Let alone, to be used for being known as the embodiment of the passive matrix liquid crystal display that timesharing drives also effective in the present invention.

The ocb mode liquid crystal display is to use the LCD of the brilliant unit of curved orientation mode liquid crystal, the rod shaped liquid crystal molecule that top area exists in the liquid crystal cell basically with lower area in the relative direction orientation (the former with the latter symmetric orientation) of rod shaped liquid crystal molecular orientation direction that exists.The brilliant unit of ocb mode liquid crystal is disclosed in U.S. Patent No. 4,583, in 825 and 5,410,422.Because symmetry in rod shaped liquid crystal molecular orientation in the liquid crystal cell top area and the lower area is so the liquid crystal cell of curved orientation has optics self compensation function.Therefore, this liquid crystal mode is also referred to as OCB (optical compensation curved) liquid crystal mode.The advantage of the mode LCD of curved orientation is to reply soon.

Illustrate in greater detail the present invention below with reference to embodiment, but scope of the present invention is not limited to these examples.

[measuring method]

(delay)

By make the light bump film of wavelength X nm in film surface normal direction, use KOBRA21ADH (Oji Scientific Instruments manufacturing) measure R e (λ) value.In addition, three length of delays that Rth (λ) value is measured based on three different directions calculate, be above-mentioned length of delay Re (λ), slow axis is measured under the condition of+40 ° of directions bumps that tilt with respect to embrane method line direction as sloping shaft and the light that makes wavelength X nm in face length of delay and slow axis is measured under the condition of-40 ° of directions bumps that tilt with respect to embrane method line direction as sloping shaft and the light that makes wavelength X nm in face length of delay, and input is as the default 1.48 and the film thickness of mean refractive index.In addition, unless refer else, the wavelength X of measure R e and Rth is set to 550nm.

(moisture rate)

Use Karl Fischer technology, drimeter and sample drying device (CA-03 and VA-05, Mitsubishi Chemical Corporation makes), measure the moisture of 7mm * 35mm sample.The moisture rate is calculated divided by sample quality (g) with moisture (g).

(percent thermal shrinkage)

Testing sample 30mm * 120mm placed respectively 24 hours and 120 hours under 90 ℃ and 5%RH condition, used automatic divider (Shinto Scientific Co., Ltd. manufacturing), along the both sides of each sample, went out the hole of 6mm φ at interval with 100mm.Minimum calibration 1/1000mm reads each actual size (L1) at interval with scale.In addition, each sample was placed 24 hours under 90 ℃-5%RH of 60 ℃-95%RH conditioned disjunction condition, measured each and went out size (L2) at interval.According to expression formula (L1-L2)/percent thermal shrinkage is determined in L1} * 100.

(glass transition temperature Tg)

Membrane sample to be measured (unstretched processing) 5mm * 30mm moisture content in 25 ℃-60%RH atmosphere is controlled at least 2 hours, using dynamic viscoelastic measuring instrument (Vibron DVA-225 then, I.T.Keisoku Seigyo K.K. makes)) measure Tg down following the setting: gripping distance is 20mm, temperature rate-of-rise is 2 ℃/min, measuring temperature range is 30～200 ℃, and frequency is 1Hz.When the energy storage elastic modulus is plotted as ordinate with logarithmic scale, temperature (℃) when being plotted as abscissa with linear graduation, transfer to from solid area under the situation in glass transition zone, find that the energy storage elastic modulus sharply descends.Draw out along with the straight line 1 that sharply descends in the solid area with along with the straight line 2 that sharply descends in the glass transition zone.The intersection point of straight line 1 and straight line 2 is as glass transition temperature Tg (dynamic viscoelastic) because it when rising corresponding to temperature the energy storage elastic modulus sharply descend so that membrane sample begins temperature softening and when beginning to transfer to the glass transition zone.

(elastic modulus)

With membrane sample 10mm * 200mm to be measured control moisture content 2 hours under 25 ℃ and 60%RH condition, use stretching testing machine (Ltd. makes for Strograph R-2, Toyo Seiki Seisaku-sho) to stretch then, impose a condition for: the former length of sample is 100mm, and draw speed is 100mm/sec.Calculate its elasticity from incipient extension stress and length growth rate.

(photoelastic coefficient)

Main shaft to membrane sample 10mm * 10mm to be measured applies drawing stress, and (M150, JASCO Corporation makes) measures the Re value under this drawing stress with ellipsometer.According to the change calculations photoelastic coefficient that postpones with stress.

(mist degree)

Use mist degree instrument (Ltd. makes for HGM-2DP, Suga Test Instruments Co.), according to the method for JIS K6714, measuring size under 25 ℃ and 60%RH is the mist degree of the sample of 40mm * 80mm.

(measuring the method for hydraulic permeability)

About measuring the method for hydraulic permeability (moisture content perviousness), can use be documented in Kobunshi Jikken Koza 4 (Course 4 in Experiments of HighPolymers)-Kobunshi no Bussei II (Physical Properties of High Polymers II)-, 285-294 page or leaf (wherein having explained the measurement (comprising gravimetric method, thermometer method, vapor pressure method and adsorbance method) of vapour permeability amount), Kyoritsu Shuppan Co., the method among the Ltd..In following example,, under 40 ℃ of temperature and humidity 90%RH, measure according to JIS standard JISZ0208, condition B.

