CN101019051A - Cellulose acylate film, polarizing plate, and liquid crystal display - Google Patents

Abstract

A cellulose acylate film for optics having an in-plane retardation Re (lambada) of 46 <= Re (630) <= 200, a retardation in a film thickness direction Rth (lambada) of 70 <= Rth (630) <= 350 and a thickness variation between every 10 mm in a breadth direction of 0.6 m or less.

Description

Cellulose acylate film, polaroid and LCD

Technical field

The present invention relates to a kind of cellulose acylate film, and polaroid and the LCD of using this film.

Background technology

LCD is because of various advantages, for example, and low-voltage, low energy consumption, and can miniaturization and thinning, therefore be widely used as the monitor of PC and portable equipment, and be used for televisor.Although from following matrix upward the matrix TN pattern of reversing about 90 ° ordered state become main flow, the LCD of various patterns has been proposed by the state of arranging liquid crystal in liquid crystal cell.

LCD is made up of liquid crystal cell, optical compensating gage and polarizer usually.Use optical compensating gage to wipe color of image and enlarge the visual angle, and will be coated with the birefringent film of stretching of liquid crystal and transparent membrane as this optical compensating gage.For example; a kind of technology that enlarges the visual angle by coating one optical compensating film on TN type liquid crystal cell is disclosed in the Jap.P. 2587398; this optical compensating film is by being coated with discotic mesogenic on the tri acetyl cellulose film, through orientation and fixing form.Yet, watch from all angles the LCD that the TV of the big plane of delineation uses in supposition, strict to view angle dependency, even this technology can not satisfy this requirement.Therefore, study the LCD different with the TN type always, for example, IPS (face internal conversion) type, OCB (optical compensation curved) type, VA (vertical orientated) type etc.Specifically, the contrast height and the productive rate of VA type are high relatively, and cause the public's attention as the LCD that TV is used.

Compare with other thin polymer film, cellulose acylate film is characterised in that its optical isotropy height (length of delay is low).Therefore, often cellulose acetate film is used for the high optically isotropic purposes of needs, for example, polaroid.(term used herein " JP-A " is meant " examine disclosed Japanese patent application ") discloses a kind of viscometric degree of polymerization and the relation of the dope that obtains with dissolving cellulos acetic acid esters cellulose acetate film method of preparing the few highly transparent of insoluble matter thereof by the regulation cellulose ethanoate in JP-A-2000-131524.In order to solve the surface imperfection of so-called mould striped (die streak), the preference relation between the viscosity p of the solid concentration y (%) of film forming solution of thickness d, cellulose acetate film of cellulose acetate film and this solution is disclosed in JP-A-2001-129838.

On the other hand, require the optical compensating gage (phase film) of LCD to have optical anisotropy (high retardation value).Specifically, in the optical compensating gage of VA type, require to postpone in the face (Re) and be 30-200nm, and the delay of thickness direction (Rth) is 70-400nm.Therefore, usually use have high retardation value the synthetic polymer film for example polycarbonate film and polysulphone film as optical compensating film.

As mentioned above, in the technical field of optical material, rule is to use the synthetic polymer film when needs optical anisotropy (high retardation value), uses cellulose acetate film when needs optical isotropy (low length of delay).

Opposite with rule, in EP 911656, disclose and also can be used for the optically anisotropic cellulose acetate film of needs with high retardation value.In the document, in order in cellulose ethanoate, to realize high retardation value, stretch with aromatic with at least two aromatic rings, particularly have the compound of 1,3,5-triazines ring by interpolation.

Cellulose ethanoate normally is difficult to the polymeric material that stretches, and knownly is difficult to make the birefraction height.Yet the document realizes high retardation value by adjuvant is orientated, and can make the birefraction height.The advantage of this film is the protective film that it can the double as polaroid, can provide inexpensive and thin LCD like this.

The advantage of disclosed method is the LCD that can provide inexpensive and thin in the top document.Yet in recent years, the length of delay of having relatively high expectations must increase the addition that postpones dose like this and improve draw ratio.Be accompanied by this trend, in curtain coating process and drawing process, present the striped inhomogeneity that is called vertical stripes of extending in the curtain coating direction, and and if only if bright spot that is comprised that presents when being assemblied in this film in the LCD and brightness and tone inhomogeneity become problem now because of the variation in thickness of Width.Particularly, be offset-1 ° to+1 ° in its maximal value with the position at Width and length direction optical axis at the cellulose acylate film that is used for the large scale liquid crystal televisor.

And optical axis is easy in the process that cellulose acylate film is assembled into polaroid or appearance when adhering to two polaroids on the liquid crystal cell for about 1 ° in its maximal value skew.When the skew of the optical axis of the polarization film optical axis between the skew of the optical axis of cellulose acylate film and two polaroids became big, the light leak during black display was obvious.When film thickness at the Width of cellulose acylate film during with narrow interval variation, light shaft offset is big more, the fuzzy uneven luminance that is observed visually when observing with big image surface is obvious more, even the absolute value of the variation of film thickness is little.Therefore, wish to solve this surface heterogeneity.And image surface is big more, if do not reduce the frequency of occurrences of bright spot inclusion, the productive rate of polaroid and LCD is low more and production cost is high more so.Therefore, this respect also needs to improve.

Summary of the invention

First aspect of the present invention provides in a kind of and the increase excellent performance of the delay of thickness direction, the little cellulose acylate film of variation in thickness of Width, and a kind of polaroid that uses this film is provided.

Second aspect of the present invention provides a kind of bright spot inclusion and surface heterogeneity is not obvious and visual angle change is little LCD.

The 3rd aspect of the present invention provides the little cellulose acylate film of variation that a kind of optical characteristics changes with ambient humidity, and provides a kind of tonal variation to change little LCD with ambient humidity.

Several aspects realize by following method above of the present invention.

(1) a kind of optics cellulose acylate film; has the delay Rth (λ) that postpones the film thickness direction of Re (λ), 70≤Rth (630)≤350 in the face of 46≤Re (630)≤200; and Width is 0.6 μ m or littler every the variation in thickness of 10mm; wherein Re (λ) postpones the Re value (unit: nm), Rth (λ) is the delay Rth value (unit: nm) of film thickness direction under the wavelength X nm in the face under the wavelength X nm.

(2) as top (1) described cellulose acylate film, it is to obtain by the dope that 33 ℃ of following viscosity coefficients of curtain coating are 10-70Pas.

(3) as top (1) or (2) described cellulose acylate film,

Wherein the degree of polymerization of cellulose acylate is 265-380.

(4) as any described cellulose acylate film in top (1) to (3),

Wherein the bulk density of cellulose acylate is 0.30-0.80.

(5) as any described cellulose acylate film in top (1) to (4); it is the film that comprises with cellulose acylate; the hydroxyl that the acyl substituted that described cellulose acylate has two or more carbon atoms constitutes cellulosic glucose unit obtains

Wherein this film satisfies equation (I) and (II):

2.0≤DS2+DS3+DS6≤2.85 (I)

DS6/(DS2+DS3+DS6)≥0.315 (II)

Wherein DS2 represents the degree of substitution with the hydroxyl on the 2-position of acyl substituted glucose unit;

The DS3 representative degree of substitution of the hydroxyl on the acyl substituted 3-position; With

The DS6 representative degree of substitution of the hydroxyl on the acyl substituted 6-position.

(6) as any described cellulose acylate film in top (1) to (5), it comprises at least a delay dose that contains bar-shaped or cylindrical compound.

(7) as any described cellulose acylate film in top (1) to (6), it comprises plastifier, ultraviolet light absorber and peels off at least a in the promoter.

(8) as any described cellulose acylate film in top (1) to (7),

Wherein the thickness of film is 40-180 μ m.

(9) as any described cellulose acylate film in top (1) to (8),

Wherein based on the film gross mass, the content of additive that joins in the cellulose acylate is 10 quality % or bigger to 30 quality % or littler.

(10) as any described cellulose acylate film in top (1) to (9),

Wherein the difference Δ Re (=Re 10%RH-Re 80%RH) of Re (Re 80%RH) value of film under (Re 10%RH) value of the Re under 25 ℃ of 10%RH and 25 ℃ of 80%RH is 12nm or littler, and the difference Δ Rth (=Rth 10%RH-Rth80%RH) of Rth (Rth 80%RH) value under Rth (Rth 10%RH) value under 25 ℃ of 10%RH and the 25 ℃ of 80%RH is 32nm or littler.

(11) as any described cellulose acylate film in top (1) to (10),

Wherein the equilibrium moisture content of film under 25 ℃ of 80%RH is 3.4% or littler.

(12) as any described cellulose acylate film in top (1) to (11),

Seepage rate (based on the thickness of 80 μ m) after wherein film leaves standstill 24 hours under 60 ℃ of 95%RH is 400-2,300g/m ²24hr.

(13) as any described cellulose acylate film in top (1) to (12),

Wherein film is 0-5% in the mass change that leaves standstill under 80 ℃ of 90%RH under 48 hours the situation.

(14) as any described cellulose acylate film in top (1) to (13),

Wherein film is leaving standstill under 24 hours the situation and is leaving standstill change in size under 24 hours the situation under 90 ℃ of 3%RH all within ± 2% under 60 ℃ of 90%RH.

(15) as any described cellulose acylate film in top (1) to (14),

Wherein glass temperature Tg is 80-180 ℃.

(16) as any described cellulose acylate film in top (1) to (15),

Its Elastic Modulus is 1,500-5,000MPa.

(17) as any described cellulose acylate film in top (1) to (16),

Wherein the photoelasticity modulus is 50 * 10 ^-13Cm ²/ dyn (5 * 10 ^-11Pa-1) or littler.

(18) as any described cellulose acylate film in top (1) to (17),

Wherein haze value is 0.01-2%.

(19) as any described cellulose acylate film in top (1) to (18), it comprises that the mean grain size of secondary granule is 0.2 μ m or bigger to 1.5 μ m or littler fine particles of silica.

(20) as any described cellulose acylate film in top (1) to (19),

Wherein Re that measures under the ambient humidity of 25 ℃ of 60%RH (630) and Rth (630) satisfy equation (A), (B) and (C):

46≤Re(630)≤100 (A)

Rth(630)＝a-5.9Re(630)(B)

520≤a≤600 (C)。

(21) as any described cellulose acylate film in top (1) to (20),

Wherein Re value by changing wavelength measurement and Rth value satisfy equation (D) and (E) under the ambient humidity of 25 ℃ of 60%RH:

0.90≤Re (450)/Re (550)≤1.10 and 0.90≤Re (650)/Re (550)≤1.10 (D)

0.90≤Rth (450)/Rth (550)≤1.25 and 0.90≤Rth (650)/Rth (550)≤

1.10(E)。

(22) as any described cellulose acylate film in top (1) to (21),

Wherein major axis is that 20 μ m or bigger bright spot inclusion number are 20 or still less in any 2.16mm * 1.72mm zone of cellulose acylate film.

(23) a kind of polaroid comprises:

Polarizer; With

Protective film,

Wherein this protective film comprises that at least one is as any described cellulose acylate film in top (1) to (22).

(24) as top (23) described polaroid,

Wherein the independent transmissivity TT (%), the parallel transmissivity PT (%) that under 25 ℃ of 60%RH, measure of this polaroid, intersect transmissivity (cross transmittance) CT (%) and degree of polarization P and satisfy at least a in the equation (a) to (d):

40.0≤TT≤45.0 (a)

30.0≤PT≤40.0 (b)

CT≤2.0 (c)

95.0≤P (d)。

(25) as top (23) or (24) described polaroid,

Wherein CT (380) (%), CT (410) (%) and CT (700) (%) satisfy in the equation (e) to (g) at least aly, prerequisite is that CT (λ) (%) is meant intersection transmissivity under wavelength X:

CT(380)≤2.0 (e)

CT(410)≤0.1 (f)

CT(700)≤0.5 (g)。

(26) as any described polaroid in top (23) to (25), wherein when this polaroid is left standstill 500 hours under 60 ℃ of 90%RH the time, the changes delta CT (%) of intersection transmissivity and the changes delta P of degree of polarization satisfy equation (h) and (i) at least a:

-3.0≤ΔCT≤3.0 (h)

-5.0≤ΔP≤0.0 (i)

Wherein said variation is meant that the measured value after test deducts the test value that measured value obtained before.

(27) as any described polaroid in top (23) to (26), wherein when this polaroid is left standstill 500 hours under 60 ℃ of 95%RH the time, the changes delta CT (%) of intersection transmissivity and the changes delta P of degree of polarization satisfy equation (j) and (k) at least a:

-6.0≤ΔCT≤6.0 (j)

-10.0≤ΔP≤0.0 (k)

Wherein said variation is meant that the measured value after test deducts the test value that measured value obtained before.

(28) as any described polaroid in top (23) to (27), when wherein this polaroid being left standstill 500 hours under 80 ℃, the changes delta P of the changes delta CT of transmissivity and degree of polarization of intersecting satisfy equation (1) and (m) at least a:

-3.0≤ΔCT≤3.0 (1)

-2.0≤ΔP≤0.0 (m)。

(29) as any described polaroid in top (23) to (28), wherein provide the one deck at least in hard conating, anti-dazzle photosphere and the anti-reflecting layer on the protective film surface that on the face relative of polaroid, provides with liquid crystal cell.

(30) as any described polaroid in top (23) to (29), it is packaged in the moisture barrier bag, and the humidity in the bag of 25 ℃ of following packed states is 43%RH to 70%RH.

(31) as any described polaroid in top (23) to (30), it is packaged in the moisture barrier bag, and the difference of humidity in the packed state bag and the humidity when sticking to polaroid on the liquid crystal board is 15%RH or littler.

(32) a kind of OCB type LCD, comprise as top (1) to (22) arbitrarily a described cellulose acylate film and as above (23) to (31) at least a in described polaroid arbitrarily.

(33) a kind of VA type LCD, comprise as top (1) to (22) arbitrarily a described cellulose acylate film and as above (23) to (31) at least a in described polaroid arbitrarily.

(34) a kind of VA type LCD, only comprise as top (1) to (22) arbitrarily a described cellulose acylate film and as above (23) to (31) a kind of in described polaroid arbitrarily.

(35) a kind of VA type LCD, shady face comprise as top (1) to (22) arbitrarily a described cellulose acylate film and as above (23) to (31) a kind of in described polaroid arbitrarily.

Description of drawings

Fig. 1 is the figure that shows the method for the plain acylate film of adhering fibre in the polaroid preparation process;

Fig. 2 is the cross-sectional view that shows the cross-sectional structure of polaroid of the present invention; With

Fig. 3 is the cross-sectional view that shows the cross-sectional structure of LCD of the present invention.

Embodiment

Describe the present invention below in detail.

Cellulose acylate:

At first, detailed description is preferred for cellulose acylate of the present invention.Constitute cellulosic β-1,4-bonding glucose unit in the 2-position, 3-position and 6-position have free hydroxyl.Cellulose acylate is the polymkeric substance that obtains by with part or all of these hydroxyls of the acyl group esterification with two or more carbon atoms.The acyl substituted degree is meant the esterification ratio (100% esterification is a degree of substitution 1) of cellulosic 2-position, 3-position and each hydroxyl of 6-position.

All acyl substituted degree, i.e. DS2+DS3+DS6, preferably 2.00-2.85, more preferably 2.22-2.82, especially preferably 2.40-2.80.And DS6/ (DS2+DS3+DS6) preferably 0.315 or bigger, preferred especially 0.320 or bigger.Here, DS2 is that degree of substitution (this paper back also is referred to as " the acyl substituted degree of 2-position "), DS3 with the hydroxyl on the 2-position of acyl substituted glucose unit are to be with the degree of substitution of the hydroxyl on the acyl substituted 6-position (this paper back also is referred to as " the acyl substituted degree of 6-position ") with the degree of substitution of the hydroxyl on the acyl substituted 3-position (this paper back also is referred to as " the acyl substituted degree of 3-position "), DS6.

The carboxyl groups that is used for cellulose acylate of the present invention can perhaps can use two or more acyl groups only for a kind of.When using two or more acyl groups, preferred a kind of acyl group is an acetyl group.When replacing total degree of substitution of the hydroxyl on 2-position, 3-position and the 6-position as DSA with acetyl group; with total degree of substitution of the hydroxyl on the acyl substituted 2-position except that acetyl group, 3-position and the 6-position during as DSB; the value of DSA+DSB is more preferably 2.2-2.85, preferred especially 2.40-2.80.DSB is 1.70 or littler, preferred especially 1.0 or littler.28 (28) % or bigger DSB are the substituting groups of hydroxyl on the 6-position, more preferably 30% or bigger be the substituting group of hydroxyl on the 6-position, even more preferably 31% or bigger, preferred especially 32% or bigger be the substituting group of hydroxyl on the 6-position.And the value of DSA+DSB is 0.75 or bigger cellulose acylate film on the 6-position of preferred cellulose acylate, more preferably 0.80 or bigger, preferred especially 0.85 or bigger.Have the solubleness excellence of cellulose acylate in all kinds of solvents of this acyl group replacement characteristic, and can obtain to contain hardly the solution of insoluble substance.And, can prepare the solution that viscosity is low and strainability is good.As a result, cellulose acylate film of the present invention contains foreign matter seldom, and the phenomenon of light leak and reflective (being referred to as the bright spot inclusion) can reduce black display and particularly be installed in this film on the LCD time.

The acyl group that is used for three or more carbon atoms of having of cellulose acylate of the present invention can be aliphatic acyl or aryl-acyl, without any restriction.Being used for cellulose acylate of the present invention for example is cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester, aromatic series carbonyl ester or aromatic series alkyl-carbonyl ester, and they can also be substituted.As the preferred embodiment of acyl group, propiono, bytyry, heptanoyl group, caproyl, caprylyl, capryl, 12 carbonic acyl radicals, 13 carbonic acyl radicals, 14 carbonic acyl radicals, 16 carbonic acyl radicals, 18 carbonic acyl radicals, isobutyryl, uncle's bytyry, cyclohexane carbonyl, oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl have been enumerated.In these groups, more preferably propiono, bytyry, 12 carbonic acyl radicals, 18 carbonic acyl radicals, uncle's bytyry, oleoyl, benzoyl, naphthyl carbonyl and cinnamoyl, preferred especially propiono and bytyry.