Embodiment 1

1. formation cellulose acylate film

(1) cellulose acylate

The cellulose acylate of the different acyl degree of substitution shown in the preparation table 1-1.More specifically, except carboxylic acid, also add sulfuric acid, under 40 ℃, carry out acylation reaction as catalyzer (7.8 mass parts/100 mass parts celluloses).Subsequently, by control sulfuric acid catalysis agent content, liquid water content and curing time, regulate total degree of substitution and 6-position degree of substitution.Under 40 ℃, carry out slaking.In addition, the low molecular weight compositions in the cellulose acylate that obtains with the acetone flush away.

(2) dope preparation

Under agitation in the cellulose acylate shown in the table 1-1; add plastifier (2: 1 potpourris of Triphenyl phosphate and phosphoric acid xenyl diphenyl), have below shown in the delay of structure express agent and mixed solvent (87: 13 quality of methylene chloride and methyl alcohol are than potpourri), the potpourri total solid concentration that makes generation is 19 quality %.Heating continues to stir down, preparation solution.Meanwhile; fine particle (silicon dioxide (primary particle size: 20nm) with 0.05 mass parts; about 7), (TINUVIN 327 for 0.375 mass parts ultraviolet light absorber B Mohr ' s hardness:; Ciba SpecialtyChemicals makes) and 0.75 mass parts ultraviolet light absorber C (TINUVIN 328; CibaSpecialty Chemicals makes) be added in each cellulose acylate of 100 mass parts, heating is stirred down.The adding ratio that agent is expressed in plastifier and delay is shown in table 1, represents with the mass parts in the cellulose acylate of per 100 mass parts.From the dope of such preparation, form film F1～F10 and F14～F17 according to following method.

Postpone to express agent

Stir down; with plastifier (2: 1 potpourris of Triphenyl phosphate and phosphoric acid xenyl diphenyl), on show structure delay express agent and methyl acetate, acetone, ethanol and butanols 81: 8: 7: the potpourri of 4 mass ratioes is added among the cellulose acylate CA3 shown in the table 1; making the potpourri total solid concentration is 16.4 quality %, thereby makes the cellulose acylate swelling.Meanwhile; stir down the fine particle of 0.05 mass parts [silicon dioxide (primary particle size: 20nm, Mohr ' s hardness: about 7)] and the ETHYL CTTRATE (1: 1 potpourri of citric acid mono ethyl ester and citric acid diethylester) of 0.04 mass parts are added in the cellulose acylate of 100 mass parts.The adding ratio that agent is expressed in plastifier and delay is shown in table 1, represents with the mass parts in the cellulose acylate of per 100 mass parts.The solution of swelling is cooled to-70 ℃, is heated to 40 ℃ of fusions then.Filter the dope that obtains like this, concentrate fast by being heated to 120 ℃, the solid concentration in dope is adjusted to about 21%.From the dope of such preparation, form film F11～F13 according to following method.

(fluid casting)

Use band casting machine to make each dope fluid casting.When residual solvent content reduces to 25～35 quality %, from the film that strips such formation, and use stenter extensibility (referring to table 2) with 15%～23% on Width to stretch, thereby form cellulose acylate film.In stenter, in the Width stretched film, use heated-air drying simultaneously, shrink about 5% then.Subsequently, stenter is carried and made the roller conveying into, and is further dry, carries out annular knurl, batches then.Film width of measuring from the stenter porch and the film width of measuring from the stenter outlet calculate extensibility, are shown in table 1-2.On each cellulose acylate film (optical compensation films) that forms like this, at Re length of delay and the Rth length of delay measured under the 25 ℃-60%RH condition under the wavelength 550nm.In addition, each film humidity regulation under 25 ℃ of following 10%RH or 80%RH was measured the Re length of delay and the Rth length of delay of each film after at least 2 hours, was clipped between two sheet glass by silicones then, further sealing.In each cellulose acylate film; the Re amount of delay Re (10%RH) that humidity causes when 80%RH changes to 10%RH-Re (80%RH); Rth amount of delay Rth (the 10%RH)-Rth (80%RH) that causes when 80%RH changes to 10%RH with humidity is shown in table 1-2, is expressed as Δ Re and Δ Rth respectively.

Table 1-1

Total degree of substitution is 2-, 3-and 6-position degree of substitution sum, equals degree of substitution with acetyl group and adds the propiono degree of substitution.

Table 1-2

No.?

Cotton

Plasticizer loading

Express agent content

Draw ratio (%)

The stenter temperature (℃)

Dry film thickness (μ m)

Re (nm)

Rth (nm)

ΔRe?

?ΔRth?

Water content (%)

The moisture content perviousness

Tg (℃)?

F1?

CA1?

11.7?

4.0?

23?

135?

92?

51?

130?

11?

?29?

2.96?

850?

143?

F2?

CA2?

11.7?

5.0?

20?

135?

92?

47?

211?

10?

?29?

2.94?

854?

143?

F3?

CA3?

11.7?

0.0?

20?

140?

92?

16?

114?

12?

?41?

3.36?

1500?

145?

F4?

CA3?

11.7?

5.0?

20?

135?

92?

74?

220?

9?

?28?

2.96?

1144?

142?

F5?

CA3?

11.7?

6.5?

15?

135?

92?

67?

237?

8?

?27?

2.95?

1037?

142?

F6?

CA3?

11.7?

6.5?

25?

135?

110?

140?

303?

10?

?32?

2.95?

867?

142?

F7?

CA3?

5.7?

6.5?

15?

145?

92?

68?

274?

8?

?29?

2.95?

1444?