The synthetic method of cellulose acylate:

Migita etc. are at Mokuzai Kagaku (Wood Chemistry), pp.180-190, and KYORITSU SHUPPAN CO. has described the ultimate principle of the synthetic method of cellulose acylate among the LTD. (1968).The liquid phase acetylation method that a kind of representational synthetic method is carboxylic acid anhydrides-acetate-sulfuric acid catalyst.Particularly, the cellulosic material of velveteen and wood pulp puts it into the carboxylated mixed solution of esterification of precooling with an amount of acetate pre-service, synthetic thus complete cellulose acylate (total acyl substituted degree of 2-position, 3-position and 6-position almost is 3.00).This carboxylated mixed solution contains acetate usually as solvent, contains carboxylic acid anhydrides as esterifying agent and contain sulfuric acid as catalyzer.Usually use stoichiometry than being present in the carboxylic acid anhydrides that treating in this system Duoed with the cellulosic total amount of carboxylic acid anhydrides and water reaction.After acylation reaction finished, () aqueous solution for example, the carbonate of calcium, magnesium, iron, aluminium or zinc, acetate or oxide was stayed excess carboxylic acid in the system and a part of esterification catalyst that neutralizes with hydrolysis to add neutralizing agent.Then; the complete cellulose acylate of gained is kept under the situation that a small amount of acetylization reaction catalyzer (normally remaining sulfuric acid) is arranged in 35-90 ℃ the temperature; carry out slaking by saponification, to become cellulose acylate with required acyl substituted degree and degree of polymerization.When obtaining required cellulose acylate; the catalyzer that to stay in this system with neutralizing agent recited above neutralizes fully; perhaps; without neutralization; come the plain acylate of defibre by cellulose acylate solution being joined (perhaps water or dilute sulfuric acid are put in the cellulose acylate solution) in water or the dilute sulfuric acid, obtain cellulose acylate thus through gathering and precipitation, washing and stabilization processes.

Cellulose acylate film of the present invention preferably consists essentially of has cellulose acylate defined above as the polymers compositions that constitutes this film." basically " be meant 55 quality % or bigger polymers compositions, preferred 70 quality % or bigger, more preferably 80 quality % or bigger.(in this manual, mass parts and quality % equal weight portion and weight % respectively.) as the material of processing film, preferably use cellulose acylate pellet.Preferred 90 quality % or bigger particles used particle diameter with 0.5-5mm.Also preferred 50 quality % or bigger particles used particle diameter with 1-4mm.If possible, cellulose acylate pellet is preferably near spherical.The bulk density of these particles (apparent density) is 0.3-0.8kg/l preferably.If bulk density is little, when this material is easy to take place bridge joint when feed bin is put into solution tank, in contrast, if bulk density is big, solubleness reduces.Therefore, preferred bulk density is 0.4-0.6.When assembling and precipitate, carry out the adjusting of particle diameter and bulk density by regulating stirring and aggregation velocity.When the concentration of cellulose acylate was low when assembling and precipitate, bulk density diminished, and in contrast, if the concentration height of cellulose acylate, it is big that bulk density becomes.

The degree of polymerization that can be used for cellulose acylate of the present invention is the viscometric degree of polymerization of 250-550, and preferred viscometric degree of polymerization is 265-380, especially preferred 280-360.Viscometric degree of polymerization can be measured according to people's such as Uda (Kazuo Uda and Hideo Saito, Sen ' i Gakkaishi (Bulletin of Fiber Institution), Vol.18, No.1, pp.105-120, (1962)) limiting viscosity method.And, in JP-A-9-95538, describe viscometric degree of polymerization in detail.Viscometric degree of polymerization is to be calculated according to equation by the intrinsic viscosity [η] of the cellulose acylate of Ostwald ' s viscosity meter measurement.

Viscometric degree of polymerization DP=[η]/Km

In this equation, [η] is the intrinsic viscosity of cellulose acylate, and Km is a constant 6 * 10 ^-4

The molecular weight distribution mw/mn of cellulose acylate (Mw is that weight-average molecular weight and Mn are number-average molecular weights) can pass through gel permeation chromatography measurement.The invention is characterized in that the viscosity with cellulose acylate solution is adjusted to preferred value.Also the viscosity of cellulose acylate solution can be adjusted to preferred value by adjusting molecular weight distribution.In this, the occurrence of Mw/Mn is 1.8-4.0 preferably, more preferably 2.1-3.5.

The amount of temperature of reaction, reaction time and catalyzer by adjusting acetylization reaction can be adjusted the degree of polymerization and the molecular weight distribution of cellulose acylate.For example, when increasing the amount of sulfuric acid catalyst, the degree of polymerization reduces easily.Therefore, preferably the amount with sulfuric acid catalyst in the cellulose of per 100 mass parts is adjusted to the 0.5-20 mass parts, more preferably the 3-15 mass parts.When in the superincumbent scope of the amount of sulfuric acid catalyst, can synthetic molecular weight distributing also be preferred cellulose acylate.

Temperature when adjusting neutralization and saponification maturation stage saponification slaking, sour surplus, in and speed and moisture, also can adjust the degree of polymerization and the molecular weight distribution of cellulose acylate.For example, when moisture was slowly carried out saponification in low in keeping reaction vessel, because the degraded during saponification is also carried out slowly, so the degree of polymerization reduced.

And, also can adjust the degree of polymerization and molecular weight distribution by removing lower-molecular-weight component.For example, can be by removing lower-molecular-weight component with an amount of organic solvent washing cellulose acylate.

The moisture that is used for cellulose acylate of the present invention is 2 quality % or littler preferably, more preferably 1 quality % or littler, preferred especially 0.7 quality % or littler.In general, cellulose acylate contains moisture, and known be 2.5-5 quality %.In order to reach top moisture, must be with the cellulose acylate drying, and this method has no particular limits, as long as guarantee target moisture content.

The synthetic method of cotton material of the present invention and cellulose acylate is described in detail in Hatsumei Kyokai Kokai Giho Kogi No.2001-1745 (March 15 calendar year 2001 is by Hatsumei Kyokai distribution), pp.7-12.

Adjuvant:

According to purpose; in each preparation process, can in cellulose acylate solution of the present invention, (for example add various adjuvants; plastifier, UV inhibitor, rottenly prevent agent, delay (optical anisotropy) correctives, particulate, peel off promoter, infrared absorbent etc.), and these adjuvants can be solid or oily mater.That is, the fusing point of these adjuvants and boiling point have no particular limits.For example, the potpourri of the potpourri of 20 ℃ or lower and 20 ℃ or higher UV absorbing agent and plastifier is that the example and they are disclosed among JP-A-2001-151901 etc.As the example of peeling off promoter, the ETHYL CTTRATE class is for example arranged.And the example of infrared absorbent is disclosed among the JP-A-2001-194522.These adjuvants can add in any stage of dope preparation process, but they can add by the interpolation process that adjuvant is provided at last in the dope preparation process.The addition of each adjuvant has no particular limits, as long as present its function.And when forming cellulose acylate film with sandwich construction, the type of adjuvant can be different with addition in each layer.The example is disclosed among the JP-A-2001-151902 etc., and they are conventional known technology.Preferably the glass temperature Tg with cellulose acylate film is adjusted to 80-180 ℃, and will be adjusted to 1,500-3,000MPa with the elastic modulus that the tensile strength measuring instrument is measured.

The details of these contents is described in the 6th page of Hatsumei Kyokai Kokai Giho Kogi No.2001-1745 (March 15 calendar year 2001 by Hatsumei Kyokai distribution) and afterwards, and preferably uses wherein said material.

Plastifier:

Film of the present invention preferably contains plastifier.Available plastifier has no particular limits; but preferably be used alone or in combination the plastifier more hydrophobic than cellulose acylate; for example enumerated phosphoric acid ester; for example; triphenyl phosphate; tricresyl phosphate; tricresyl phosphate base-diphenyl; octyl diphenyl phosphate; di(2-ethylhexyl)phosphate phenyl-biphenyl ester; trioctyl phosphate and tributyl phosphate; phthalate; for example; diethyl phthalate; DMEP; repefral; dioctyl phthalate; dibutyl phthalate and di-2-ethylhexyl phthalate; the ethyl glycolate class; for example, triacetin; tributyrin; glycollic acid butyl phthalyl butyl ester; glycollic acid ethyl phthalyl ethyl ester; glycollic acid methyl phthalyl ethyl ester and glycollic acid butyl phthalyl-butyl ester.If necessary, two or more plasticizer combinations can be used.

Postpone dose:

In the present invention, in order to increase length of delay, can preferably use compound as postponing dose with at least two aromatic rings.The preferred delay dose that uses the 0.05-20 mass parts in the polymkeric substance of per 100 mass parts, more preferably 0.1-10 mass parts, even more preferably 0.2-5 mass parts, most preferably 0.5-2 mass parts.Two or more can be postponed dose is used in combination.

Postpone dose and preferably have absorption maximum, and preferably postpone dose in visible region not absorption basically at the wavelength zone of 250-400nm.

In instructions of the present invention, " aromatic rings " comprises aromatic heterocycle and aromatic hydrocarbon ring.

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

Aromatic heterocycle is unsaturated heterocycle normally.Aromatic heterocycle is 5-, 6-or 7-unit ring preferably, more preferably 5-or 6-unit ring.Aromatic heterocycle has the maximum two keys of possibility usually.As heteroatoms, preferred nitrogen atom, oxygen atom and sulphur atom, nitrogen atom.The example of aromatic heterocycle comprises furan nucleus, thiphene ring, pyrrole ring,  azoles ring, different  azoles 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, the 5-triazine ring.

As aromatic rings, preferred phenyl ring, fused benzene rings and xenyl especially preferably use the 1,3,5-triazines ring.Particularly, preferably use disclosed compound among the JP-A-2001-166144.

The carbon atom that postpones the aromatic rings that dose has is 2-20 preferably, more preferably 2-12, even more preferably 2-8, most preferably 2-6.

The bonding of two aromatic rings relation can be divided into the situation that situation that situation that (a) form fused rings, (b) directly link to each other through singly-bound and (c) link to each other through linking group (because they are aromatic rings, so can not form be spirally connected).This bonding relation can be a situation arbitrarily in (a) to (c).

(a) example of fused rings (fused rings of two or more aromatic rings) comprises the indenes ring, naphthalene nucleus, azulenes, the fluorenes ring, phenanthrene ring, anthracene nucleus, the acenaphthene ring, the biphenylene ring, the naphtho-naphthalene nucleus, the pyrene ring, indole ring, the iso-indoles ring, the coumarone ring, the benzothiophene ring, the indolizine ring, the benzoxazol ring, the benzothiazole ring, the benzimidazole ring, the benzotriazole ring, purine ring, the indazole ring, the chromene ring, the quinoline ring, the isoquinoline ring, the quinolizine ring, the quinazoline ring, the cinnolines ring, quinoline  quinoline ring, the phthalazines ring, pteridine ring, the carbazole ring, the acridine ring, the phenanthridines ring, the xanthene ring, the azophenlyene ring, the phenothiazine ring, the fen thiophene oh encircles, fen  piperazine ring and thianthrene ring.In these rings, preferred naphthalene nucleus, azulenes, indole ring, benzoxazol ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring.

(b) singly-bound in is the key between the carbon atom of two aromatic rings preferably.Two aromatic rings can pass through two or more singly bounds, and can form aliphatic series ring or aromatic heterocycle between this aromatic rings.

Also the linking group in preferred (c) links to each other with the carbon atom of two aromatic rings.These linking groups preferably alkylidene, alkenylene, alkynylene ,-CO-,-O-,-NH-,-combination of S-or these groups.The example that shows the linking group that comprises combination below.The left side of the example of following linking group and the relation on the right can be opposite.

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:-alkylidene-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 rings and linking group can have substituting group.

These substituent examples comprise halogen atom (F; Cl; Br; I); hydroxyl; carboxyl; cyano group; amino; nitro; sulfo group; carbamyl; sulfamoyl; urea groups; alkyl; thiazolinyl; alkynyl; aliphatic acyl; the aliphatic series acyloxy; alkoxy; alkoxy carbonyl; alkoxycarbonyl amino; alkylthio group; alkyl sulphonyl; the aliphatic series acylamino-; the aliphatic series sulfonamido; the amino that aliphatic group replaces; the carbamyl that aliphatic group replaces; the sulfamoyl that aliphatic group replaces; urea groups and nonaromatic heterocycles group that aliphatic group replaces.

Alkyl preferably has 1-8 carbon atom.Chain-like alkyl is more preferred than cyclic alkyl, and preferred especially straight chained alkyl.Alkyl can also have substituting group (for example, the amino of hydroxyl, carboxyl, alkoxy, alkyl replacement).The example of alkyl (alkyl that comprises replacement) comprises methyl, ethyl, normal-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxy ethyl and 2-diethylamino ethyl.

Thiazolinyl preferably has 2-8 carbon atom.The chain thiazolinyl is more preferred than ring-type thiazolinyl, and preferred especially straight-chain alkenyl.Thiazolinyl can also have substituting group.The example of thiazolinyl comprises vinyl, allyl and 1-hexenyl.

Alkynyl preferably has 2-8 carbon atom.The chain alkynyl is more preferred than ring-type alkynyl, and preferred especially straight-chain alkynyl.Alkynyl can also have substituting group.The example of alkynyl comprises ethinyl, 1-butynyl and 1-hexin base.

Aliphatic acyl preferably has 1-10 carbon atom.The example of aliphatic acyl comprises acetyl group, propiono and bytyry.

The aliphatic series acyloxy preferably has 1-10 carbon atom.The example of aliphatic series acyloxy comprises acetoxyl group.

Alkoxy preferably has 1-8 carbon atom.Alkoxy can also have substituting group (for example, alkoxy).The example of alkoxy (alkoxy that comprises replacement) comprises methoxyl, ethoxy, butoxy and methoxy ethoxy.

Alkoxy carbonyl preferably has 2-10 carbon atom.The example of alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.

Alkoxycarbonyl amino preferably has 2-10 carbon atom.The example of alkoxycarbonyl amino comprises the amino and ethoxy-carbonylamino of methoxycarbonyl.

Alkylthio group preferably has 1-12 carbon atom.The example of alkylthio group comprises methyl mercapto, ethylmercapto group and hot sulfenyl.

Alkyl sulphonyl preferably has 1-8 carbon atom.The example of alkyl sulphonyl comprises mesyl and ethylsulfonyl.

The aliphatic series acylamino-preferably has 1-10 carbon atom.The example of aliphatic series acylamino-comprises acetylamino.

The aliphatic series sulfonamido preferably has 1-8 carbon atom.The example of aliphatic series sulfonamido comprises methanesulfonamido, fourth sulfonamido and positive hot sulfonamido.

The amino that aliphatic group replaces preferably has 1-10 carbon atom.The example of the amino that aliphatic group replaces comprises dimethylamino, diethylamino and 2-carboxy ethyl amino.

The carbamyl that aliphatic group replaces preferably has 2-10 carbon atom.The example of the carbamyl that aliphatic group replaces comprises methylamino formoxyl and diethylamino formoxyl.

The sulfamoyl that aliphatic group replaces preferably has 1-8 carbon atom.The example of the sulfamoyl that aliphatic group replaces comprises methyl sulfamoyl and diethyl amino sulfonyl.

The urea groups that aliphatic group replaces preferably has 2-10 carbon atom.The example of the urea groups that aliphatic group replaces comprises the methyl urea groups.

The nonaromatic heterocycles examples of groups comprises piperidino and morpholino base.

The molecular weight of delay dose is 300-800 preferably.

Bar-shaped compound with straight-chain molecular structure except the compound with 1,3,5-triazines ring, also is preferred for the present invention.Straight-chain molecular structure is meant that the molecular structure of bar-shaped compound is a straight chain in the stable structure of thermodynamics.The stable structure of thermodynamics can obtain by analyzing crystalline texture or calculating molecular orbit.For example, calculate the molecular structure that forms the heat minimum that molecular orbit can be found compound with Molecular Orbital Calculation software (for example, WinMOPAC2000 is made by Fujitsu Limited).Molecular structure is that straight chain is meant that the angle that is made of the main chain in the molecular structure is 140 ° or bigger in as above by the stable structure of the thermodynamics that calculates.

As bar-shaped compound with at least two aromatic rings, the compound of preferred following formula (1) representative.

Ar ¹-L1-Ar ² (1)

In following formula (1), Ar ¹And Ar ²Represent aromatic group independently of one another.

In instructions of the present invention, aromatic group comprises the aromatic heterocycle group of aryl, aromatic heterocycle group and the replacement of aryl (aryl radical), replacement.

The aryl of aryl and replacement is more preferred than the aromatic heterocycle group of aromatic heterocycle group and replacement.The heterocycle of aromatic heterocycle group is normally undersaturated.Aromatic heterocycle group is 5-, 6-or 7-unit ring preferably, more preferably 5-or 6-unit ring.Aromatic heterocycle group has the maximum two keys of possibility usually.Heteroatoms is nitrogen-atoms, oxygen atom or sulphur atom preferably, is more preferably nitrogen-atoms or sulphur atom.

As the aromatic rings of aromatic group, preferred phenyl ring, furan nucleus, thiphene ring, pyrrole ring,  azoles ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring and pyrazine ring, preferred especially phenyl ring.

Substituent example as the aromatic heterocycle group of aryl that replaces and replacement; halogen atom is for example arranged (for example; F; Cl; Br; I); hydroxyl; carboxyl; cyano group; amino; alkyl amino (for example; methylamino; ethylamino; butyl amino; dimethylamino); nitro; sulfo group; carbamyl; alkyl-carbamoyl (for example; N-methylamino formoxyl; N-ethylamino formoxyl; N; the N-formyl-dimethylamino); sulfamoyl; alkylsulfamoyl group (for example; N-methyl sulfamoyl; N-ethyl sulfamoyl; N; N-dimethylamino sulfonyl); urea groups; the alkyl urea groups (for example; N-methyl urea groups; N; N-dimethyl urea groups; N; N; N '-trimethyl urea groups); alkyl (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; lauroyl); acyloxy (for example; acetoxyl group; butyryl acyloxy; hexylyloxy; the 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; amoxy-carbonyl; heptan oxygen base carbonyl); aryloxycarbonyl (for example; phenyloxycarbonyl); alkoxycarbonyl amino (for example; butoxy-carbonylamino; hexyloxy carbonyl amino); alkylthio group (for example; methyl mercapto; ethylmercapto group; the rosickyite base; butylthio; penta sulfenyl; heptan sulfenyl; hot sulfenyl); arylthio (for example; thiophenyl); alkyl sulphonyl (for example; methyl sulphonyl; ethylsulfonyl; the sulfonyl propyl base; the butyl sulfonyl; the amyl group sulfonyl; the heptyl sulfonyl; the octyl group sulfonyl); acylamino-(for example; acetylamino; the butyl acylamino-; hexanoyl amino; lauroyl amino) and nonaromatic heterocycles group (for example, morpholino base; pyrazinyl).

At first, as preferred substituents, halogen atom, cyano group, carboxyl, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acylamino-, alkoxy carbonyl, alkoxy, alkylthio group and alkyl are for example arranged.

The moieties of alkyl amino, alkoxy carbonyl, alkoxy, alkylthio group and alkyl can also have substituting group.The substituent example of this 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 nonaromatic heterocycles group.As the substituting group of moieties and alkyl, preferred halogen atom, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acyl amino, alkoxy carbonyl and alkoxy.

In formula (1), L ¹Representative be selected from alkylidene, alkenylene, alkynylene ,-O-,-divalent linker of the group that CO-and these moiety combinations are formed.

Alkylidene can have ring texture.As cyclic alkylidene, preferred cyclohexylidene, preferred especially 1, the 4-cyclohexylidene.As the chain alkylidene, straight-chain alkyl-sub-is more preferred than branched alkylidene.

Alkylidene preferably has 1-20 carbon atom, more preferably 1-15, even more preferably 1-10, more preferably 1-8, most preferably 1-6 once more.

As the structure of alkenylene and alkynylene, chain structure is more preferred than ring texture, and linear chain structure than branched structure more preferably.

Alkenylene and alkynylene preferably have 2-10 carbon atom, more preferably 2-8, even more preferably 2-6, more preferably 2-4, most preferably 2 (ethenylidene or ethynylenes) once more.

Arlydene preferably has 6-20 carbon atom, more preferably 6-16, even more preferably 6-12.

In the molecular structure of formula (1), by clipping L ¹Ar ¹And Ar ²Preferably 140 ° or bigger of the angles that forms, more preferably 140 °-220 °.

As bar-shaped compound, the more preferably compound of following formula (2) representative.

Ar ¹-L ²-X-L ³-Ar ² (2)

In formula (2), Ar ¹And Ar ²Represent aromatic group independently of one another.Ar in the definition of aromatic group and example and the formula (1) ¹And Ar ²Identical.

In formula (2), L ²And L ³Representative independently of one another be selected from alkylidene ,-O-,-divalent linker of the group that CO-and these moiety combinations are formed.

As the structure of alkylidene, chain structure is more preferred than ring texture, and linear chain structure than branched structure more preferably.

Alkylidene preferably has 1-10 carbon atom, more preferably 1-8, even more preferably 1-6, more preferably 1-4, most preferably 1 or 2 (methylene or ethylidene) once more.

L2 and L2 separately especially preferably representative-O-CO-or-CO-O-.

In formula (2), X represents 1,4-cyclohexylidene, ethenylidene or ethynylene.

The instantiation of the compound of following display type (1) representative.

Instantiation (1) to (34), (41) and (42) have two unsymmetrical carbons in the 1-position and the 4-position of cyclohexane ring.Yet because instantiation (1), (4) to (34), (41) and (42) have symmetrical internal compensation shape molecular structure, so they do not have optical isomer (optical activity), and geometric isomeride (trans and cis) is only arranged.Trans (1-is trans) and the cis (1-cis) that show instantiation (1) below.

(1-is trans)

(1-cis)

As mentioned above, preferred bar-shaped compound has straight-chain molecular structure.Therefore, trans more preferred than cis.

Instantiation (2) and (3) have optical isomer (four kinds of isomeride altogether) and geometric isomeride.As for geometric isomeride, trans similarly more preferred than cis.Optical isomer does not have quality, and can be D, L or raceme arbitrarily.

In (45), center ethenylidene key exists trans and cis at instantiation (43).For the same reason, trans more preferred than cis.

The compound of also preferred following formula (3) representative.

Formula (3)

In formula (3), R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Represent hydrogen atom or substituting group independently of one another, R ¹, R ², R ³, R ⁴And R ⁵In at least one represents electron donating group, R ⁸Represent hydrogen atom, have the alkyl of 1-4 carbon atom, thiazolinyl, alkynyl, aryl, alkoxy, aryloxy group, alkoxy carbonyl, acyl amino, cyano group or halogen atom with 2-12 carbon atom with 2-12 carbon atom with 6-12 carbon atom with 1-12 carbon atom with 6-12 carbon atom with 2-6 carbon atom with 2-6 carbon atom.

The solution that has the bar-shaped compound of 250nm or shorter absorption maximum (λ max) under ultra-violet absorption spectrum can be mixed with two or more and use.

Bar-shaped compound scientific research is synthetic with reference to the method described in the various documents, for example can enumerate Mol.Cryst.Liq.Cryst, Vol.53, p.229 (1979), ditto, Vol.89, p.93 (1982), ditto, Vol.145, p.1ll (1987), ditto, Vol.170, p.43 (1989), J.Am.Chem.Soc, Vol.113, p.1349 (1991), ditto, Vol.118, p.5346 (1996), ditto, Vol.92, p.1582 (1970), J.Org.Chem., Vol.40, p.420 (1975) and Tetrahedron, Vol.48, No.16, p.3437 (1992).

The addition of delay dose is the 0.1-30 quality % of amount of polymers, more preferably 0.5-20 quality % preferably.

In the cellulose ethanoate of per 100 mass parts, the preferred amount ranges of aromatic is the 0.01-20 mass parts, more preferably 0.05-15 mass parts, even more preferably 0.1-10 mass parts.Two or more aromatics can be used in combination.

The organic solvent of dissolving cellulose acylate of the present invention is described below.

Chlorine solvent:

When preparation cellulose acylate solution of the present invention, preferably use the chlorine organic solvent as primary solvent.The type of chlorine organic solvent has no particular limits, as long as can the dissolving cellulos acylate, curtain coating forms film, realizes purpose of the present invention thus.The chlorine organic solvent is methylene chloride and chloroform preferably, preferred especially methylene chloride.The organic solvent of dechlorination outside the organic solvent can be mixed with the chlorine organic solvent and no problem.When using other organic solvent, the essential methylene chloride that uses at least 50 quality %.Describe below with chlorine organic solvent one and be used from non-chlorine organic solvent of the present invention.

As non-chlorine organic solvent, preferred use has the solvent that is selected from ester, ketone, ether, pure and mild hydrocarbon of 3-12 carbon atom separately.Ester, ketone, ether and alcohol can have ring texture.Also can use and have ester, ketone and ether (that is, and-O-,-CO-and-COO-) in the compound of any two or more functional groups as solvent, for example, can have other functional group simultaneously, for example, alcoholic extract hydroxyl group.Under for the situation of solvent with two or more functional groups, carbon number can be in the scope of the regulation of the compound with any functional group.Example with ester of 3-12 carbon atom comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.Example with ketone of 3-12 carbon atom comprises acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone.Example with ether of 3-12 carbon atom comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-two  alkane, 1,3-dioxolanes, tetrahydrofuran, anisole and phenetol.Example with organic solvent of two or more functional groups comprises acetate 2-ethoxy ethyl ester, 2-methyl cellosolve and butoxy ethanol.

The alcohol that is used in combination with the chlorine organic solvent can be straight chain, side chain or ring-type, especially preferably uses saturated aliphatic hydrocarbon.The hydroxyl of alcohol can be a kind of arbitrarily in primary hydroxyl, secondary hydroxyl and the 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.As alcohol, also can use fluorine alcohol.For example, 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3 have been enumerated, 3-tetrafluoro-1-propyl alcohol.Hydrocarbon can be straight chain, side chain or ring-type.Aromatic hydrocarbon and aliphatic hydrocrbon can use.Aliphatic hydrocrbon can be saturated or undersaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.

Combination as the chlorine organic solvent of preferred primary solvent among the present invention enumerate following combination, but the present invention is not limited to this.

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

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

Methylene chloride/acetone/methanol/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/two  alkane/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 acetate/ethanol/butanols/hexane (65/10/10/5/5/5, mass parts)

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

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

Non-chlorine solvent:

Secondly, the non-chlorine organic solvent that is preferred for preparing cellulose acylate solution of the present invention is described.Non-chlorine organic solvent has no particular limits, as long as can the dissolving cellulos acylate, curtain coating forms film, realizes purpose of the present invention thus.As non-chlorine organic solvent, the preferred solvent that is selected from the ester, ketone and the ether that have 3-12 carbon atom separately that uses.Ester, ketone and ether can have ring texture.Also can use and have ester, ketone and ether (that is, and-O-,-CO-and-COO-) in the compound of any two or more functional groups as primary solvent, and can have other functional group, for example, alcoholic extract hydroxyl group.Under for the situation of primary solvent with two or more functional groups, carbon number can be in the scope of the regulation of the compound with any functional group.Example with ester of 3-12 carbon atom comprises ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.Example with ketone of 3-12 carbon atom comprises acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methyl cyclohexanone.Example with ether of 3-12 carbon atom comprises Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, 1,4-two  alkane, 1,3-dioxolanes, tetrahydrofuran, anisole and phenetol.Example with organic solvent of two or more functional groups comprises acetate 2-ethoxy ethyl ester, 2-methyl cellosolve and butoxy ethanol.

The non-chlorine organic solvent that is used for the dissolving cellulos acylate goes out to send selection according to various viewpoints as mentioned above, and is preferably as follows.The preferred solvent that cellulose acylate of the present invention is used is the mixed solvent of three kinds or more kinds of solvents that differ from one another.First solvent is to be selected from least a solvent in methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolanes and the two  alkane or the mixed solvent of these solvents.Second solvent is selected from ketone or the acetoacetic ester with 4-7 carbon atom, and the 3rd solvent is selected from alcohol or the hydrocarbon with 1-10 carbon atom, more preferably has the alcohol of 1-8 carbon atom.When first solvent is the mixed solvent of two or more solvents, can not contain second solvent.First solvent is more preferably the mixed solvent of methyl acetate, acetone, methyl formate, ethyl formate or these solvents.Second solvent is more preferably the mixed solvent of methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetoacetate or these solvents.

The alcohol of the 3rd solvent can be straight chain, side chain or ring-type, and saturated aliphatic hydrocarbon is particularly preferred hydrocarbon.The hydroxyl of alcohol can be a kind of arbitrarily in primary hydroxyl, secondary hydroxyl and the 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.As alcohol, also can use fluorine alcohol.For example, 2-fluoroethanol, 2,2,2 tfifluoroethyl alcohol and 2,2,3 have been enumerated, 3-tetrafluoro-1-propyl alcohol.Hydrocarbon can be straight chain, side chain or ring-type.Aromatic hydrocarbon and aliphatic hydrocrbon can use.

Aliphatic hydrocrbon can be saturated or undersaturated.The example of hydrocarbon comprises cyclohexane, hexane, benzene, toluene and dimethylbenzene.Pure and mild hydrocarbon can use separately as the 3rd solvent or two or more mix use, and without limits.

The preferred embodiment of the 3rd solvent, comprise that methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols and 2-butanols are as alcohol, and comprise cyclohexanol, cyclohexane and hexane as hydrocarbon, and in these solvents, special particular methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol and 1-butanols.

These three kinds of solvents are that 20-95 quality %, second solvent are that 2-60 quality %, the 3rd solvent are the ratio use of 2-30 quality % with first solvent preferably.More preferably the ratio of first solvent is 30-90 quality %, and second solvent is 3-50 quality %, and the alcohol of the 3rd solvent is 3-25 quality %.Even more preferably the ratio of first solvent is 30-90 quality %, and second solvent is 3-30 quality %, and the alcohol of the 3rd solvent is 3-15 quality %.When first solvent is a mixed solvent and when not using second solvent, the content ratio of preferred first solvent is 20-90 quality %, the content ratio of the 3rd solvent is 5-30 quality %, and more preferably the ratio of first solvent is 30-86 quality %, and the 3rd solvent is 7-25 quality %.Hatsumei Kyokai Kokai Giho Kogi No.2001-1745 (March 15 calendar year 2001, by Hatsumei Kyokai distribution) describes in detail in the 12-16 page or leaf and is used for non-chlorine organic solvent of the present invention.The preferred compositions that shows non-chlorine organic solvent below, but the present invention is not limited to this.

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/two  alkane/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)

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

And, also can prepare cellulose acylate solution by the following method.

-with methyl acetate/acetone/butanols (81/8/7/4, mass parts) preparation cellulose acylate solution,, in filtrate, add the method for the butanols of 2 mass parts then with this solution filtering and concentrating.

-with methyl acetate/acetone/butanols (84/10/4/2, mass parts) preparation cellulose acylate solution,, in filtrate, add the method for the butanols of 4 mass parts then with this solution filtering and concentrating.

-with methyl acetate/acetone (84/10/6, mass parts) preparation cellulose acylate solution,, in filtrate, add the method for the butanols of 5 mass parts then with this solution filtering and concentrating.

The feature of cellulose acylate solution:

The preferred in the present invention cellulose acylate with 13-27 quality % is dissolved in the organic solvent, more preferably dissolves 15-25 quality %, especially the cellulose acylate of preferred dissolution 15-20 quality %.In order to prepare the cellulose acylate in this concentration range; can prepare solution in the stage of dissolving cellulos acylate with described concentration; perhaps preparation earlier have a low concentration solution (for example; 9-14 quality %); can concentration be increased to normal concentration by concentration method then; perhaps prepare solution in advance with high concentration; by adding various adjuvants concentration is reduced to normal concentration then; and any means can be used for the present invention, as long as can prepare cellulose acylate solution to reach top concentration.

Secondly, the molecular weight of the aggregation of rare cellulose acylate solution that the organic solvent diluting cellulose acylate solution that preferred preferred in the present invention usefulness has same composition obtains to 0.1-5 quality % is 150,000-15,000,000.More preferably, the molecular weight of this aggregation is 180,000-9,000,000.The molecular weight of aggregation can record by the static light scattering method.Preferably dissolve, make that square radius of the inertia that the while can record is 10-200nm.Square radius of preferred inertia is 20-200nm.Less preferred again the dissolving makes that second virial coefficient is-2 * 10 ^-4To 4 * 10 ^-4, more preferably second virial coefficient is-2 * 10 ^-4To 2 * 10 ^-4

Molecular weight, square radius of inertia and the definition of second virial coefficient of aggregation are described.They all are to measure by the static light scattering method according to the methods below.Because this measurement of cause of surveying instrument is carried out in the dilution zone, but this measured value reacts the behavior of dope of the present invention at high concentration region.At first, cellulose acylate is dissolved in dope with in the solvent, makes the solution that concentration is respectively 0.1 quality %, 0.2 quality %, 0.3 quality % and 0.4 quality %.In order to prevent suction, under 25 ℃ of 10%RH, use and weigh at 120 ℃ of following cellulose acylates of dry 2 hours.Dissolve according to the dissolving method (normal-temperature dissolution, hot-cold lysis, high-temperature digestion) that dope adopted.Then, be the Teflon filtrator filtration of 0.2 μ m with solution and solvent via hole diameter.With light scattering apparatus (DLS-700, by OTSUKAELECTRONICS CO., LTD. makes) under 25 ℃ with 10 ° of static light scatterings of measuring filtrate of angle intervals of 30 ° to 140 °.The gained data are analyzed according to the Berry drawing.As analyzing required refractive index, use the value of the solvent of measuring with Abbe refractometer.As for the concentration gradient (dn/dc) of refractive index, use differential refractometer (DRM-1021, by OTSUKAELECTRONICS CO., LTD. makes), and measure with solvent used in the light scattering measurement and solution.

The preparation of dope:

The dissolving method of cellulose acylate solution of the present invention (dope) has no particular limits, and can pass through the combination dissolving cellulos acylate of arbitrary method in normal-temperature dissolution method, hot-cold lysis method, the high-temperature digestion method or these methods.The preparation method of cellulose acylate solution is disclosed in 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, JP-A-11-323017 and JP-A-11-302388.The disclosed technology that cellulose acylate is dissolved in the organic solvent can arbitrarily be used for the present invention within the scope of the invention in these patents.Its details is non-chlorine solvent especially, is described in Hatsumei Kyokai Kokai Giho Kogi No.2001-1745 (March 15 calendar year 2001 is by Hatsumei Kyokai distribution), the 22-25 page or leaf, and also these methods can be used for the present invention.Rich liquor solution of the present invention is usually through concentrating and filter, and these contents are in Hatsumei Kyokai Kokai Giho KogiNo.2001-1745 (March 15 calendar year 2001 is by Hatsumei Kyokai distribution), and the 25th page also has a detailed description.When at high temperature dissolving, solution temperature is higher than the boiling point of used organic solvent in nearly all situation, and dissolves under pressure in this case.

Cellulose acylate solution of the present invention can obtain with high concentration as mentioned above, thereby can obtain the dope of concentration height and excellent in stability, and does not depend on concentrated mode.For easier dissolving, can use to prepare the method that low concentration solution improves concentration then.Method for concentration without limits, and can use and a kind ofly in cylinder and cylinder, add low concentration solution between the rotational trajectory with the rotating blade periphery of circumferencial direction rotation, and give the temperature difference between cylinder and the solution, thus (for example with solvent evaporation and the method that obtains highly concentrated solution, JP-A-4-259511), in container, blow out hot low concentration solution with a kind of from nozzle, make solvent flashing in the time before solution strikes on the chamber wall from nozzle, make solvent vapour leave container simultaneously, and the method for taking out highly concentrated solution in the container (for example, United States Patent (USP) 2,541,012,2,858,229,4,414,341 and 4,504,355).