147?

F8?

CA3?

11.7?

6.5?

15?

130?

80?

63?

223?

8?

?26?

2.95?

1190?

142?

F9?

CA3?

11.7?

6.5?

15?

130?

92?

72?

256?

9?

?27?

2.95?

1035?

142?

F10?

CA3?

11.7?

5.0?

23?

135?

60?

48?

132?

8?

?25?

2.96?

1689?

142?

F11?

CA3?

11.7?

0.0?

20?

135?

80?

17?

155?

10?

?44?

3.36?

1725?

145?

F12?

CA3?

11.7?

5.0?

22?

135?

86?

58?

275?

10?

?28?

2.96?

1265?

142?

F13?

CA3?

11.7?

6.5?

20?

135?

110?

80?

298?

11?

?27?

2.95?

954?

142?

F14?

CA4?

11.7?

5.0?

20?

135?

92?

51?

274?

9?

?28?

3.17?

1127?

142?

F15?

CA5?

11.7?

5.0?

20?

135?

92?

52?

277?

9?

?31?

3.18?

1130?

142?

F16?

CA6?

11.7?

5.0?

20?

135?

80?

55?

121?

9?

?26?

2.34?

1420?

138?

F17?

CA7?

11.7?

5.0?

15?

135?

92?

66?

278?

9?

?36?

3.2?

1136?

141?

In addition, to each film that forms measure glass transition temperature (Tg), after moisture is regulated under 25 ℃ and the 80%RH water content and at 60 ℃, the moisture content perviousness under 95%RH and the 24 hours conditions, the measured value that obtains also is shown in table 2.Its haze value of all these films is 0.1～0.9, and the mean diameter of used matting agent secondary is 1.0 μ m, tensile modulus of elasticity be 4Gpa or more than, the mass change that left standstill 48 hours under the condition of 80 ℃ and 90%RH is 0～3%.In addition, left standstill 24 hours under the condition of 60 ℃ and 95%RH and condition at 90 ℃ and 5%RH under leave standstill 24 hours after, change in size is 0～4.5%.In addition, the photoelastic coefficient of each sample film is 50 * 10 ^-13Cm ²/ dyne or following.

Other films by and blooming F13 same way as shown in the table 2 form, except their dry thickness becomes 143 μ m and 176 μ m respectively, be 1.3 times and 1.6 times of F13 dry thickness.Can confirm that from these films roughly the Re of proportional increase and Rth value and thickness almost are inversely proportional to thickness and moisture content perviousness.The humidity correlativity of Re and Rth, i.e. Δ Re and Δ Rth, glass transition temperature Tg and water content, all irrelevant with thickness, film has identical value on each of these factors.

Each cellulose acylate film (F1～F17) at band contact side 1.0N potassium hydroxide solution (solvent: water/isopropyl alcohol/propylene glycol=69.2 mass parts/15 mass parts/15.8 mass parts) with 10cc/m ²Coating, aqueous slkali remain on film last 30 second under about 40 ℃ of temperature.Then, discard solution,, further remove water droplet with air knife with pure water washing film surface.Subsequently, following dry 15 seconds at 100 ℃.The contact angle on pure water and alkali treatment surface is 42 °.

(formation of alignment films)

Be used to form the commercial composite (JALS-204R, JSR Corporation makes) of vertical alignment layer with methyl ethyl ketone with 1: 1 dilution proportion, use line bar spreader with 2.4ml/m ²Coverage is applied to cellulose membrane and (on the F1～F17), uses 120 ℃ of heated-air dryings 120 seconds then immediately.

Next, by in the 9.2g methyl ethyl ketone, showing the rod shaped liquid crystal compound under the dissolving 3.8g, 0.06g Photoepolymerizationinitiater initiater (Irgacure907, Ciba Geigy AG produces), 0.02g photosensitizer (KAYACURE DETX, Nippon Kayaku Co., Ltd. produces) and 0.002g under show air interface side vertical-tropism agent, prepare solution.On the alignment layer surface side, to each film, use metal bar to form alignment films on the film solution coat with following numbering.Film for each solution coat is stacked in metal frame, and heating is 2 minutes in 100 ℃ of constant temperature enclosures, thereby makes bar-shaped compound molecule orientation.Then, use 120W/cm high-pressure mercury vapour lamp, between the rod shaped liquid crystal molecule, form crosslinked 80 ℃ of following UV irradiations 20 seconds.Subsequently, each film cool to room temperature.Therefore, make optical anisotropic film.

The viscosity of each optical anisotropic film that records under 90 ℃ of film-surface temperatures is 495cp.This viscosity number is to use hot type rotary viscosity measuring and optical anisotropic layer to have the result of the liquid crystal layer (remove and desolvate) of same composition.

The rod shaped liquid crystal compound

Air interface side vertical-tropism agent:

The exemplary compounds of putting down in writing among the Jap.P. No.2003-119959 (II-4)

Use automatic birefringence measurement instrument (KOBRA-21ADH, Oji Scientific Instruments makes, measure wavelength: 550nm), measure the Re correlativity of each film that forms like this to angle of light, and, calculate the optical characteristics of each optical anisotropic layer by deducting the predetermined contribution portion of supporter.Consequently, find that KH-01 and KH-H1 respectively have the Re value and be 0nm, the Rth value is-225nm, the Re value of KH-02 is 0nm, and the Rth value is-295nm that the Re value of KH-03 is 0nm, the Rth value is-180nm, the Re value of KH-04 is 0nm, and the Rth value is-260nm, thereby confirms that the rod shaped liquid crystal molecule is vertical orientated in each film.