Preferably before curtain coating, remove foreign matter for example insoluble substance, dust and impurity with the suitable filtrator of wire screen or flannel.For the plain acylate solution of filter fiber, use the filtrator of absolute filtering accuracy as 0.1-100 μ m, more preferably use the filtrator of absolute filtering accuracy as 0.5-25 μ m.The thickness of filtrator is 0.1-10mm preferably, more preferably 0.2-2mm.In this case, preferably at preferred 1.6MPa or littler, more preferably 1.2MPa or littler, even more preferably 1.0MPa or littler filter under preferred especially 0.2MPa or the littler filter pressure.As filter material, can preferably use material known, for example, glass fibre, cellulose fibre, filter paper and fluororesin, for example, tetrafluoroethylene resin, and especially preferably use pottery and metal.

Preferred viscosity coefficient with cellulose acylate solution is adjusted to particular range among the present invention.Viscosity coefficient (unit: Pas) be sample solution to about 1ml, for example, with stress rheometer (CVO 120, made by Bohlin Instruments) in the frequency of 33 ℃ dope temperature, 1Hz with apply and measure under the condition of load of 1% displacement.

The viscosity coefficient of solution can be adjusted with the characteristic of cellulose acylate and the concentration of cellulose acylate.Described in synthetic method, the intrinsic viscosity characteristic of cellulose acylate can change by adjusting viscometric degree of polymerization and molecular weight distribution.

Described in the solution properties of cellulose acylate, the preferred concentration of cellulose acylate is 13-27 quality %.The result; the preferred viscosities coefficient of the cellulose acylate solution that obtains is 10-70Pas (a measurement temperature: 33 ℃); and when viscosity is higher than this scope; mobile variation; so that be difficult to filter and curtain coating; and when viscosity was lower than this scope, the internal pressure of curtain coating mould reduced and can not carry out uniform curtain coating at Width, and the variation of Width is tending towards increasing like this.The viscosity coefficient of dope is more preferably 15-45Pas, most preferably 20-35Pas.

When viscosity coefficient was in above-mentioned scope, filter loading reduced, and so just can use the filtrator that the aperture is less and precision is higher.As a result, cellulose acylate film of the present invention contains seldom foreign matter, and can reduce black display, the phenomenon of light leak and flash of light (being referred to as the bright spot inclusion) when particularly being installed in film in the LCD.

Film forms:

A kind of method of using cellulose acylate formulations prepared from solutions film is described below.As the preparation method and the equipment of cellulose acylate film of the present invention, can use the solution casting that is usually used in preparing cellulose triacetate to become embrane method and solution casting film-forming apparatus.Dope (cellulose acylate solution) taking-up from dissolver (dryer) that makes is housed in the feed bin then, makes dope slough foam for final preparation.With this dope from the dope floss hole through for example through revolution can be highly accurately the reinforced pressure-type volume of volume adjustment adjust gear-type pump and be delivered on the pressure-type mould, from the pressure-type mould with this dope equably curtain coating to the metallic carrier of the curtain coating part of ring-type operation, and from metallic carrier, almost become the pick-up point of a circle that half-dried dope film (being also referred to as the width of cloth) is peeled off at metallic carrier.Clamp with clip at these width of cloth two ends, and the width of cloth transports and drying through stenter under the situation that keeps width, and then the roller of drying device transports and finishes drying, and is rolled into predetermined length with coiler.The combination of the roller of stenter and exsiccator changes with purpose.Solution casting at the function and protecting film that is used for electronic console becomes embrane method, except the solution casting film-forming apparatus, also is equipped with coating apparatus under the surface-treated situation of for example bottom, antistatic backing, anti-halo layer, protective seam etc.Simple each process of description, but the present invention is not limited to this.

Solvent cast method by the preparation cellulose acylate film with cellulose acylate solution (dope) curtain coating that makes to cylinder or be with, thus with solvent evaporation and form film.Preferably before curtain coating, adjust the concentration of dope, so that solids content is 5-40 quality %.The preferred surface that offsets cylinder or band in advance.Preferred curtain coating dope on the surface of 30 ℃ or lower cylinder or band, and be curtain coating dope on-10 ℃ to 20 ℃ the metallic carrier in temperature more preferably.

And, the technology described in the following patent can be used for the present invention: JP-A-2000-301555, JP-A-2000-301558, JP-A-7-032391, JP-A-3-193316, JP-A-5-086212, JP-A-62-037113, JP-A-2-276607, JP-A-55-014201, JP-A-2-111511 and JP-A-2-208650.

The multilayer curtain coating:

Can be with cellulose acylate solution with the individual layer solution casting to metallic carrier, for example, on smooth zone or the cylinder, perhaps can two or more cellulose acylate solution of curtain coating.Under the situation of the multiple cellulose acylate solution of curtain coating; a plurality of curtain coatings that can provide at interval curtain coating cellulose acylate solution from the working direction of metallic carrier; it is simultaneously laminated to form film thus, and the method described in JP-A-61-158414, JP-A-1-122419 and the JP-A-11-198285 can be used for the present invention.

Also preferably form film, and for example can use disclosed method preparation among JP-B-60-27562 (term used herein " JP-B " is meant " it is open to examine Jap.P. "), JP-A-61-94724, JP-A-61-947245, JP-A-61-104813, JP-A-61-158413 and the JP-A-6-134933 from two curtain coatings curtain coating cellulose acylate solution.And; the cellulose acylate film of the casting method acquisition of also preferably using low-viscosity cellulose acylate solution to surround high-viscosity cellulose acylate flow of solution and will this full-bodied and low viscous cellulose acylate solution extruding simultaneously is as disclosed among the JP-A-56-162617.As other method, the amount of alkoxide component that also preferred outside solution contains hazardous solvent is greater than internal solution, as disclosed among JP-A-61-94724 and the JP-A-61-94725.Perhaps, can use with two curtain coating capitiforms to become film and the film that forms on the metallic carrier is peeled off by the first curtain coating head, then by the second curtain coating head with face that the surface of metallic carrier contacts on the method for curtain coating, as disclosed among the JP-B-44-20235.Cellulose acylate solution can be same solution or different solutions, and has no particular limits.In order to give a plurality of cellulose acylate layer functions, the cellulose acylate solution of extruding corresponding to each function from each curtain coating head is effective.And, can be by cellulose acylate solution while other functional layer of curtain coating (for example, bonding coat, dye coating, antistatic backing, anti-halo layer, UV-absorbing layer, polarization layer etc.).

In order to obtain required thickness by conventional individual layer solution; must extrude high concentration and high-viscosity cellulose acylate solution; the poor stability of cellulose acylate solution in this case produces solid matter, and is accompanied by the problem that peace-breaking face that solid matter causes destroys.As the means that prevent this problem; by from the multiple cellulose acylate solution of a curtain coating curtain coating; can simultaneously high viscosity solution be expressed on the metallic carrier; the result; not only can improve the plane performance and can form the surface property good film, and by using dense cellulose acylate solution can reduce dry load and can improving the film speed of producing.

Under situation, the outside have no particular limits, but preferred outer face thickness is the 1-50% of total film thickness, more preferably 2-30% with thickness inside for curtain coating altogether.Under three layers of curtain coatings altogether or more multi-layered situation, the layer that contact with metallic carrier with contact with air layer total film thickness be defined as outside thickness.Under situation for curtain coating altogether, by curtain coating adjuvant altogether for example the different cellulose acylate solution of concentration of plastifier, ultraviolet light absorber and matting agent can form the cellulose acylate film of laminate structures.For example, can form the cellulose acylate film of structure with cortex/core layer/cortex.For example, can add a large amount of matting agents to cortex, perhaps only add cortex to.Can add amount to core layer than big plastifier and ultraviolet light absorber in the cortex, perhaps can only add core layer to.Can change the interior plastifier of cortex and core layer and the type of ultraviolet light absorber.For example, can add low volatility plastifier and/or ultraviolet light absorber to cortex, and the ultraviolet light absorber that has the plastifier of excellent plasticising performance or have an excellent UV absorbing properties is added in the core layer.With peeling off in the cortex that promoter only adds the metallic carrier side to also is a kind of preferred implementation.Also preferably will measure than the big hazardous solvent alcohol that is used for this solution of gelling (according to cooling drums method cool metal carrier) in the core layer and add cortex to.The Tg of cortex and core layer can be different, and the Tg of preferred core layer is lower than the Tg of cortex.The viscosity of solution that contains cellulose acylate during curtain coating may be different between cortex and core layer, and the viscosity of preferred cortex is less than core layer, but the viscosity of core layer can be littler than the cortex.

Curtain coating:

Casting method as solution, in case have from pressing mold the dope that makes to be expressed into method dope curtain coating on the metallic carrier equably and to adjust the reverse roll method of the thickness of dope according to the method for scraping the skill in using a kitchen knife in cookery adjusts dope with scraper thickness with reverse roll after to metallic carrier, and preferably use the method for pressing mold.Pressing mold has clothes hanger type (coat hanger) and T pressing mold type, and these two types all can preferably be used.Except the method that shows above, can use the known method of various routines by curtain coating cellulose triacetate solution film forming, and the difference of the boiling point by considering solvent for use etc. is adjusted membrance casting condition, can obtain and similar effect described in each patent.As the metallic carrier that is used for ring-type operation preparation cellulose acylate film of the present invention, use the surface through the cylinder of chromium plating finish rolling with through the stainless steel band (or band) of surface finish finish rolling.As the pressing mold that is used to prepare cellulose acylate film of the present invention, a mould can be installed in the upper part of metallic carrier or two or more moulds is installed, preferably one or two.When two or more mould is installed, the dope amount for the treatment of curtain coating can be divided into the different proportion of each mould relatively, perhaps dope can be regulated pumps with ratio separately from a plurality of precise volumes and be added to each mould.Be used for curtain coating cellulose acylate solution temperature preferably-10-55 ℃, more preferably 25-50 ℃.Each process can be uniform temp separately or can be different temperatures.When temperature not simultaneously, before curtain coating, guarantee temperature required just enough at once.

Dry:

The drying of the dope in cellulose acylate film processing on metallic carrier is normally undertaken by following method: from the surface of metallic carrier (cylinder or band), promptly from the method for the surface of the width of cloth on metallic carrier blowing hot-air; Method from the back side blowing hot-air of cylinder or band; The contact of perhaps that temperature control fluid is relative with dope curtain coating face band or the back side of cylinder, through conducting heat heating cylinder or with the liquid heat transfer method of control surface temperature thus; Preferred back side liquid heat transfer method in these methods.The surface temperature of metallic carrier can be an arbitrary temp before the curtain coating, as long as it is lower than the boiling point of solvent used in the dope.Yet, in order to quicken dry and to avoid on metallic carrier, flowing, preferably temperature is adjusted to temperature than low 1-10 ℃ of the boiling point of solvent with minimum boiling point.Yet this rule is not suitable for not to be needed to cool off and the dry situation of just peeling off the curtain coating dope.

Stretch processing:

The delay of cellulose acylate film of the present invention can be adjusted by stretch processing.Have at Width and have a mind to the method for oriented film, and these methods are disclosed among JP-A-62-115035, JP-A-4-152125, JP-A-4-284211, JP-A-4-298310 and the JP-A-11-48271.In order to postpone in the face that improves cellulose acylate film, the film of processing is stretched.

The stretching of film is carried out under room temperature or heating.Heating-up temperature preferably is lower than the glass temperature of film.The stretching of film can be only at the uniaxial tension of vertical direction or horizontal direction, perhaps can be simultaneously or continuous biaxial stretch-formed.The 1-200% that stretches normally stretches, and preferred 1-100% stretches, and especially preferred 1-50% stretches.In the birefringence of optical thin film, the refractive index of preferable width direction is greater than the refractive index of length direction.Therefore, preferably carry out bigger stretching at Width.A stretched processing of curling of formation can be carried out or can be made to stretching in film forming procedure.Under the former situation, stretching can be carried out under the situation of residual solvent and can be to stretch under the 2-30% at amount of residual solvent containing.

In the present invention, the thickness of (after the drying) cellulose acylate film of finishing is different and different with purpose, but common in the scope of 5-500 μ m, preferred 20-300 μ m, and for the especially preferred 40-110 μ m of VA LCD.On the other hand, be 110-180 μ m by making thickness, the dry load during casting film-forming increases, but the size of optical characteristics and thickness are proportional, can obtain required optical characteristics by increasing thickness like this.Because seepage rate and thickness reduce inversely, therefore make seepage rate reduce by increasing thickness, and more difficult infiltration moisture, this is useful in polaroid continues 500 hours under 60 ℃ of 90%RH serviceability test.

Thickness can be adjusted to desired thickness by solid concentration, the gap of die head, the extrusion pressure of mould and the speed of metallic carrier of adjusting dope.The width of thus obtained cellulose acylate film is 0.5-3m preferably, more preferably 0.6-2.5m, even more preferably 0.8-2.2m.The preferably every volume of the length of film to be rolled 100-10,000m, more preferably 500-7,000m, even more preferably 1,000-6,000m.When rolling, preferably provide embossing at film one end at least, and width 3-50mm preferably, more preferably 5-30mm highly is 1-50 μ m, preferred 2-20 μ m, more preferably 3-10 μ m.This embossing can be single-acting extruding or double acting extruding.

The film thickness difference of Width preferably 5 μ m or littler, more preferably 3 μ m or littler except embossed portion is divided.When the film thickness difference of Width was big, when surpassing 4 with film is long, the film of 000m was easy to be referred to as the distortion owing to the black-tape of thickness inhomogeneity when rolling.Thickness Variation unexpected under the narrow width not only can see with the vertical stripes deformity from the teeth outwards, and is easy to cause uneven luminance when being installed in this film on the LCD, so this problem especially.Preferably when the time at Width continuous coverage thickness, be 0.6 μ m or littler every the thickness difference of 10mm, and every the thickness difference of 10mm 0.5 μ m or littler preferably.

The haze value of the maintenance transparency is 0.01-2% preferably.In order to reduce haze value, the particulate matting agent that fully disperses to add is effectively with the amount that reduces aggregated particle, perhaps matting agent is only joined cortex to reduce addition.

The optical characteristics of cellulose acylate film:

The optical characteristics Re length of delay of cellulose acylate film of the present invention and Rth length of delay satisfy following equation (V) and (VI) respectively

46nm≤Re(630)≤200nm (V)

70nm≤Rth(630)≤350nm (VI)。

At equation (V) with (VI), Re (λ) is that (unit: nm), Rth (λ) is the length of delay (unit: nm) of film thickness direction under the wavelength X nm to the interior length of delay of the face under the wavelength X nm.

Re (λ) can throw the light birefringence refractometer of wavelength X nm in the normal direction of film, and for example, KOBRA 21ADH (being made by Oji Scientific Instruments) measures.Effective value 1.48 and thickness by the input mean refractive index, with the length of delay of three orientation measurements of top Re (λ), with retardation axis in the face as sloping shaft from the normal direction with film tilt length of delay that+40 ° the light of direction projection wavelength X nm measures and based on retardation axis in the face as sloping shaft from the length of delay that-40 ° the light of direction projection wavelength X nm measures that tilts of the normal direction with film, can calculate Rth (λ).

More preferably satisfy following equation (VII) and (VIII)

46nm≤Re(630)≤100nm (VII)

160nm≤Rth(630)≤350nm (VIII)。

For only with the VA LCD of an optical thin film, preferred polaroid of the present invention except satisfy equation (VII) and (VIII) also satisfy following equation (IX) and (X)

Rth(630)＝a-5.9Re(630)nm (IX)

520≤a≤600nm (X)。

It is 560nm that the y of the straight line of equation (IX) representative intersects the central value of a, and a is offset to than downside from 560, and it is big that the black brightness value of VA LCD becomes.That is, light leak and not blackening of black take place.Along with a is offset to upper side from 560, along with the angle of observing LCD changes, the variation of tone also becomes greatly, so is not preferred.Equation (X) has shown the scope of a value.Specifically, with regard to only with regard to the VA LCD of a polaroid, preferred 55nm≤Re (630)≤85nm and 535≤a≤585nm.Re (630) and Rth (630) change with the Δ nd value of used VA liquid crystal cell.For example, when the Δ nd of VA liquid crystal cell value was 300nm, most preferred Re (630) and Rth (630) were respectively 55-60 and 185-275.When the Δ nd of VA liquid crystal cell value was 300nm, most preferred Re (630) and Rth (630) were respectively 60-65 and 160-240.

Preferably the dispersion of the Re value of all width is ± 5nm, more preferably ± and 3nm.The dispersion of Rth value preferably ± 10nm, more preferably ± 5nm.Also preferred Re value and Rth value are in the dispersion of the machine direction also scope in the dispersion of Width.

The optical characteristic value of Re and Rth along with high temperature through constantly humidity variation and mass change and change.The variation of Re and Rth value is preferably as far as possible little.In order to reduce the change of optical property that humidity causes, can use big cellulose acylate of the acyl substituted degree of 6-position and various hydrophobic additive (plastifier, postpone dose, ultraviolet light absorber etc.) to reduce the seepage rate and the equilibrium moisture content of film.60 ℃ of following preferred seepage rates that continue 24 hours of 95%RH are 400-2,300g/m ²Preferred equilibrium moisture content under 25 ℃ of 80%RH is 3.4% or littler.The change of optical property Re value of preferred 25 ℃ of following humidity when 10%RH becomes 80%RH is 12nm or littler, and the Rth value is 32nm or littler.Based on cellulose acylate, the preferred addition of hydrophobic additive is 10-30%, more preferably 12-25%, especially preferably 14.5%-20%.When adjuvant volatilization with when decomposing the mass change that causes film and change in size, optical characteristics also changes.Therefore, preferably under 80 ℃ of 90%RH the mass change through film after 48 hours be 5% or littler.Similarly, under 60 ℃ of 90%RH through 24 hours after and the change in size after through 24 hours is preferably ± 2% or littler under 90 ℃ of 3%RH.And even change in size and mass change are little, the photoelasticity modulus of film hour change of optical property reduces.Therefore, the photoelasticity modulus of film preferably 50 * 10 ^-13Cm ²/ dyn (5.0 * 10 ^-10m ²/ N) or littler.

Polaroid:

Two transparent protective films that provide on the two sides of polaroid by polarizer and polarizer are formed.Cellulose acylate film of the present invention can be used as a protective film.Can use common cellulose acetate film as other protective film.As polarizer, the dye polarizing device and the polyenoid polarizer of the dyestuff of known iodine polarizer, two kinds of colors of use.Iodine polarizer and dye polarizing device are normally made with polyvinyl alcohol film.When cellulose acylate film of the present invention was used as the protective film of polaroid, the preparation method of polaroid had no particular limits and can use commonsense method.A kind of like this method is arranged: alkali treatment gained cellulose acylate film and use fully saponified vinyl alcohol aqueous solution with this film adhere to polyvinyl alcohol film soaked in iodine solution and the two sides of the polarizer that obtains of stretching on.Replace alkali treatment, can use disclosed easy Method for bonding among JP-A-6-94915 and the JP-A-6-118232.As the bonding agent that is used for bonding protective film and polarizer, poly (vinyl alcohol) binder is for example arranged, for example, polyvinyl alcohol (PVA) and polyvinyl butyral and vinyl latex, for example, butyl acrylate.Polaroid is made up of the protective film on polarizer and protection polarizer two sides.And, protective film is adhered on the one side of polaroid, and an independent film is adhered on the another side.Protective film and separately film be used to transport and the purpose of protection polaroid when detecting polaroid.In this case, adhere to the purpose of protective film, and protective film is adhered on the relative face of the face of waiting to adhere to liquid crystal board with the surface of protection polaroid.Use independent film to wait to adhere on the bonding coat of liquid crystal board, and adhere on the face of waiting to adhere to the polaroid on the liquid crystal board with covering.

The method that cellulose acylate film of the present invention is adhered to polarizer is preferably such, adheres to retardation axis that polarizer and cellulose acylate film make the axis of homology of polarizer and cellulose acylate film concentrically with respect to one another.The polaroid that evaluation makes under polaroid intersects Nicol; found that when the retardation axis of cellulose acylate film and the absorption axes of polarizer (axle that intersects with the axis of homology) intersect precision during greater than 1 °, polaroid intersects that Nicol polarization property down reduces and the generation light leak.In this case, by not obtaining enough black level and contrast with the liquid crystal cell combination.Therefore, the direction of the principal refractive index nx of preferred cellulose acylate film of the present invention is 1 ° or littler from the skew of the direction of the axis of homology of polaroid, more preferably 0.5 ° or littler.

Measure independent transmissivity TT, the parallel transmissivity PT of polaroid and the transmissivity CT that intersects with UV3100PC (making) by Shimadzu Corporation.Measure independent transmissivity, parallel transmissivity and the transmissivity of intersecting respectively at the wavelength zone of 380-780nm, and get the mean value of measuring for 10 times.The serviceability test of polaroid has two kinds: (1) only has polaroid and (2) to be adhered to polaroid on the glass sheet with bonding agent.When measurement only had polaroid, optical compensating film was clipped between two polarizers, and makes two same sample.(about 5cm * 5cm) adheres to polaroid and makes optical compensating film make in glass sheet one side on the glass sheet sample of test (2), and prepares two identical samples.When measuring independent transmissivity, place sample and make film side face toward light source.Measure two samples and average conduct transmissivity separately.Preferable range as polarization property, transmissivity TT, parallel transmissivity PT and the transmissivity CT that intersects are respectively 40.0≤TT≤45.0,30.0≤PT≤40.0, CT≤2.0 separately, more preferably 41.0≤TT≤44.5,34≤PT≤39.0, CT≤1.3 (unit is %).In the serviceability test of polaroid, deviation is preferably as far as possible little.

When polaroid of the present invention leaves standstill 500 hours under 60 ℃ of 95%RH, the deviation delta P of the deviation delta CT (%) of independent transmissivity and degree of polarization of intersecting satisfy following equation (j) and (k) at least a

-6.0≤ΔCT≤6.0 (j)

-10.0≤ΔP≤0.0 (k)

Here, deviation is meant that the measured value after test deducts the test value that measured value obtained before.

By satisfying this requirement, guaranteed the stability of polaroid between use and preservation term.

Moisture barrier bag:

Among the present invention, " moisture barrier bag " uses the seepage rate of measuring according to cylindrical plate method (JIS Z208) to stipulate.Preferred use that seepage rate is 30g/ (m under 40 ℃ of 90%RH ²Day) or lower material.When seepage rate is 30g/ (m ²Day) or when higher, be difficult to prevent the influence of outside environment moisture.More preferably 10g/ (m ²Day) or lower seepage rate, most preferably 5g/ (m ²Day) or lower.

The material of moisture barrier bag has no particular limits, if the seepage rate above satisfying, and can use material known.(referring to Hoso Zairyo Binran (wrappage handbook), Nippon Hoso Gijutsu Kyokai (1995), Hoso Zairyo no Kiso Chishiki (ABCs of wrappage), Nippon Hoso Gijutsu Kyokai (November calendar year 2001), Kinosei Hoso Nyumon (function packaging introduction) first published, 21 Seiki Hoso KenkyuKyokai (on February 28th, 2002).) in the present invention, preferred low, the in light weight and easy to handle material of seepage rate.Especially preferably use compound substance for example to deposit silicon dioxide, aluminium oxide or the plastic sheeting of pottery and the laminate film of plastics and aluminium foil.The thickness of aluminium foil has no particular limits, as long as the moisture in the bag is not subjected to the influence of ambient moisture, preferred several microns to the hundreds of micron, more preferably 10-500 μ m.Moisture in the preferred moisture barrier bag of the present invention satisfies any following condition:

Under the state of packing polaroid, be preferably 43%RH-70%RH under 25 ℃, more preferably 45%-65%, even more preferably 45%-63%.

The difference of the humidity when humidity and polaroid adhere on the liquid crystal board in the bag of packing polaroid is 15%RH or littler.

Surface treatment:

By handling the surface of cellulose acylate film of the present invention, can improve the viscosity of cellulose acylate film and other functional layer (for example, internal coating and backing layer).As surface treatment, for example, can use glow discharge processing, ultraviolet treatment with irradiation, corona treatment, flame treatment and acid or alkali treatment.It can be 10 that glow discharge is handled ^-3Low Temperature Plasma Treating under the low-pressure gas of-20Torr perhaps can be the Cement Composite Treated by Plasma under the atmospheric pressure.Plasma exciatiaon gas be can plasma exciatiaon under the superincumbent condition gas, for example, enumerated argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide and fluorohydrocarbon, for example, the potpourri of tetrafluoromethane and these gases.These processing are described in detail in Hatsumei KyokaiKokai Giho Kogi No.2001-1745 (March 15 calendar year 2001 is by Hatsumei Kyokai distribution), 30-32 page or leaf.The present atmospheric pressure of public attention Cement Composite Treated by Plasma use 10-1 down, the irradiation energy of 20-500 kGy under 000 keV is preferably the irradiation energy of 20-300kGy under the 30-500 keV.The surface treatment that is used for cellulose acylate film is handled in special preferred bases saponification.

The alkali soap processing preferably by directly in the saponification liquid bath, soak the method for cellulose acylate film or on cellulose acylate film the method for coating saponification liquor carry out.

Can use dip-coating, curtain coating, extrusion coated, rod is coated with and the coating of E-type as coating process.In order to be coated with saponification liquor on transparent carrier, the solvent that preferred saponification is handled with the alkali coating fluid has good wet performance, does not form inhomogeneity on the surface of transparent carrier, and can keep good surface properties.Special preferred alcohols solvent, especially preferred isopropyl alcohol.Also can use the aqueous solution of surfactant as solvent.In the preferred superincumbent solvent of the alkali of alkali soap coating fluid is alkali-soluble, and more preferably KOH and NaOH.The pH of alkali soap coating fluid preferably 10 or higher, and more preferably 12 or higher.Reaction conditions during alkali soap is room temperature and 1 second to 5 minute preferably, more preferably 5 seconds to 5 minute, especially preferred 20 seconds to 3 minute.After the alkali soap reaction, preferred water or acid, and then wash the surface that is coated with saponification liquor with water.

Anti-reflecting layer:

Preferably on the transparent protective film that is installed in the polaroid on the relative face of the face that provides liquid crystal cell, provide function film, for example, anti-reflecting layer.Specifically in the present invention, preferably use at the laminated anti-reflecting layer that comprises light scattering layer and low-index layer on the transparent protective film successively or on transparent protective film, comprise the laminated anti-reflecting layer of middle index layer, high refractive index layer and low-index layer successively.The preferred embodiment of anti-reflecting layer is described below.

Description is provided at the preferred embodiment of the anti-reflecting layer that comprises light scattering layer and low-index layer on the transparent protective film.

In light scattering layer of the present invention, and the refractive index of the component except that the delustring particle is preferably in the scope of 1.50-2.00 in light scattering layer with the delustring particle dispersion, and the refractive index of low-index layer is preferably in the scope of 1.35-1.49.In the present invention, light scattering layer plays the dual-use function of anti-dazzle and hard conating performance, and can comprise one deck or multilayer, for example, and layer 2-4.

Surface heterogeneity as anti-reflecting layer, decision design provides the average peak of the center line average roughness Ra of 0.08-0.40 μ m, 10 times of Ra or littler 10 mean roughness Rz, 1-100 μ m and paddy convex surface height and the standard deviation of deepest point, 20 μ m or littler average peak and the paddy apart from Sm, 0.5 μ m or littler inhomogeneity to have 10% or bigger surface apart from Sm and pitch angle as the standard deviation of the center line of standard and 0-5 °, can obtain the uniform delustring sensation of enough anti-dazzle performances and visual inspection thus.

By making catoptrical tone a under the illuminant-C ^*Value is-2 to 2, b ^*Value is for-3 to 3, and is 0.5-0.99 in the minimum value of the scope internal reflection rate of 380-780nm and the ratio of maximal value, and catoptrical tone becomes neutrality and is preferred.And, by making catoptrical b ^*Value is for 0-3, yellowly when white shows when anti-reflecting layer is used for image display reduces and is preferred.

When the standard deviation of the Luminance Distribution of measuring on lattice that inserts 120 μ m * 40 μ m between surface source of light and the anti-reflection film of the present invention and film is 20 or more hour, the dazzle when preferably film of the present invention being used for high precision plates reduces.

When anti-reflecting layer of the present invention has optical characteristics for example 2.5% or littler specular reflectance, 90% or bigger transmissivity and 70% or during littler 60 ° of glossiness, can limit external reflection of light and improve visibility.Specular reflectance is more preferably 1% or littler, and most preferably 0.5% or littler.By make haze value for the ratio of 20-50%, internal haze value/total haze value for 0.3-1, the haze value that provides haze value after the low-index layer when light scattering layer is provided reduce by 15% or littler, light comb width (comb breadth) during for 0.5mm the visibility of transmission image be the transmissivity of 20-50% and the transmitted light vertical and ratio with the transmissivity of the transmitted light of the direction of 2 ° of vertical banks is 1.5-5.0 with anti-reflecting layer, can prevent the dazzle on the high precision LCD plate and can realize fuzzy reduction such as letter.

Low-index layer:

The refractive index of the low-index layer of anti-reflection film of the present invention is 1.20-1.49, preferred 1.30-1.44.In order to reduce refractive index, preferred low-index layer satisfies following equation (XI).

(m/4)×0.7≤n ^-4d ^-4≤(m/4)×1.3 (XI)

In this equation, m represents positive odd number, n ^-4Represent the refractive index of low-index layer, d ^-4Represent the bed thickness (nm) of low-index layer, λ is the wavelength in the scope of 500-550nm.

Describe below and form the material that low-index layer is used.

Low-index layer of the present invention contains fluoropolymer as the low-refraction bonding agent.As fluoropolymer, preferably use kinetic friction coefficient as 0.03-0.20, with the contact angle of water as 90-120 ° and can be heated or the fall angle of pure water is 70 ° or the littler crosslinked fluoropolymer of ionising radiation.When being installed in anti-reflection film of the present invention on the image display, low more from the power of peeling off on the adhesive tape of commercially available acquisition, sticker, memo pad etc. bonding after them peel off easy more, preferred 5N or littler, more preferably 3N or littler, most preferably 1N or littler.And hard more with the skin hardness that the microhardness measuring instrument is measured, the surface almost can not be scratched, preferred 0.3GPa or bigger, more preferably 0.5GPa or bigger.

As the fluoropolymer that is used for low-index layer, for example have contain perfluoroalkyl silane compound (for example, (17 fluoro-1,1,2,2-tetrahydrochysene decyl)-triethoxysilane) hydrolysate and dehydration and condense product and comprise fluorine-containing monomer unit and the fluorinated copolymer of the structural unit of cross-linking reaction is provided.

The example of fluorochemical monomer comprises that fluoroolefins (for example, fluorothene, vinylidene fluoride, tetrafluoroethene, perfluoro capryl ethene, hexafluoropropylene, perfluor-2,2-dimethyl-1,3-dioxole etc.), (methyl) acrylic acid part and complete fluorinated alkyl ester derivant are (for example, Viscoat 6FM (making) by Osaka Organic Chemical Industry Ltd., M-2020 (making) etc.) by Daikin Industries Ltd., the vinyl ether of fluoridizing wholly or in part, from refractive index, dissolubility, transparency and availability aspect are considered, preferred fluoroolefins, preferred especially hexafluoropropylene.

As the structural unit that cross-linking reaction is provided, for example having can be by will having the monomer of the functional group of self-crosslinkable in advance in the molecule, for example, and the structural unit that (methyl) glycidyl acrylate and the polymerization of glycidyl vinyl ether obtain; The structural unit that monomer (for example, (methyl) acrylic acid, (methyl) acrylic acid hydroxyl methyl esters, (methyl) acrylic acid hydroxy alkyl ester, allyl acrylate, hydroxyethyl vinyl ether, hydroxy butyl vinyl ether, maleic acid, the crotonic acid etc.) polymerization with carboxyl, hydroxyl, amino or sulfo group can be obtained; With in these structural units, introduce for example structural unit that obtains of (methyl) acryloyl group (for example, cross-linking reaction group can by the technology introducing of acryloyl chloride and hydroxyl reaction) of cross-linking reaction group by polyreaction.

From the solubleness solvent with in order to give the angle of film clarity, except top fluorine-containing monomer unit with provide the structural unit of cross-linking reaction, the also not fluorine-containing monomer of copolymerization at random.The monomeric unit that can be used in combination has no particular limits, for example, can enumerate alkene (ethene, propylene, isoprene, vinyl chloride, vinylidene chloride etc.), esters of acrylic acid (for example, methyl acrylate, ethyl acrylate, 2-EHA etc.), methyl acrylic ester (for example, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, ethylene glycol dimethacrylate etc.), styrene derivative (for example, styrene, divinylbenzene, vinyltoluene, α-Jia Jibenyixi etc.), vinyl ethers (for example, methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether etc.), vinyl ester (for example, vinyl acetate, propionate, vinyl cinnamate etc.), acrylic amide (for example, N tert butyl acrylamide, N-cyclohexyl-acrylamide etc.), methacryl amine and acrylic nitrile derivates.

Hardening agent arbitrarily can be used for these polymkeric substance, as disclosed among JP-A-10-25388 and the JP-A-10-147739.

Light scattering layer:

In order to provide light scattering by surface light scattering and/or interior lights scattering and to provide hard conating to form light scattering layer with the mar resistance that improves film.Therefore, by containing bonding agent, the delustring particle that light scattering is provided that hard conating is provided and providing if necessary, increase refractive index, prevent that crosslinked contraction and the inorganic filler of gaining in strength from forming light scattering layer.

From hard conating being provided, preventing to produce the angle of curling and suppressing the brittleness reduction, the thickness of light scattering layer is 1-10 μ m preferably, more preferably 1.2-6 μ m.

As the bonding agent of light scattering layer, preferably have saturated hydrocarbon chain or polyether chain polymkeric substance, and more preferably have the polymkeric substance of saturated hydrocarbon chain as main chain as main chain.And binder polymer preferably has cross-linked structure.As having the binder polymer of saturated hydrocarbon chain, the polymkeric substance of preferred alkylene unsaturated monomer as main chain.As having saturated hydrocarbon chain, preferably has (being total to) polymkeric substance of the monomer of two or more alkylene unsaturated groups as main chain and binder polymer with cross-linked structure.In order to make binder polymer have high index of refraction, it is effective that use has at least a monomer that is selected from halogen atom, sulphur atom, phosphorus atoms and nitrogen-atoms except that fluorine atom.

Example with monomer of two or more alkylene unsaturated groups (for example comprises polyvalent alcohol and (methyl) acrylic acid ester; ethylene glycol bisthioglycolate (methyl) acrylate; butylene glycol two (methyl) acrylate; hexanediol two (methyl) acrylate; 1; 4-cyclohexane diacrylate; pentaerythrite four (methyl) acrylate; pentaerythrite three (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; trimethylolethane trimethacrylate (methyl) acrylate; dipentaerythritol four (methyl) acrylate; dipentaerythritol five (methyl) acrylate; dipentaerythritol six (methyl) acrylate; pentaerythrite six (methyl) acrylate; 1; 2; 3-cyclohexane four (methyl) acrylate; polyurethane polyureas acrylate and polyester polyacrylate); the product of the ethylene oxide modification of above-mentioned monomer; vinyl benzene and derivant thereof are (for example; 1; the 4-divinylbenzene; 4-vinyl benzoic acid-2-acryloyl group-ethyl ester and 1; 4-divinyl cyclohexanone); vinyl sulfone (for example; divinylsulfone); acrylamide (for example, methylene two-acrylamide); and Methacrylamide.These monomers can two or more mix use.

As the instantiation of high refractive index monomers, two (4-methacryl thiophenyl) thioether, vinyl-naphthalene, ethenylphenyl thioether and 4-methacryloxy phenyl-4-methoxyphenyl thioether are for example arranged.These monomers also can two or more mix use.