＜making polarization board protective film 1 〉

Following composition is added in the mixer each composition of dissolving under heated and stirred, preparation cellulose acylate solution A.

The composition of cellulose acetate solution A:

Cellulose acetate 100 mass parts of degree of substitution 2.86

Triphenyl phosphate (plastifier) 7.8 mass parts

Phosphoric acid xenyl diphenyl (plastifier) 3.9 mass parts

Methylene chloride (first solvent) 300 mass parts

Methyl alcohol (second solvent) 54 mass parts

1-butanols 11 mass parts

Following composition is added in another mixer its composition of dissolving under heated and stirred, preparation additive solution B-1.

The composition of＜additive solution B-1 〉

Methylene chloride 80 mass parts

Methyl alcohol 20 mass parts

Optical anisotropy depressant 40 mass parts of showing down

The additive solution B-1 of 40 mass parts is added among the cellulose acetate solution A of 477 mass parts, fully stirs the preparation dope.From being cooled to the casting die casting dope of 0 ℃ drum barrel top.The solvent of peeling off formation from drum barrel reaches the film of 70 quality %, under film edge, carry out drying by peg type stenter (JP-A-4-1009's is shown in Figure 3) fixed width direction, keep this distance simultaneously, make that laterally the extensibility of (perpendicular to machine direction) reaches 3% when solvent arrives 3-5 quality %.Subsequently, by the further desciccator diaphragm of conveying between the roller in being installed in annealing device, thereby make the polarization board protective film 1 that thickness is 80 μ m.

Use automatic birefringence measurement instrument (KOBRA-21ADH, Oji Scientific Instruments makes), measure the Re correlativity of the film of formation like this, and calculate the optical characteristics of membrane angle of light.Based on this calculating, determine that Re is 1nm, Rth is 6nm.

(the making polarizer)

Use polyvinyl alcohol (PVA) type bonding agent that optical compensation films (KH-01～KH-04, and KH-H1) is stacked on the light polarizing film, its state is to abut against on the light polarizing film on transparent support side.In addition, antagonistic reflex film (Ltd. makes for Fiji Film CV Clear View UA, Fuji Photo Film Co.) carries out saponification to be handled, and uses polyvinyl alcohol (PVA) type bonding agent to be stacked to the opposition side of light polarizing film then.

The thick tri acetyl cellulose film of commercially available 80 μ m (Ltd. makes for TD-80U, Fuji Photo Film Co.) is carried out saponification handle, use polyvinyl alcohol (PVA) type bonding agent to be stacked to the opposition side of light polarizing film then.

Arrange light polarizing film, transparent supporting body and commercially available tri acetyl cellulose film, make their length direction parallel to each other.In this way, make the polarizer (polaroid 1) with optical compensation.

In addition; the polarization board protective film 1 that uses polyvinyl alcohol (PVA) type bonding agent will carry out the saponification processing is stacked to light polarizing film one side; use the commercially available 80 μ ms thick tri acetyl cellulose film (TD-80U of polyvinyl alcohol (PVA) type bonding agent with saponification in advance; Fuji Photo Film Co., Ltd. makes) be stacked to the opposite side of light polarizing film.

Arrange light polarizing film, transparent supporting body and commercially available tri acetyl cellulose film, make their length direction parallel to each other.In this way, make the polarizer (polaroid 2) with optical compensation films and anti-reflective film.

Each polarizer that forms in by combination embodiment and cellulose acylate film make film be positioned on the inboard polaroid for preparing of the polarizer; use spectrophotometer (UV3100PC), measure veneer transmissivity TT, parallel transmissivity PT and the intersection transmissivity CT of 380～780nm wavelength zone under 25 ℃ and 60%RH condition.From these are measured, determine its mean value and the degree of polarization P of 400～700nm wavelength zone.Consequently, TT is 40.8～44.7, and PT is 34～38.8, CT be 1.0 or below, P is 99.98～99.99.In addition, the intersection transmissivity CT (380) under wavelength 380nm, 410nm and the 700nm, CT (410) and CT (800) be respectively 1.0 following 0.5 or following and 0.3 or below.In addition, under 60 ℃ and 95%RH condition in 500 hours the endurancing, all polaroids drop on-scope of 0.1≤Δ CT≤0.2 and-2.0≤Δ P≤≤ 0 in, and in the endurancing under 60 ℃ and the 90%RH, they drop on-scope of 0.05≤Δ CT≤0.15 and-1.5≤Δ P≤0 in.

A part of former state of polaroid 1 and 2 (shown in Figure 2 with the incorporate polaroid of optical compensation films no functional membrane) is kept in the damp proof bag, and another part carries out moisture content control in 2 hours under 25 ℃ and 60%RH, be kept at then in damp proof bag.Damp proof bag is the wrappage of being made by polyethylene terephthalate, aluminium and poly lamination, and its moisture content perviousness is 0.01mg/m ²(24 hours).

The brilliant unit of＜making IPS mode liquid crystal 〉

As shown in Figure 1, electrode (2 among Fig. 1 and 3) places on a slice glass substrate, makes that the distance between adjacent electrode remains 20 μ m.Polyimide film is set thereon, and carries out friction treatment with the preparation alignment films.Carry out friction treatment by direction shown in Figure 14.Prepare another alignment films by polyimide film being set and carrying out friction treatment on a side of another sheet glass substrate.Pile up this two glass substrates, make alignment films face with each other, the gap (d) between two sheet glass substrates remains on 3.9 μ m, and their frictional direction is parallel, and bonded to one another.Wherein sealed refractive index anisotropy (Δ n) and be 0.0769, dielectric constant anisotropy (Δ ε) is+4.5 nematic phase liquid crystal composition.The value d Δ n of liquid crystal layer is 300nm.