Polyreaction with these monomers of alkylene unsaturated group can be undertaken by ionization radiation irradiation or heating under the situation that optical free radical polymerization initiator or hot radical polymerization initiator are arranged.

Therefore, can be by following formation anti-reflection film: preparation contains the coating fluid of monomer, optical free radical polymerization initiator or hot radical polymerization initiator, delustring particle and the inorganic filler of band alkylene unsaturated group, this coating fluid is applied on the transparent carrier, carries out polyreaction by ionization radiation irradiation or heating then and thus coating is solidified.Can use known optical free radical polymerization initiator.

As having the polymkeric substance of polyether chain, the ring-opening polymerization polymer of the epoxy compound of preferred function groups as main chain.The ring-opening polymerization of the epoxy compound of function groups can carry out by ionization radiation irradiation or by heating under the situation that photoacid generator or hot acid agent are arranged.

Therefore, the coating fluid that can contain epoxy compound, photoacid generator or hot acid agent, delustring particle and the inorganic filler of function groups by preparation, this coating fluid is applied on the transparent carrier, carries out polyreaction by ionising radiation or heating then and solidify this coating thus and form anti-reflection film.

Replace having the monomer of two or more alkylene unsaturated groups or except this monomer, use has the monomer of crosslinkable functionality can introduce crosslinkable functionality in polymkeric substance, and can introduce cross-linked structure by the reaction of these crosslinkable functionalities in binder polymer.

The example of crosslinkable functionality comprises isocyanate group, epoxy radicals, a word used for translation '-aziridino,  azoles quinoline base, aldehyde radical, carbonyl, diazanyl, carboxyl, methylol and active methylene group.Also can use vinyl sulfonic acid, acid anhydrides, cyanacrylate derivant, melamine, etherificate methylol, ester and urethane and metal alcoholate, tetramethoxy-silicane for example is as adding the monomer that cross-linked structure is used.Also can use decomposition reaction to cause showing the functional group of bridging property, blocked isocyanate base for example is as crosslinkable functionality.That is, in the present invention, crosslinkable functionality can be to decompose to cause showing reactive those crosslinkable functionalities, and is reactive even they do not show immediately.

The binder polymer that has these crosslinkable functionalities by coating heats then, can form cross-linked structure.

In order to give anti-dazzle photosensitiveness, containing mean grain size in the light scattering layer is 1-10 μ m, the delustring particle of preferred 1.5-7.0 μ m, and for example inorganic compound particle or resin particle are big than filler particles for they.

As the instantiation of delustring particle, for example preferably have inorganic compound particle, for example, silica dioxide granule and TiO ₂Particle and resin particle, for example, acrylic particles, crosslink propylene granulates, granules of polystyrene, cross-linked styrene particle, melamine resin particle and benzoguanamine resin particle.In these particles, preferred cross-linked styrene particle, crosslink propylene granulates, crosslink propylene base styrene particle and silica dioxide granule.The delustring particle can be spherical or amorphous.

And the delustring particle that two or more can be had separately different-grain diameter uses together.Big delustring particle can give anti-dazzle photosensitiveness and less delustring particle can be given other optical property.

The delustring particle grain size distribution most preferably is single dispersion.All particle grain size are preferably equal as far as possible.With particle diameter ratio mean grain size big 20% or more particles as coarse particle, coarse grained ratio preferably all amounts of particles 1% or littler, more preferably 0.1% or littler, even more preferably 0.01% or littler.Delustring particle with this size distribution obtains by classification after the common synthetic reaction.By increasing the classification number of times or improving grade, can obtain to have the more preferably delustring particle of size distribution.

Add the content 10-1 preferably in the light scattering layer that this delustring particle make to form, 000mg/m ², more preferably 100-700mg/m ²

Measure the delustring particle grain size distribution and convert the size distribution of measuring to the granule number distribution with the Coulter-counter method.

In order to increase the refractive index of this layer, except the delustring particle, preferably inorganic filler is joined in the light scattering layer.For example, the preferred use comprises that at least a oxide and the mean grain size that is selected from the metal of titanium, zirconium, aluminium, indium, zinc, tin and antimony is 0.2 μ m or littler, preferred 0.1 μ m or littler, more preferably 0.06 μ m or littler inorganic filler.

In contrast, in containing the light scattering layer of high index of refraction delustring particle,, also preferably use the oxide of silicon for the refractive index that keeps this layer is low slightly with the refractive index difference between the raising delustring particle.Preferred particle diameter is identical with top inorganic filler.

The instantiation that is used for the inorganic filler of light scattering layer comprises TiO ₂, ZrO ₂, Al ₂O ₃, In ₂O ₃, ZnO, SnO ₂, Sb ₂O ₃, ITO and SiO ₂In order to increase the especially preferred TiO of refractive index ₂And ZrO ₂Handle with silane coupling agent or titanium coupling agent on the surface of also preferred inorganic filler, and preferred on the surface of filler, use have can with the surface conditioning agent of the functional group of adhesive reaction.

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

The particle diameter ratio light wavelength of these fillers is much smaller, light scattering can not take place like this, and the dispersion that comprises the binder polymer that wherein is dispersed with these fillers plays the optics homogeneous material.

Total refractive index of the potpourri of bonding agent and inorganic filler preferably 1.48-2.00, more preferably 1.50-1.80 in the light scattering layer.By selecting bonding agent and the kind of inorganic filler and the refractive index that quantitative proportion can obtain top scope.This selection can easily be recognized in advance by rule of thumb.

In order to guarantee even face performance, for example, anti-coating inhomogeneity, anti-drying mark and anti-point defect, light scattering layer contains surfactant, for example, in forming the coating composition that anti-dazzle photosphere uses, contain the surfactant of fluorine surfactant or silicone surfactant or the two all contains.Because fluorine surfactant just has the effect of the planar defect of improvement anti-reflection film of the present invention as coating inhomogeneity, drying mark and point defect with less addition, therefore especially preferably use fluorine surfactant.The purpose that adds fluorine surfactant is to increase throughput rate by the high-speed coating performance, increases the homogeneity of face performance simultaneously.

Next, description comprises the laminated successively anti-reflecting layer that the transparent protective film of middle index layer, high refractive index layer and low-index layer is arranged on it.

Design comprise have successively on the matrix at least in index layer, high refractive index layer and low-index layer (outermost layer) layer structure anti-reflecting layer with have satisfy below shown in the refractive index of relation.

The refractive index of the refractive index 〉=low-index layer of the refractive index 〉=transparent carrier of the refractive index of high refractive index layer 〉=middle index layer.

Between transparent carrier and middle index layer, can provide hard conating.And this anti-reflecting layer can comprise middle refractive index hard conating, high refractive index layer and low-index layer.(referring to JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906 and JP-A-2000-111706.) each layer can have other function, and as these examples, for example, enumerate antifouling low-index layer and electrostatic prevention high refractive index layer (for example, JP-A-10-206603 and JP-A-2002-243906).

The haze value of anti-reflecting layer preferably 5% or littler, more preferably 3% or littler.The pencil hardness test of film strength by JIS K5400 be H or higher, more preferably 2H or higher, most preferably 3H or higher preferably.

High refractive index layer and middle index layer:

The layer that has high index of refraction in the anti-reflection film comprises and contains the ultra-fine grain that at least a mean grain size is 100nm or littler high index of refraction mineral compound and the dura mater of matrix binder.

As the mineral compound particulate with high index of refraction, having enumerated refractive index is 1.65 or bigger, and preferred index is 1.9 or bigger mineral compound.For example, enumerate the oxide of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In etc. and contain the composite oxides of these metallic atoms.

In order to obtain this ultra-fine grain, (for example enumerated useful surface conditioning agent, use JP-A-11-295503, disclosed silane coupling agent among JP-A-11-153703 and the JP-A-2000-9908, with disclosed anionic compound among the JP-A-2001-310432 or organic metal coupling agent) surface of handling these particles, obtain the nuclear core/shell mechanism (JP-A-2001-166104 and JP-A-2001-310432) of high refractive index particle as the nuclear core, and be used in combination specific dispersant (JP-A-11-153703, U.S.Patent 6,210,858 and JP-A-2002-2776069).

As the material that forms matrix, known thermoplastic resin and thermoset resin have been enumerated.

And, the preferred at least a following composition that is selected from: contain the function groups compound compositions of at least two polymerizable groups in band free redical polymerization group and/or the cationically polymerizable group and contain the organometallics of being with hydrolyzable groups and the composition of the part condensation product of this compound.For example, enumerated disclosed composition among JP-A-2000-47004, JP-A-2001-315242, JP-A-2001-31871 and the JP-A-2001-296401.

And the also cured film that obtains of the colloidal metal oxide that preferably can be obtained by hydrolysis and the condensation product with metal alkoxide and metal alkoxide compositions is as disclosed among the JP-A-2001-293818.

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

The refractive index of middle index layer is adjusted between the refractive index of the refractive index of low-index layer and high refractive index layer.The refractive index of middle index layer is 1.50-1.70 preferably.The thickness of middle index layer is 5nm-10 μ m, more preferably 10nm-1 μ m preferably.

Low-index layer:

Low-index layer is laminated on the 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 forms with the outermost layer with mar resistance and soil resistance.As the mode that significantly improves mar resistance, give this surface sliding and be effectively, and can adopt to provide as this mode and comprise the thin layer of introducing known siloxane and introducing fluorine.

The refractive index of fluorochemicals is 1.35-1.50 preferably, more preferably 1.36-1.47.As fluorochemicals, the crosslinkable or polymerisable functional group of preferred contain fluorine atoms accounts for the compound of 35-80 quality %.

For example, as this compound, enumerated JP-A-9-222503 [0018] to [0026] section, JP-A-11-38202 [0019] to [0030] section, among JP-A-2001-40284 [0027] and [0028] section and the JP-A-2000-284102 disclosed compound.

Silicone compounds is the compound with polysiloxane structure, and those compounds that preferably have curable functional group or polymerizable functional group in polymer chain, have cross-linked structure in film.For example, the polysiloxane of enumerating responding property siloxane (for example, Silaplane is made by ChissoCorporation) and containing silanol group at two ends (for example, JP-A-11-258403).

Preferably have the cross-linking reaction of fluorine-containing and/or siloxane polymer of crosslinkable groups or polymerizable groups or polyreaction and be coating contain the coating composition that is used to form outermost polymerization initiator and emulsion after rayed or heating simultaneously or carry out at once afterwards.

Also preferably have under the situation of catalyzer by containing specific hydrofluorocarbons organometallics for example the condensation reaction of silane coupling agent and silane coupling agent solidify the cured film that transforms through collosol and gel.

For example, enumerate the partial hydrolysis condensation product (disclosed compound among JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, JP-A-9-157582 and the JP-A-11-106704) of the silane compound that contains poly-fluoroalkyl or this compound and contain poly-(perfluoroalkyl ethers) base, that is the silyl compound of fluorine-containing long chain alkyl group (disclosed compound among JP-A-2000-117902, JP-A-2001-48590 and the JP-A-2002-53804).

Except top adjuvant, the mean grain size that low-index layer can contain primary granule is that for example filler is (for example for the low-refraction mineral compound of 1-150nm, silicon dioxide (silica)), fluorine-containing particle (for example, magnesium fluoride, calcium fluoride, barium fluoride), JP-A-11-3820 [0020] are to the disclosed organic particulate of [0038] section, silane coupling agent, antiseize paste and surfactant.

When forming low-index layer as surface layer under outermost, low-index layer can form (for example, vacuum deposition method, sputtering method, ion plating, plasma CVD method) by vapor phase method.From the preferred rubbing method of the angle that can prepare inexpensively.

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

And, hard conating, direct scattering layer, prime coat, antistatic backing, internal coating and protective seam can be provided.

Hard conating:

To provide the transparent protective film of anti-reflecting layer physical strength in order giving, on the surface of transparent carrier, to provide hard conating.Particularly preferably in providing hard conating between transparent carrier and the high refractive index layer.Hard conating preferably by light-and/or the cross-linking reaction or the polyreaction of heat-curable compound provide.As curable functional group, preferred light-polymerizable functional group, and conduct contains the organometallics of the functional group of hydrolyzable decomposition, preferred organic polyglycidyl compounds.

The instantiation of these compounds can be enumerated just like the same compound shown in the high refractive index layer.The specific composition composition of hard conating for example is disclosed among JP-A-2002-144913, JP-A-2000-9908 and the WO 00/46617.

The high refractive index layer effect of hard conating of can having held concurrently.When high refractive index layer has been held concurrently time spent of doing of hard conating, preferably form hard conating by in hard conating, adding particulate as fine dispersions according to the method described in the high refractive index layer.

Hard conating is the effect (back is described) of anti-dazzle photosphere with anti-dazzle function of can having held concurrently of the particle of 0.2-10 μ m by containing mean grain size.

The thickness of hard conating can suitably design according to purpose.The thickness of hard conating is 0.2-10 μ m preferably, more preferably 0.5-7 μ m.

According to the hardness of the pencil hardness test hard conating of JIS K5400 preferably H or higher, more preferably 2H or higher, most preferably 3H or higher.In according to the taper of JIS K5400 test, sample strip before test and wearing and tearing afterwards preferably as far as possible little.

Antistatic backing:

When antistatic backing was provided, preferably giving specific volume resistance was 10 ^-8(Ω cm ^-3) or littler conductivity.Use hygroscopic materials, water-soluble inorganic salt, some surfactant, cationic polymer, anionic polymer and cataloid can provide 10 ^-8(Ω cm ^-3) or littler specific volume resistance, but to be the temperature and humidity dependence big and can not obtain enough conductivity under low humidity for the problem that exists.Therefore, the preferable alloy oxide is as conductive material.Nonferrous metal oxides is arranged, but when using this nonferrous metal oxides as conductive material, film is also coloured usually, therefore not preferred, the metal that does not have the metal oxide of color as formation, can enumerate Zn, Ti, Al, In, Si, Mg, Ba, Mo, W and V, and preferred the use contained the metal oxide of these metals as principal ingredient.

As instantiation, preferred ZnO, TiO ₂, SnO ₂, Al ₂O ₃, In ₂O ₃, SiO ₂, MgO, BaO, MoO ₃, V ₂O ₅, or their composite oxides, preferred especially ZnO, TiO ₂And SnO ₂As the example that contains other kind atom, for example, Al and In are joined among the ZnO, Sb, Nb and halogen atom are joined SnO ₂In and Nb and TA joined TiO ₂In be effective.And, as disclosed among the JP-B-59-6235, can use top metal oxide is adhered to other crystal metal particle or the last material that obtains of fibrous matter (for example, titanium oxide).

Can not easily compare although volume resistance value and sheet resistance value are different physical values and they, be 10 in order to guarantee specific volume resistance ^-8(Ω cm ^-3) or littler conductivity, conductive layer has 10 usually ^-10(Ω/) or littler, more preferably 10 ^-8(Ω/) or littler sheet resistance value are just enough.The sheet resistance value of conductive layer must be measured as outermost value with antistatic backing, and the measurement midway that this value can described in this manual formation laminate film.

LCD:

Cellulose acylate film, comprise the optical compensating gage of this film and use the polaroid of this film to can be used for the liquid crystal cell and the LCD of various display modes; and various display modes have been proposed; for example, TN (twisted-nematic), IPS (face internal conversion), FLC (ferroelectric liquid crystals), AFLC (anti-ferroelectric liquid crystals), OCB (optical compensation curved), STN (supertwist is to row), VA (vertical orientated) and HAN (hybrid orientation is to row).In these patterns, optical material of the present invention can be preferred for OCB type or VA type.

OCB type liquid crystal cell is to use in the top and bottom of liquid crystal cell the LCD of the liquid crystal cell of the curved orientation type of reverse direction (symmetry) orientation rod shaped liquid crystal molecule basically, and is disclosed in United States Patent (USP) 4,583, in 825 and 5,410,422.Because rod shaped liquid crystal molecule is in the top and bottom of liquid crystal cell symmetric orientation, so the liquid crystal cell of curved orientation type has from optical compensation function.Therefore, this liquid crystal type is also referred to as OCB (optical compensation curved) liquid crystal type.The LCD of curved orientation type has the fast advantage of reaction velocity.

In VA type liquid crystal cell, when not applying voltage, rod shaped liquid crystal molecule perpendicular orientation.

VA type liquid crystal cell comprise (1) when not applying voltage perpendicular orientation rod shaped liquid crystal molecule and when applying voltage the substantial horizontal orientation narrow sense VA type liquid crystal cell (for example, JP-A-2-176625), (2) has VA type multidomain (MVA type) to enlarge the liquid crystal cell (SID97 at visual angle, Digest of Tech.Papers, (rough draft) 28, described in 845 (1997)), perpendicular is not orientated rod shaped liquid crystal molecule and liquid crystal cell (n-ASM type) (the Liquid Crystal Forum of the type that the distortion multidomain is orientated when applying voltage when (3) not applying voltage, Japan is described in the rough draft of 58-59 (1998)), (4) SURVAIVAL type liquid crystal cell (open) at LCD International 98.

VA type LCD comprises two polaroids arranging on the two sides of liquid crystal cell and liquid crystal cell.Liquid crystal cell is loaded with liquid crystal between two electrodes.In an embodiment of transmission type lcd device of the present invention, a slice optical compensating gage of the present invention is installed between liquid crystal cell and the polaroid, and perhaps two optical compensating gages all are installed between liquid crystal cell and two polaroids.

In another embodiment of transmission type lcd device of the present invention, use the optical compensating gage that comprises cellulose acylate film of the present invention as the transparent protective film that is installed in the polaroid between liquid crystal cell and the polarizer.This optical compensating gage can or can be used for two transparent protective films (polaroid is between liquid crystal cell and polarizer) of two polaroids as the protective film of the polaroid of a side (polaroid is between liquid crystal cell and the polarizer) only.When optical compensating gage being used for the polaroid of a side only, especially preferably use this sheet as protective film in the liquid crystal cell side of the polaroid of liquid crystal cell backlight side.Preferably make cellulose acylate film of the present invention during adhesion on the VA component side.Protective film can be the plain acylate film of general fibre, but preferably thin than cellulose acylate film of the present invention.For example, the thickness of preferred 40-80 μ m, and enumerate KC4UX2M (the 40 μ m of commercially available acquisition, by Konica Opto, Inc. manufacturing), (80 μ m are by Fuji Photo Film Co. for KC5UX (60 μ m are made by Konica Opto Co.) and TD80, Ltd. make), but the present invention is not limited to this.