(making LCD)

On a side of the brilliant unit of IPS mode liquid crystal; pile up polaroid 1; make frictional direction that the slow axis of cellulose acylate film is parallel to liquid crystal cell (promptly; in the black liquid crystal cell that shows; the slow axis of cellulose acylate film is parallel to the slow axis of liquid crystal liquid crystal property molecule); in addition, bar-shaped compound layer is positioned at the liquid crystal cell side.

Then, on the opposite side of the brilliant unit of IPS mode liquid crystal (1 among Fig. 1), pile up polaroid 2, make its polarization board protective film 1 side to the liquid crystal cell side, in addition,

polaroid

1 and 2 is in the cross-polarized light state to be arranged, thereby makes LCD.Check the light leak of the LCD that makes like this.Under all situations that uses film KH-01～04 and KH-H1, when when 60 ° the direction of being tilted to the left is observed, light leak be 0.1% or below.

On the other hand, do not using under the situation of optical compensation films, light leak is 0.6%.

In addition, after preserving for 1 week respectively under 25 ℃-80%RH condition and the 25 ℃-10%RH condition, check the LCD of using KH-01 and the viewing angle characteristic that uses the LCD of KH-H1.

(evaluation of LCD)

The 55Hz square-wave voltage is applied on the liquid crystal cell.When normally deceiving pattern, black demonstration is arranged on 0V, and white the demonstration is arranged on 7V.Transmittance (the white demonstration/black the demonstration) is spent ratio as a comparison, measures from black show (L1) to the white 8 stage visual angles that show (L8).In addition, also measure positive contrast (CR: white display brightness/black display brightness).

Gained the results are shown in table 1-3.

Table 1-3

Embodiment 2

1. formation cellulose acylate film

(1) cellulose acylate

The cellulose acylate of the different acyl degree of substitution shown in the preparation table 2-1.More specifically, except carboxylic acid, also add sulfuric acid (7.8 mass parts/100 mass parts celluloses) and, under 40 ℃, carry out acylation reaction as catalyzer.Subsequently, by control sulfuric acid catalysis agent content, liquid water content and curing time, regulate total degree of substitution and 6-position degree of substitution.Under 40 ℃, carry out slaking.In addition, the low molecular weight compositions in the cellulose acylate that obtains with the acetone flush away.

(2) dope preparation

Under agitation in each cellulose acylate shown in the table 2-1; add plastifier (2: 1 potpourris of Triphenyl phosphate and phosphoric acid xenyl diphenyl), have below shown in the delay of structure express agent and mixed solvent; or (87: 13 mass ratioes) potpourri of methylene chloride, the potpourri total solid concentration that makes generation is 19 quality %.Heating continues to stir down, preparation solution.Simultaneously; fine particle (silicon dioxide (primary particle size: 20nm) with 0.05 mass parts; about 7), (TINUVIN 327 for 0.375 mass parts ultraviolet light absorber B Mohr ' s hardness:; Ciba SpecialtyChemicals makes) and 0.75 mass parts ultraviolet light absorber C (TINUVIN 328; CibaSpecialty Chemicals makes) be added in each cellulose acylate of 100 mass parts, heating is stirred down.The adding ratio that agent is expressed in plastifier and delay is shown in table 1, represents with the mass parts in the cellulose acylate of per 100 mass parts.From the dope of preparation, form film F1～F10 and F14～F17 according to following method.

Postpone to express agent

Stir down; with plastifier (2: 1 potpourris of Triphenyl phosphate and phosphoric acid xenyl diphenyl), on show structure delay expressed agent and methyl acetate, acetone, ethanol and butanols 81: 8: 7: the potpourri of 4 mass ratioes is added among the cellulose acylate CA3 shown in the table 1; making the potpourri total solid concentration is 16.4 quality %, thereby makes the cellulose acylate swelling.Simultaneously; stir down the fine particle of 0.05 mass parts [silicon dioxide (primary particle size: 20nm, Mohr ' s hardness: about 7)] and the ETHYL CTTRATE (1: 1 potpourri of citric acid mono ethyl ester and citric acid diethylester) of 0.04 mass parts are added in the cellulose acylate of 100 mass parts.The adding ratio that agent is expressed in plastifier and delay is shown in table 1, represents with the mass parts in the cellulose acylate of per 100 mass parts.The solution of swelling is cooled to-70 ℃, is heated to 40 ℃ of fusions then.Filter the dope that obtains like this, concentrate fast by being heated to 120 ℃, the solid concentration in dope is adjusted to about 21%.From the dope of such preparation, form film F11～F13 according to following method.

(fluid casting)

Each dope fluid casts on the band casting machine.When amount of residual solvent reduces to 25～35 quality %, from each film that strips such formation, and use stenter extensibility (referring to table 2-2) with 15%～23% on Width to stretch, thereby form cellulose acylate film.In stenter, in the Width stretched film, use heated-air drying simultaneously, shrink about 5% then.Subsequently, stenter is carried and made the roller conveying into, and is further dry, carries out annular knurl, batches then.Film width of measuring from the stenter porch and the film width of measuring from the stenter outlet calculate extensibility, are shown in table 2-2.On each cellulose acylate film (optical compensation films) that forms like this, at Re length of delay and the Rth length of delay measured under the 25 ℃-60%RH under the wavelength 550nm.In addition, each film of humidity regulation was measured the Re length of delay and the Rth length of delay of each film after at least 2 hours under 25 ℃ of following 10%RH or 80%RH, was clipped between two sheet glass by silicones then, further sealing.In each cellulose acylate film; the Re amount of delay Re (10%RH) that humidity causes when 80%RH changes to 10%RH-Re (80%RH); Rth amount of delay Rth (the 10%RH)-Rth (80%RH) that causes when 80%RH changes to 10%RH with humidity is shown in table 2-2, is expressed as Δ Re and Δ Rth respectively.

Table 2-1

Table 2-2

No.?

Cotton

Plasticizer loading

Express agent content

Draw ratio (%)

The stenter temperature (℃)

Dry film thickness (μ m)

Re (nm)

Rth (nm)

ΔRe?

?ΔRth?

Water content (%)

The moisture content perviousness

Tg (℃)?

F1?

CA1?

11.7?

4.0?

23?

135?

92?

51?

130?

11?

?29?

2.96?

850?

143?

F2?

CA2?

11.7?

5.0?

18?

135?

92?

40?

205?

10?

?29?

2.94?

854?

143?

F3?

CA3?

11.7?

0.0?

20?

140?

92?

16?

114?

12?

?41?

3.36?

1500?

145?

F4?

CA3?

11.7?

4.5?

22?

135?

92?

45?

200?

8?

?28?

2.96?

1144?

142?

F5?

CA3?

11.7?

6.0?

25?

135?

92?

80?

220?

7?

?27?

2.95?

867?

142?

F6?

CA3?

11.7?

5.5?

17?

135?

88?

38?

175?

5?

?23?

2.95?

1037?

142?

F7?

CA3?

11.7?

7.5?

15?

145?

92?

68?

274?

8?

?29?

2.95?

1444?

147?

F8?

CA3?

11.7?

6.2?

18?

145?

80?

40?

180?

8?

?18?

2.95?

1190?

142?

F9?

CA3?

11.7?

7.5?

15?

130?

92?

75?

250?

9?

?27?

2.95?

1035?

142?

F10?

CA3?

11.7?

4.0?

23?

135?

60?

48?

132?

7?

?25?

2.96?

1689?

142?

F11?

CA3?

11.7?

0.0?

20?

135?

80?

17?

155?

10?

?44?

3.36?

1725?

145?

F12?

CA3?

11.7?

5.0?

22?

135?

86?

58?

275?

10?

?28?

2.96?

1265?

142?

F13?

CA3?

11.7?

6.5?

20?

135?

110?

80?

298?

11?

?27?

2.95?

954?

142?

F14?

CA4?

11.7?

5.0?

20?

135?

92?

51?

274?

9?

?28?

3.17?

1127?

142?

F15?

CA5?

11.7?

5.0?

20?

135?

92?

52?

277?

9?

?31?

3.18?

1130?

142?

F16?

CA6?

11.7?

5.0?

20?

135?

80?

55?

121?

9?

?26?

2.346?

1420?

138?

F17?

CA7?

11.7?

4.0?

15?

135?

92?

40?

180?

9?

?40?

3.2?

1136?

141?

In addition, each film that forms is measured glass transition temperature (Tg), the water content after moisture is regulated under 25 ℃ and 80%RH and at 60 ℃, the moisture content perviousness under 95%RH and the 24 hours conditions, the measured value that obtains also is shown in table 2.Its haze value of all these films is 0.1～0.9, and the mean diameter of used matting agent secondary is 1.0 μ m, tensile modulus of elasticity be 4Gpa or more than, the mass change that left standstill 48 hours under the condition of 80 ℃ and 90%RH is 0～3%.In addition, left standstill 24 hours under the condition of 60 ℃ and 95%RH and condition at 90 ℃ and 5%RH under leave standstill 24 hours after, change in size is 0～4.5%.In addition, the photoelastic coefficient of each sample film is 50 * 10 ^-13Cm ²/ dyne or following.

By forming other films,, be 1.3 times and 1.6 times of the dry thickness of F13 except dry thickness becomes 143 μ m and 176 μ m respectively with the blooming F13 same way as shown in the table 2.Can confirm that from these films roughly the Re of proportional increase and Rth value and thickness almost are inversely proportional to thickness and moisture content perviousness.The humidity correlativity of Re and Rth, i.e. Δ Re and Δ Rth, glass transition temperature Tg and water content, all irrelevant with thickness, each film all has identical value about each of these factors.

Each cellulose acylate film (F1～F17) with 1.0N potassium hydroxide solution (solvent: water/isopropyl alcohol/propylene glycol=69.2 mass parts/15 mass parts/15.8 mass parts) with 10cc/m ²In band contact side coating, aqueous slkali remains on film last 30 second under about 40 ℃ of temperature.Then, remove solution,, further remove water droplet with air knife with pure water washing film surface.Subsequently, following dry 15 seconds at 100 ℃.The contact angle on pure water and alkali treatment surface is 42 °.

(formation of alignment films)

(on each alkali treatment surface of F1～F17), use #16 line bar spreader at cellulose acylate film with 2.8ml/m ²Amount coating have the coating solution that is used to form alignment films of following composition.Then, the solution of coating is used 90 ℃ of heated-air dryings 150 seconds again with 60 ℃ of heated-air dryings 60 seconds, thereby forms alignment films.