Embodiment

Describe the present invention with reference to embodiment, but the present invention is not limited to this.

Measuring method:

Measure the various features of cellulose acylate film by the following method.Postpone Re, Rth:

Delay is to measure with birefringence refractometer KOBRA 21ADH (being made by Oji Scientific Instruments) at the light of the normal direction projection wavelength X nm of film.Effective value 1.48 and thickness by the input mean refractive index, with the length of delay of three orientation measurements of top Re (λ), with retardation axis in the face as sloping shaft from the normal direction with film tilt length of delay that+40 ° the light of direction projection wavelength X nm measures and based on retardation axis in the face as sloping shaft from the length of delay that-40 ° the light of direction projection wavelength X nm measures that tilts of the normal direction with film, calculating Rth (λ).

Moisture:

Sample humidity under 25 ℃ of 80%RH of 7mm * 35mm was nursed one's health 2 hours, and measured moisture with Karl Fischer method micro-moisture instrument LE-20S (by Hiranuma Sangyo Co., Ltd. makes).The amount of moisture (g) of sample is calculated moisture divided by the quality (g) of sample.

Thermal Contraction Coefficient:

With the sample of 30mm * 120mm under 25 ℃ of 60%RH through 2 hours.Beat the hole of 6mm  with the interval of 100mm on the two sides of sample, and full-scale with the distance (L1) between automatic pin gauge (by Shinto Scientific Co., the Ltd. makes) measured hole to 1/1, the minimum scale of 000mm.Sample also 60 ℃ of 90%RH or under 90 ℃ of 3%RH through 24 hours, again under 25 ℃ of 60%RH through 2 hours, and the size between the measured hole (L2).With [(L1-L2)/L1] * 100 calculating Thermal Contraction Coefficients.

Glass temperature Tg:

Sample (unstretched) humidity under 25 ℃ of 60%RH of 5mm * 30mm was nursed one's health 2 hours or bigger, and with automatic viscoelasticity measurement instrument (Vibron, DVA-225, make by ITKeisoku Seigyo Co.) under the frequency of the programming rate of the distance between the clip (holding point) of 20mm, 2 ℃/min, 30 ℃-200 ℃ measurement temperature range and 1Hz, measure viscoelasticity, and with the storage elastic modulus be logarithmic axis on the axis of ordinates and temperature (℃) as the transverse axis on the abscissa axis measured value is drawn.At this moment, when carrying out the transition to the glass zone of transition, solid area sees that at the storage elastic modulus storage elastic modulus reduces suddenly, in solid area setting-out 1 and in glass zone of transition setting-out 2.The temperature that the storage elastic modulus reduced suddenly and film begins to soften when the point of crossing of line 1 and line 2 was the temperature rising, it is the temperature that begins to move on to the glass zone of transition, so this point is considered to glass temperature Tg (dynamics viscoelasticity).

The quantity of bright spot inclusion:

Above the sample thin film and following polaroid be adjusted to intersect the state of Nicol, with polarizing microscope with 50 enlargement ratios at 30 some observation samples, and by the record 1,280 * 1,024 density is with digital image recording, and this moment, viewing area was 2.16mm * 1.72mm.The image enlargement ratio is adjusted to 108mm * 86mm, observes image with personal computer, the major axis that dodges white light on the counting diagram picture is the quantity of 1mm or bigger inclusion, the quantity of the inclusion of 30 points in each sample is gathered and counts the data of measurement.Filter blockage factor:

With the cellulose acylate solution process filter paper (aperture: 47 μ m, thickness: 1.32mm, density: 0.32g/m under the flow velocity of 7ml/min that remains on 36 ℃ ³) filter, described filter paper is supported by the ring-type porous plate in the hole that to provide 61 diameters be 3.8mm, and useful area is 12.5cm ²When filter pressure was stablized temporarily, the pressure of observing 3.5-4 hour increased.With the filtration time is transverse axis and PO/P ^0.64For the longitudinal axis is drawn, and find the curve approximation straight line.P and PO are meant filter pressure and inceptive filtering pressure.

The slope substitution of filtering blockage factor Ks and be the straight line that will find is filtered blockage factor equation [Ks=3.5 * slope] and is obtained.Here, the aperture of used filter paper is the value by the foaming point value calculating of filter paper.Using gear-type pump KA1 (by Kawasaki HeavyIndustries, Ltd. makes) to carry out liquid feeds in raw material.

Elastic modulus:

Sample humidity under 25 ℃ of 60%RH of 10mm * 200mm was nursed one's health 2 hours, and calculate by stress and the length growth rate that initially draws, wherein initial sample length is that 100mm and draw speed are 100mm/min, the stretching measuring instrument is Strograph R2 (by ToyoSeiki Seisaku-Sho, Ltd. makes).

The photoelasticity modulus:

At long axis direction the film sample of 10mm * 100mm is applied drawing stress, and measure the Re of this moment with ellipsometer M150 (making) and postpone by JASCO Corporation.By the change calculations photoelasticity modulus that postpones with stress.

Mist degree:

Measure the mist degree of sample under 25 ℃ of 60%RH of 40mm * 80mm according to JIS K6714 with mist degree instrument HGM-2DP (by Suga Test Instruments Co., Ltd. makes).

Embodiment 1

The preparation of cellulose acylate film

(1) cellulose acylate

Preparation has the cellulose acylate film of the degree of substitution of different acyl shown in the table 1.Can be by using sulfuric acid as catalyzer; add carboxylic acid and carboxylic acid anhydrides that acylation reaction is used; neutralization then, saponification and slaking prepare cellulose acylate film; but, can obtain to have the cellulose acylate of degree of substitution, bulk density and the degree of polymerization of various complete degree of substitution, 6-position by changing catalyzer, the addition of neutralizing agent, the addition of water, temperature of reaction, curing temperature.Remove lower-molecular-weight component in every kind of cellulose acylate with washing with acetone.

(2) preparation of dope

＜1-1〉cellulose acylate solution

Following composition is put into mixing channel, and each component of stirring and dissolving about 10 minutes of 90 ℃ of heating, is that the filter paper of 34 μ m quantitatively filters with average pore size then.The filtration blockage factor that calculates each sample is at 200-500m ^-3Between.Each solution through filter paper filtering is the sintered metal filter filtration of 10 μ m again with average pore size.

Cellulose acylate solution:

Cellulose acylate 100.0 mass parts shown in the table 1

Triphenyl phosphate 8.0 mass parts

Xenyl diphenyl phosphoester 4.0 mass parts

Methylene chloride 403.0 mass parts

Methyl alcohol 60.2 mass parts

＜1-2〉dispersion liquid of matting agent

The following composition that will contain the cellulose acylate solution that makes in top mode is put into the dispersion liquid of decollator preparation matting agent.

The dispersion liquid of matting agent:

Mean grain size is the silica dioxide granule (Aerosil R972,2.0 mass parts are by Nippon Aerosil Co., Ltd. makes) of 16nm

Methylene chloride 72.4 mass parts

Methyl alcohol 10.8 mass parts

Cellulose acylate solution 10.3 mass parts

＜1-3〉delay dose solution A

The following composition that will contain the cellulose acylate solution that makes in top mode is put in the mixing channel, and under agitating heating said composition is dissolved, and makes to postpone the dose solution A.

Postpone the dose solution A:

Postpone dose A 20.0 mass parts

Methylene chloride 58.3 mass parts

Methyl alcohol 8.7 mass parts

Cellulose acylate solution 12.8 mass parts

The delay dose solution A of the matting agent dispersion liquid of the top cellulose acylate solution of 100 mass parts, 1.35 mass parts and the ratio shown in the following table 2 is mixed as to be used to prepare the dope of film.The gained dope is used to prepare film F 1-F5 and F8-F14.Postpone dose A

＜1-4〉delay dose solution B

The following composition that will contain the cellulose acylate solution that makes in top mode is put in the mixing channel, and under agitating heating said composition is dissolved, and makes to postpone the dose solution B.

Postpone the dose solution B:

Postpone dose A 8.0 mass parts

Postpone dose B 12.0 mass parts

Methylene chloride 58.3 mass parts

Methyl alcohol 8.7 mass parts

Cellulose acylate solution 12.8 mass parts

The delay dose solution B of the matting agent dispersion liquid of the top cellulose acylate solution of 100 mass parts, 1.35 mass parts and the ratio shown in the following table 2 is mixed as to be used to prepare the dope of film.The gained dope is used to prepare film F 6 and F7.

The amount of the cellulose acylate of corresponding 100 mass parts, table 2 have shown the adding proportion in the delay dose of mass parts.Table 2 has also shown the viscosity of each dope under 33 ℃.

Postpone dose B

(curtain coating)

With the dope above the band casting machine curtain coating.When amount of residual solvent is 25-35 quality %,, obtain cellulose acylate film thus from stretching with stenter at the draw ratio (shown in the table 2) of Width with 15-25% with the film of peeling off.In stenter by in the blowing hot-air drying after Width stretches, it is about 5% that film shrinks, be transported on the roller from stenter further dry, embossing, and with 1, the width of 500mm is rolled.As draw ratio, table 2 has shown the value of being calculated by thin-film width at the entrance and exit of stenter.

Table 1

Remarks	The cotton material numbering	Degree of substitution with acetyl group	The propiono degree of substitution	The degree of substitution of 6-position	The degree of substitution of 6-position/total degree of substitution	The degree of polymerization	Bulk density (kg/liter)
								Comparative Examples	CA1	2.849	0.000	0.934	0.328	260	0.61
Comparative Examples	CA2	2.847	0.000	0.947	0.333	207	0.72
								The present invention	CA3	2.785	0.000	0.910	0.327	302	0.455
The present invention	CA4	2.753	0.000	0.903	0.328	291	0.68
								The present invention	CA5	2.745	0.000	0.882	0.321	324	0.64
The present invention	CA6	1.952	0.808	0.897	0.325	287	0.55
								Comparative Examples	CA7	2.860	0.000	0.887	0.310	369	0.515
The present invention	CA8	2.794	0.000	0.902	0.323	294	0.32

Total degree of substitution is the acyl substituted degree sum of 2-position, 3-position and 6-position.Total degree of substitution is suitable with the value of passing through degree of substitution with acetyl group and propiono degree of substitution addition acquisition.

Measure Re length of delay and the Rth length of delay of cellulose acylate film (optical compensating gage) under the wavelength of 25 ℃ of 60%RH and 630nm that makes with birefringence refractometer KOBRA 21ADH (making) by Oji Scientific Instruments.And, make film humidity conditioning 2 hours or longer time under 25 ℃ of 10%RH and 25 ℃ of 80%RH, Re length of delay of measuring respectively at 630nm and Rth length of delay.Δ Re and Δ Rth are counted in the variation of the delay of the cellulose acylate film from 80%RH to 10%RH (Re (10%RH)-Re (80%RH) and Rth (10%RH)-Rth (80%RH)), and are shown in table 2.Measure the thickness of Width with continuous thickness gauge (by Anritsu Denki Co., Ltd. make), and will remove that the maximum film thickness variation is shown in table 2 between the poor and 10mm of thickness of the whole width of embossed portion dividing.And, the quantity of measurement bright spot inclusion.Gained the results are shown in table 2.

Table 2

Film number	The cotton material numbering	Used delay dose solution	The addition (mass parts) that postpones dose	Dope viscosity (Pas)	Draw ratio (%)	Average film thickness (μ m)	The maximum ga(u)ge of Width poor (μ m)	Maximum ga(u)ge between the Width 10mm changes	Re (nm)	Rth (nm)	ΔRe (nm)	ΔRth (nm)	Remarks
														F1	CA3	-	0.0	17	20	92	3.4	0.5	16	114	12.1	41.0	Comparative Examples
F2	CA7	A	5.0	68	25	92	4.6	0.6	45	189	10.4	28.6	Comparative Examples
														F3	CA3	A	6.0	16	15	92	3.8	0.6	62	234	8.3	26.6	Embodiment
F4	CA3	A	5.0	16	25	86	3	0.5	62	225	10.5	27.9	Embodiment
														F5	CA1	A	6.5	9	23	92	5.8	0.7	63	209	10.5	29.3	Comparative Examples
F6	CA3	B	6.5	16	15	110	2.7	0.6	63	223	9.9	29.8	Embodiment
														F7	CA3	B	6.5	16	20	92	3.5	0.5	68	248	8.9	29.1	Embodiment
F8	CA3	A	6.5	16	20	89	3.2	0.5	65	240	9.2	24.7	Embodiment
														F9	CA8	A	7.5	22	25	92	2.4	0.4	66	202	8.5	26.2	Embodiment
F10	CA2	A	6.5	7	23	92	7.2	0.9	66	211	10.6	28.7	Comparative Examples
														F11	CA4	A	5.0	14	18	92	3.4	0.6	70	228	8.6	28.4	Embodiment
F12	CA5	A	5.0	25	18	92	2.2	0.4	72	235	8.6	30.8	Embodiment
														F13	CA3	A	5.0	16	20	92	3.4	0.6	74	220	8.8	28.2	Embodiment
F14	CA6	A	5.0	11	23	92	4.5	0.5	81	163	9.2	30.4	Embodiment

The glass temperature of each film (Tg) is between 138-147 ℃.Moisture under 25 ℃ of 80%RH after the humidity conditioning is between 2.9%-3.4%.The seepage rate of film is 800-2 after 60 ℃ of 95%RH left standstill 24 hours, 000g/m ²/ 24hr.The mist degree of all films all is 0.1-0.9.The average secondary particle diameter of delustring particle is 1.0 μ m or littler, tensile modulus of elasticity is 4GPa or bigger, mass change after 80 ℃ of 90%RH leave standstill 48 hours is 0-3%, change in size after 60 ℃ of 90%RH and 90 ℃ of 3%RH leave standstill 24 hours is-1.2% to 0.2%, and the photoelasticity modulus of each sample is 50 * 10 ^-13Cm ²/ dyn (5 * 10 ^-11m ²/ N) or littler.

The preparation dry thickness is 1.5 times (that is 138 μ m) and the film of 1.9 times (176 μ m) of the size of optical thin film F13 shown in the table 2.Re and Rth almost increase pro rata with thickness, and seepage rate and thickness are inversely proportional to.The value of the humidity dependence of Re and Rth, Δ Re and Δ Rth, glass temperature Tg and moisture is identical, and is irrelevant with thickness.

Change wavelength and under the ambient humidity of 25 ℃ of 60%RH, use ellipsometer M150 (making) measure R e and Rth by JASCO Corporation.According to measured value, the sample of embodiments of the invention satisfies requirement of the present invention (46≤Re (630)≤200,70≤Rth (630)≤350, and the variation in thickness of Width is 0.6 μ m or littler) as can be seen, and comparative sample does not satisfy.And except that F1, all optical thin films are 0.90≤Re (450)/Re (550)≤1.10 and 0.90≤Re (650)/Re (550)≤1.10,0.90≤Rth (450)/Rth (550)≤1.25 and 0.90≤Rth (650)/Rth (550)≤1.10.

On the other hand, F10 is 7≤Re (450)/Re (550)≤0.8,1≤Re (650)/Re (550)≤1.2,0.90≤Rth (450)/Rth (550)≤1.25 and 0.90≤Rth (650)/Rth (550)≤1.10.

As for film number is the sample thin film of F4, the physical property of the processing conditions when having gathered curtain coating below, the film of acquisition and the details of measuring condition.

Processing conditions:

Amount of residual solvent when peeling off: 35 quality %

Zone tensile force: 100N/m

(zone termination) finished in the zone: methyl alcohol/(methylene chloride+methyl alcohol) 26 quality %

The draw speed of operation C: 24%/min

The environment temperature of operation C: 140 ℃

The stretching ratio of operation C: 1.25 times

Film temperature when stretching beginning: 47 ℃

Amount of residual solvent when beginning to stretch: 34 quality %

Film temperature when stretching end: 108 ℃

The termination that stretches: methyl alcohol/(methylene chloride+methyl alcohol): 4 quality %

Concentration dichloromethane in the environment of process B: 18 volume %

Concentration dichloromethane in the environment of operation C: 18 volume % remarks)

Operation A: cast film is peeled off the operation that afterwards film is transported to stenter

Process B: the operation that keeps end portion at the Width of stenter

Operation C: in the operation of the Width oriented film of stenter

Measuring method:

Amount of residual solvent: amount of residual solvent in the film: [(A-B)/A] * 100

A: the weight during the film sampling

B: the weight of film after 120 ℃ of dryings 2 hours

The ratio of methyl alcohol, methylene chloride

With methylene chloride in the vapor-phase chromatography MEASUREMENTS OF THIN and methyl alcohol

The physical property of gained film is as follows.

Re：62nm

Rth：225nm

The distribution of the angle of orientation: ± 0.5 ° or littler

Postpone the distribution of (Re): 2.7%

Postpone the distribution of (Rth): 1.3%

Thickness (aVe): 86.0 μ m

Maximum film thickness (max): 87.6 μ m

Minimum thickness (min): 84.6 μ m

Mist degree: 0.7%

Change in size (MD) :-0.05%

Change in size (TD) :+0.08%

Tear strength (MD): 23g

Tear strength (TD)+28g

Elastic modulus (MD): 400kgf/mm ²

Elastic modulus (TD): 487kgf/mm ²

Breakpoint stress (MD): 7.9kgf/mm ²

Breakpoint stress (TD): 11kgf/mm ²

Breakpoint draw ratio (MD): 17%

Breakpoint draw ratio (TD): 12%

Measuring method:

A) angle of orientation distributes

Surveying instrument: KOBRA 21ADH (Oji Scientific Instruments) temperature and relative humidity: after 25 ℃ of 60% time humidity are nursed one's health 2 hours, measure measuring condition: measure the angle of orientation at 13 points by the pattern of differing (degree 1) every 10cm

B) postpone to distribute

Measuring equipment: KOBRA 21ADH (Oji Scientific Instruments) temperature and relative humidity: after 25 ℃ of 60% humidity is nursed one's health 2 hours, measure measuring condition: every Re value and the Rth value of 20cm under the wavelength of 7 point measurement 630nm,

Postpone distribution=(maximal value-minimum value)/mean value * 100

C) mist degree

Measuring equipment: nephelometer NDH2000 (by Nippon Denshoku Industries Co., Ltd. makes)

Measuring condition: JIS K-6714

D) change in size

Measuring equipment: pin gauge

Sample size: 250mm * 50mm, reference length: be about 200mm

Step: witness mark length L 1, sample in 60 ℃ of 90%RH air-conditioning grooves, leave standstill 24 hours, under 25 ℃ of 60%RH through after the humidity conditioning, witness mark length L 2.