The coating solution that alignment films is used is formed:

Under show modified polyethylene alcohol 10 mass parts

Water 371 mass parts

Methyl alcohol 119 mass parts

Glutaraldehyde (crosslinking chemical) 0.5 mass parts

Citrate (Ltd. makes for AS3, Sankyo Chemical Co.)

0.35 mass parts

Modified polyethylene alcohol

(friction treatment)

When each transparent supporting body that has the alignment films that forms in the above described manner on it is carried with speed 20m/min, utilize friction roller (measuring diameter 300mm) to make the alignment layer surface generation friction treatment that is formed on the transparent supporting body, friction roller is configured to make friction treatment to carry out with the angle at 45 with respect to length direction, and rotates with 650rpm.Here, the contact length between friction roller and the transparent supporting body is set to 18mm.

(formation of optical anisotropic layer)

The discoid liquid crystal compounds that in the 102Kg methyl ethyl ketone, shows under the dissolving 41.01Kg, 4.06Kg the trimethylolpropane triacrylate (V#360 of oxirane modification, OsakaOrganic Chemical Industry Ltd. makes), 0.35Kg cellulose acetate butyric ester (CAB531-1, Eastman Chemical Company makes), 1.35Kg (Irgacure 907 for Photoepolymerizationinitiater initiater, Ciba Geigy AG makes) and 0.45Kg photosensitizer (KAYACUREDETX, Nippon Kayaku Co., Ltd. makes).In the solution that obtains, add 0.1Kg and contain the multipolymer (Incorporated makes for Megafac F780, Dainippon Ink andChemicals) of the aliphatic group of fluoridizing, thereby prepare coating solution.Use, is applied to the coating solution for preparing like this on the surface of the alignment films on each transparent supporting body of carrying with speed 20m/min at the #3.2 line bar that the equidirectional with the film direction of the supply rotates continuously with the 391rpm rotating speed.

Discoid liquid crystal compounds:

From room temperature to 100 ℃ heating continuously down, dry removing desolvated, and then each film delivered to 130 ℃ of dry sections.In dry section, each film heated about 90 seconds, and condition is that the film surface wind speed in the discoid laminar surface of optical anisotropy is adjusted to 2.5m/sec, thereby makes the molecular orientation of discoid liquid crystal compounds.Next, the film that obtains is delivered to 80 ℃ of dry sections, surface temperature is about 100 ℃, use ultraviolet lamp (UV-lamp of output 160W/cm and emission length 1.6m), shine with the ultraviolet ray that illumination 600mW carried out 4 seconds, thereby carry out cross-linking reaction, the alignment state of discoid liquid crystal compounds molecule is fixed.Subsequently, each film cool to room temperature forms volume by twining on cylinder.Therefore, form scroll optical compensation films (KH-01～17).

The viscosity of each optical anisotropic film that records under 127 ℃ of film-surface temperatures is 695cp.This viscosity number is to use hot type rotary viscosity measuring and optical anisotropic layer to have the result of the liquid crystal layer (remove and desolvate) of same composition.

Downcut part preparation sample by optical compensation films, and measure the optical characteristics of these samples from such formation.When measuring under wavelength 546nm, the Re length of delay of optical anisotropic layer is 380nm.The angle (pitch angle) that the disc face of the discoid liquid crystal compounds in the optical anisotropic layer and supporting body surface form changes continuously with the depth direction of layer, and average slope angle is 28 °.In addition, only peel off optical anisotropic layer from each sample.In measuring optical anisotropic layer, during the mean direction of molecule axis of symmetry, find the mean direction angle at 45 with respect to the length direction of optical compensation films.

(the making polarizer)

Use polyvinyl alcohol (PVA) type bonding agent that each optical compensation films (KH-06, KH-08 and KH-17) is stacked on the light polarizing film, its state is the light polarizing film in abutting connection with the transparent support side.In addition, the thick tri acetyl cellulose film of commercially available 80 μ m (Ltd. makes for TD-80U, Fuji Photo Film Co.) is carried out saponification handle, use polyvinyl alcohol (PVA) type bonding agent to be stacked to the opposite side of light polarizing film then.

Arrange light polarizing film, transparent supporting body and commercially available tri acetyl cellulose film, make their length direction parallel to each other.In this way, make the polarizer with different optical compensate film.

In addition, use polyvinyl alcohol (PVA) type bonding agent each optical compensation films to be stacked on the side of light polarizing film, its state is the light polarizing film in abutting connection with the transparent support side.In addition, antagonistic reflex film (Ltd. makes for Fiji FilmCV Clear View UA, Fuji Photo Film Co.) carries out saponification to be handled, and uses polyvinyl alcohol (PVA) type bonding agent to be stacked to the opposite side of light polarizing film then.

Arrange light polarizing film, transparent supporting body and commercially available tri acetyl cellulose film, make their length direction parallel to each other.In this way, make the polarizer with optical compensation films and anti-reflective film.

Making film on the inboard polaroid for preparing of the polarizer by making up the cellulose acylate film that forms among each polarizer and the embodiment; use spectrophotometer (UV3100PC), measure veneer transmissivity TT, the parallel transmissivity PT of 380～780nm wavelength zone under 25 ℃-60%RH condition and the transmissivity CT that intersects.From these measured values, measure the mean value and the degree of polarization P of 400～700nm wavelength zone.Consequently, TT is 40.8～44.7, and PT is 34～38.8, CT be 1.0 or below, degree of polarization P is 99.98～99.99.In addition, the intersection transmissivity CT (380) under wavelength 380nm, 410nm and the 700nm, CT (410) and CT (800) be respectively 1.0 or below, 0.5 or following and 0.3 or below.In addition, under 60 ℃-95%RH condition in 500 hours the endurancing, all polaroids drop on-scope of 0.1≤Δ CT≤0.2 and-2.0≤Δ P≤0 in, in the endurancing under 60 ℃-90%RH, they drop on-0.05≤Δ CT≤0.15 and-1.5≤≤ scope of Δ P≤0 in.

A part of former state of polaroid A1～A17 is kept in the damp proof bag, and another part carries out moisture content control in 2 hours under 25 ℃ and 60%RH, be kept at then in the damp proof bag.Damp proof bag is the wrappage of being made by polyethylene terephthalate, aluminium and poly lamination, and its moisture content perviousness is 0.01mg/m ²(24 hours).

＜making curved orientation liquid crystal cell 〉

On glass substrate, polyimide film is set, and carries out friction treatment with the preparation alignment films with ITO electrode.Pile up two glass substrates making like this, make alignment films face with each other, their frictional direction is parallel, and brilliant first gap (d) is set to 4.5 μ m.Injection Δ n is 0.1396 liquid-crystal compounds (Japan makes for ZLI1132, Merck Ltd.) in the first gap of crystalline substance, thereby makes the curved orientation liquid crystal cell.The liquid crystal cell diagonal distance is 20 inches.

In the brilliant unit of the curved orientation that makes, pile up the polarizer with optical compensation films (separately) and the polarizer that has optical compensation films and anti-reflective film simultaneously, make brilliant unit be clipped between the polarizer.Here, the polarizer that has optical compensation films and anti-reflective film simultaneously places the observation side.The optical anisotropic layer of the polarizer is in the face of brilliant first substrate, configuration liquid crystal cell and make their frictional direction antiparallel in the face of the optical anisotropic layer of liquid crystal cell.

(evaluation of LCD)

The 55Hz square-wave voltage is applied on the liquid crystal cell.The white demonstration is arranged on 2V, and black demonstration is arranged on 5V.Transmittance (the white demonstration/black the demonstration) is spent ratio as a comparison, measures from black show (L1) to the white 8 stage visual angles that show (L8).In addition, also measure positive contrast (CR: white display brightness/black display brightness).

In addition, after preserving for 1 week respectively under 25 ℃-80%RH condition and the 25 ℃-10%RH condition, check the viewing angle characteristic of LCD.

Gained the results are shown in table 2-3.

Table 2-3

Those skilled in the art obviously can make various modifications and variations to embodiment of the present invention in the spirit or scope of the present invention.Therefore, the invention is intended to comprise and claims and consistent all modifications of the present invention and the variation of its equivalent.

The application requires the Japanese patent application No.JP2005-81401 of submission on March 22nd, 2005 and the foreign priority of JP2005-82211, is incorporated herein by reference in this content with them.

Claims

1. LCD comprises: liquid crystal cell and optical compensation films,

Wherein said liquid crystal cell is the IPS pattern,

Described optical compensation films comprises:

Cellulose acylate film:

The optical anisotropic layer that comprises liquid crystal compounds, wherein said liquid crystal compounds is the rod shaped liquid crystal compound, and the molecule of described rod shaped liquid crystal compound is in perpendicular direction orientation and be fixed on alignment state, wherein " perpendicular " refers to that the film surface and the angle of the direction formation of rod shaped liquid crystal compound are 70 °～90 °

Wherein said cellulose acylate film comprises the cellulose with glucose unit, and the acyl group that the hydroxyl of described glucose unit is had at least two carbon atoms replaces, and described cellulose acylate film satisfies relation (I) and (II):

(I)：2.0≤DS2+DS3+DS6≤3.0

(II)：DS6/(DS2+DS3+DS6)≥0.315

Wherein DS2 represents the degree of substitution of acyl group to glucose unit 2-position hydroxyl, and DS3 represents the degree of substitution of acyl group to glucose unit 3-position hydroxyl, and DS6 represents the degree of substitution of acyl group to glucose unit 6-position hydroxyl, and

The Re of wherein said cellulose acylate film (550) value is 20nm～150nm; Rth (550)/Re (550) is than being 1.5～7; and the Re of described optical anisotropic layer (550) value is 0nm～10nm; Rth (550) value for-80nm～-400nm; wherein Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm.

2. LCD as claimed in claim 1, wherein said cellulose acylate film contain the delay that comprises one of bar-shaped compound and discoid compound expresses agent.

3. LCD as claimed in claim 1, it is under 25 ℃-10%RH and 25 °-80%RH condition, the difference DELTA Re of its length of delay Re (550), promptly, Re10%RH-Re80%RH, be 12nm or following, and under 25 ℃-10%RH and 25 °-80%RH condition, its length of delay Rth (550) difference DELTA Rth, that is, Rth10%RH-Rth80%RH is below 32nm, wherein Re (λ) is a length of delay in the face of representing with the nm of unit under the wavelength X nm, and Rth (λ) is the thickness direction retardation value of representing with the nm of unit under the wavelength X nm.

4. LCD as claimed in claim 1 also comprises polaroid, and described polaroid comprises the polarizer and described optical compensation films.