Change in size (%)=[(L2-L1)/L1] * 100

E) tear strength

Measuring equipment: underloading is torn measuring instrument (by Toyo Seiki Seisaku-Sho, Ltd. makes)

Scope: 0-90g

Dead weight: 90g

Sample size: 64 * 51mm

Temperature and relative humidity: after 25 ℃ of 65% humidity is nursed one's health 2 hours, measure

F) breakpoint stress, process judging point, elastic modulus

Measuring equipment: Strograph R2 (by Toyo Seiki Seisaku-Sho, Ltd. makes)

Sample size: width 10mm * chuck distance (chuck distance) 100mm

Temperature and relative humidity: after 25 ℃ of 65% humidity is nursed one's health 2 hours, measure

Draw speed: 10mm/min

Comparative Examples 1

Prepare cellulose acylate film in the mode identical with embodiment 1, just the quantitative change with cellulose acylate in the composition of cellulose acylate solution is 120.0 mass parts.As cellulose acylate, use CA5 as shown in table 1.Next, with the solution that makes through have with embodiment 1 in the filter paper of 34 μ m of used same apertures filter.Used cellulose acylate solution is big 4 times in the film F 12 that makes among the inceptive filtering pressure ratio embodiment 1.The filtration blockage factor of Comparative Examples 1 is 1,117m ^-3, and the filtration blockage factor of the solution that formation F12 uses is 305m ^-3The required filtration yield of filter pressure (filter material replace standard) that reaches 0.8MPa is 1/5 times of amount that forms the solution that F12 uses, and it shows this sample shortcoming aspect practical.

Embodiment 2

<2-1-1>

The preparation of polaroid-1

By preparing polarizer on the polyvinyl alcohol film that iodine is adsorbed onto stretched.

Each cellulose acylate film (F1-F14 is corresponding to the TAC1 of Fig. 1-3) that embodiment 1 is made with poly (vinyl alcohol) binder adheres on the one side of polarizer.Followingly carry out saponification and handle.

The sodium hydrate aqueous solution of preparation 1.5N also remains on 55 ℃.The dilute sulfuric acid aqueous solution of preparation 0.01N also remains on 35 ℃.The cellulose acylate film that makes was soaked in sodium hydrate aqueous solution 2 minutes, and immersion fully rinses out sodium hydrate aqueous solution in water then.Afterwards, cellulose acylate film was soaked in dilute sulfuric acid aqueous solution 1 minute, immersion fully rinses out dilute sulfuric acid aqueous solution in water then.

Final sample is fully dry down at 120 ℃.

The cellulose iii acylate film of commercially available acquisition (Fuji TAC TD-80UF; by FujiPhoto Film Co.; Ltd. make; the TAC2-1 or the 2-2 that are equivalent to function film TAC2, Fig. 3 of Fig. 2) handle through saponification; adhere to the opposite face of polarizer with poly (vinyl alcohol) binder, and 70 ℃ dry 10 minutes or longer down.

The retardation axis of the cellulose acylate film that the axis of homology and the embodiment 1 of this polarizer made be arranged in parallel (Fig. 1).Retardation axis cross arrangement with the cellulose iii acylate film of the axis of homology of polarizer and commercially available acquisition.

With cellulose acylate film and the combination of this polarizer that makes among the embodiment 1; make cellulose acylate film be positioned at polarizer; and measure the independent transmissivity TT of the 380-780nm of this polaroid, parallel transmissivity PT and intersect transmissivity CT, thereby obtain mean value under the 400-700nm with spectrophotometer (UV3100PC).TT is 40.8-44.7, and PT is 34-38.8, and CT is 1.0 or lower.And in the serviceability test that 60 ℃ of 95%RH continue 500 hours, Δ CT and Δ P in the scope of-0.1≤Δ CT≤0.2 and-2.0≤Δ P≤0 and under 60 ℃ of 90%RH are-0.05≤Δ CT≤0.15 and-1.5≤Δ P≤0 at polaroid.

Among the polaroid A 1-A14 that makes thus (the integrated-type polaroid that does not have the optical compensating film of function film among Fig. 2), a part is kept in the moisture barrier bag, not through the humidity conditioning, other parts humidity conditioning under 25 ℃ of 60%RH was kept in the moisture barrier bag in 2 hours then.Moisture barrier bag is the wrappage with polyethylene terephthalate/aluminium/poly laminate structures, and seepage rate is 0.01mg/m ²(24 hours) or littler.

<2-2-1>

The preparation of light scattering layer coating fluid:

The potpourri of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (PETA, by Nippon Kayaku Co., Ltd. makes) (50g) is used the dilution with toluene of 38.5g.And (Irgacure 184, made by Ciba Specialty Chemicals Inc. to join in this solution and mix and stir with the polymerization initiator of 2g.By the gained coating fluid is coated with and shines the refractive index of solidifying the film that obtains with ultraviolet ray is 1.51.

30% the mean grain size that in this solution, adds 1.7g again be in the toluene dispersion liquid of crosslinked polystyrene particle of 3.5 μ m (refractive index: 1.60, SX-350 is by The SokenChemical ﹠amp; Engineering Co., Ltd. make), 10,000rpm disperseed 20 minutes down with the polytron decollator, and 30% the mean grain size that adds 13.3g be crosslink propylene acyl group-styrene particle of 3.5 μ m the toluene dispersion liquid (refractive index: 1.55, by The SokenChemical ﹠amp; Engineering Co., Ltd. makes), add the fluorine surface modifier (FP-1) of 0.75g and the silane coupling agent of 10g (KBM-5103, by Shin-Etsu ChemicalCo., Ltd. makes) at last, obtain final solution.

The solution via hole diameter that mixes above is that the polypropylene filter of 30 μ m filters, and makes the light scattering layer coating fluid thus.

<2-2-2>

The preparation of low-index layer coating fluid:

At first, be prepared as follows sol solution.(KBM 5103 with methyl ethyl ketone (120 parts), acryloxy-propyl trimethoxy silicane of 100 parts, by Shin-Etsu Chemical Co., Ltd. make) and 3 parts diisopropoxy aluminium ethyl acetate put into the reaction vessel of belt stirrer and reflux condenser and mix, to wherein adding 30 parts ion exchange water and reaction solution being reacted 4 hours down at 60 ℃, then temperature is reduced to room temperature, obtains sol solution a thus.The quality mean molecular weight of solution is 1,600.In oligomer or higher component, molecular weight is 1,000-20,000 ingredients constitute 100%.By gas chromatographic analysis, confirm that raw material propylene acyloxy propyl trimethoxy silicane is surplus not at all.With refractive index 1.42 thermally cross-linkable polymkeric substance (JN-7228, solids content concn: 6%, make by JSR) (13g), the silicon dioxide gel (silicon dioxide of 1.3g, different with the particle diameter of MEK-ST, mean grain size: 45nm, solids content concn: 30%, by Nissan Chemical Industries, Ltd. makes), the cyclohexanone of the methyl ethyl ketone of sol solution a, the 5g of 0.6g and 0.6g mixes and stir.Making this reaction mixture is the polypropylene filter filtration of 1 μ m by the aperture, makes the low-index layer coating fluid thus.

<2-2-3>

Preparation with transparent protective film 01 of light scattering layer:

With thickness is web-like tri acetyl cellulose film (the Fuji TAC-TD80U of 80 μ m; by Fuji Photo Film Co.; Ltd. make) launch; use diameter as 50mm and have the nick version print roller of the degree of depth of several 180/ inch intaglio printing pattern of line and 40 μ m and scraper at the intaglio printing revolution as 30rpm and travelling speed under the condition as 30m/min; the top coating fluid that will form functional layer (light scattering layer) usefulness is applied on this film, then with this film 60 ℃ of following dry 150 seconds.After the drying, the air cooling metal halide lamp (by EYEGRAPHICS, CO., LTD. manufacturing) with 160W/cm under the nitrogen flushing passes through 400mW/cm ²Illumination and 250mJ/cm ²The ultraviolet ray irradiation of radiant quantity this coating is solidified, form the functional layer that thickness is 6 μ m thus, and this film rolled again.

Again the tri acetyl cellulose film that is coated with functional layer on it is launched; and be that the nick version print roller and the scraper of the 50mm and the degree of depth with the several 180/ inch intaglio printing pattern of line and 40 μ m is that 30rpm and travelling speed are under the condition of 15m/min at the intaglio printing revolution with diameter; low-index layer coating fluid on the coating of light scattering layer side; then with this film 120 ℃ of following dry 150 seconds, again 140 ℃ dry 8 minutes down.After the drying, the air cooling metal halide lamp (by EYEGRAPHICS, CO., LTD. manufacturing) of using 240W/cm under the nitrogen flushing is at 400mW/cm ²Illumination and 900mJ/cm ²Radiant quantity under make this coating through the ultraviolet ray irradiation, form the low-index layer that thickness is 100nm thus, and this film rolled (corresponding to the function film TAC2 of Fig. 2 or the TAC2-1 of Fig. 3) again.

<2-3-1>

The preparation of polaroid-2:

By preparing polarizer on the polyvinyl alcohol film that iodine is adsorbed on stretched.

The transparent protective film with light scattering layer 01 that makes with＜2-1-1 described in identical mode handle through saponification, and will not have the one side of the face of function film and polarizer bonding on the protective film with poly (vinyl alcohol) binder.

Make each the cellulose acylate film (F1-F14 that makes among the embodiment 1; TAC1 corresponding to Fig. 1) handles through identical saponification; adhere to poly (vinyl alcohol) binder on the one side of polarizer, and at 70 ℃ of following dryings 10 minutes or longer (structure of complete form among Fig. 2).

The retardation axis that makes the cellulose acylate film that makes among the axis of homology of this polarizer and the embodiment 1 is (Fig. 1) horizontally.The axis of homology of polarizer is arranged in intersection with the retardation axis with transparent protective film 01 of light scattering layer.Make polaroid (B1-B14, the integrated-type polaroid of function film and optical compensating film) thus.With polaroid＜2-1-1〉preparation similar, some just are stored in the moisture barrier bag without humidity conditioning, and other humidity conditionings under 25 ℃ of 60%RH were stored in moisture barrier bag in 2 hours then.

By preparing polarizer on the polyvinyl alcohol film that iodine is adsorbed on stretched.＜2-2-3〉in the transparent protective film with light scattering layer 01 that makes and the thickness that does not have functional layer be tri acetyl cellulose film (the Fuji TAC TD-80UF of 80 μ m; by Fuji Photo FilmCo.; Ltd. make) to handle through saponification with top identical mode; and to be adhered on the polarizer with poly (vinyl alcohol) binder with top identical mode; make polaroid (B0, the function film of Fig. 2, optical compensating film) thus.With polaroid＜2-1-1〉preparation similar, some will be stored in the moisture barrier bag through after humidity conditioning, and other just will be stored in the moisture barrier bag without the humidity conditioning.

At the wavelength zone of 380-780nm, be 5 ° spectral reflectivity with spectrophotometer (by JASCO Corporation manufacturing) measurement incident angle from the function film side.Integrating sphere average reflectance under the 450-650nm that obtains is 2.3%.

<2-4-1>

The preparation of hard conating coating fluid:

Trimethylolpropane triacrylate (TMPTA to 750.0 mass parts, by NipponKayaku Co., Ltd. the quality mean molecular weight that adds 270.0 mass parts manufacturing) is 3, the cyclohexanone of 000 poly-(glycidyl methacrylate), the methyl ethyl ketone of 730.0g, 500.0g and the Photoepolymerizationinitiater initiater of 50.0g (Irgacure 184, made by Ciba SpecialtyChemicals Inc.) also stir.This solution is the polypropylene filter filtration of 0.4 μ m through the aperture, obtains the hard conating coating fluid thus.

<2-4-2>

The preparation of titania fine particle dispersion liquid:

As the titania particulate, use and contain cobalt and use aluminium hydroxide and the surface treated titania particulate of zirconium hydroxide (MPT-129C is made by Ishihara Sangyo Kaisha Ltd.).

Spreading agent (38.6g) shown in following and the cyclohexanone of 704.3g are joined in the top particle of 257.1g, and disperse this potpourri, make the titanium oxide dispersion that mass median diameter is 70nm thus with DYNO-MILL.

<2-4-3>

The preparation of middle index layer coating fluid:

Add dipentaerythritol five acrylate of 58.4g and the potpourri (DPHA of dipentaerythritol acrylate in the titanium oxide dispersion above 88.9g, by NipponKayaku Co., Ltd. manufacturing), the Photoepolymerizationinitiater initiater (Irgacure 907) of 3.1g, photosensitizer (the Kayacure DETX of 1.1g, by Nippon Kayaku Co., Ltd. manufacturing), the methyl ethyl ketone and 1 of 482.4g, 869.8g cyclohexanone, and stir.This solution is fully stirred and be that the polypropylene filter of 0.4 μ m filters index layer coating fluid in obtaining thus by the aperture.

<2-4-4>

The preparation of high refractive index layer coating fluid:

Add dipentaerythritol five acrylate of 47.9g and the potpourri (DPHA of dipentaerythritol acrylate in the titanium oxide dispersion above 586.8g, by NipponKayaku Co., Ltd. manufacturing), (Irgacure 907 for the Photoepolymerizationinitiater initiater of 4.0g, make by CibaSpecialty Chemicals Inc.), photosensitizer (the Kayacure DETX of 1.3g, by Nippon Kayaku Co., Ltd. manufacturing), the methyl ethyl ketone and 1 of 455.8g, 427.8g cyclohexanone, and stir.Making this solution is the polypropylene filter filtration of 0.4 μ m by the aperture, obtains the high refractive index layer coating fluid thus.

<2-4-5>

The preparation of low-index layer coating fluid:

The multipolymer that will have a following structure is dissolved in the methyl isobutyl ketone with the concentration of 7 quality %, and will contain the acrylate-based silicone resin X-22-164C of terminal methyl group (by Shin-Etsu Chemical Co., Ltd. make) join respectively in the top solution with the concentration of solid content meter 5% with the concentration of solid content meter 3% and optical free radical initiating agent Irgacure 907 (trade name), obtain the low-index layer coating fluid thus.

(50/50, mol ratio)

<2-4-6>

Preparation with transparent protective film 02 of anti-reflecting layer:

With the intaglio printing spreader hard conating coating fluid is applied on the tri acetyl cellulose film that thickness is 80 μ m (Fuji TAC-TD80U, by Fuji Photo Film Co., Ltd. makes).After 100 ℃ of following dryings, pass through 400mW/cm with the air cooling metal halide lamp of 160W/cm (by EYEGRAPHICS, CO., LTD. makes) under with the environment that reaches 1.0 volume % or lower oxygen concentration in nitrogen flushing ²Illumination and 300mJ/cm ²The ultraviolet ray irradiation of radiant quantity this coating is solidified, form the hard conating that thickness is 8 μ m thus.

With the intaglio printing spreader with three coating positions continuously index layer, high refractive index layer and low-index layer in the coating on this hard conating.

In the drying condition of index layer be 100 ℃ and continue 2 minutes, and the nitrogen flushing with the environment that reaches 1.0 volume % or lower oxygen concentration under with the air cooling metal halide lamp of 180W/cm (by EYEGRAPHICS, CO., LTD. makes) at 400mW/cm ²Illumination and 400mJ/cm ²Radiant quantity under carry out ultraviolet curing.After solidifying should in the refractive index of index layer be 1.630 and thickness be 67nm.

The drying condition of high refractive index layer and low-index layer is 90 ℃ and continues 1 minute, then be 100 ℃ and continue 1 minute, and nitrogen flushing with the environment that reaches 1.0 volume % or lower oxygen concentration under with the air cooling metal halide lamp of 240W/cm (by EYEGRAPHICS, CO., LTD. makes) at 600mW/cm ²Illumination and 600mJ/cm ²Radiant quantity under carry out ultraviolet curing.

After solidifying the refractive index of this high refractive index layer be 1.905 and thickness be 107nm, after solidifying the refractive index of low-index layer be 1.440 and thickness be 85nm.Obtain to have the transparent protective film 02 (being equivalent to the function film TAC2 of Fig. 2 or the TAC2-1 of Fig. 3) of anti-reflecting layer thus.

<2-5-1>

The preparation of polaroid-3:

With with＜2-3-1 identical mode prepares polaroid (C1-C14, the integrated-type polaroid of function film and optical compensating film among Fig. 2), only is to use the transparent protective film 02 with anti-reflecting layer to replace having the transparent protective film 01 of light scattering layer.And; in the same manner; preparation comprises that thickness is the tri acetyl cellulose film (Fuji TAC TD80UF, by Fuji Photo Film Co., Ltd. makes) of 80 μ m and not with the polaroid (C0) of transparent protective film 02, polarizer and the functional layer of anti-reflecting layer.

At the wavelength zone of 380-780nm, be 5 ° spectral reflectivity with spectrophotometer (by JASCO Corporation manufacturing) measurement incident angle from the function film side.The integrating sphere average reflectance at 450-650nm that obtains is 0.4%.

Embodiment 3

Install onboard:

Embodiment 3-1

Be installed in by (a slice type) on the VA plate:

Prepare LCD shown in Figure 3.Promptly, from observe side (above), laminated upside polaroid (TAC2-1 (have function film/do not have function film), polarizer, TAC1-1), VA type liquid crystal cell, downside liquid crystal, downside polaroid (TAC1-2, polarizer, TAC2-2), and, back light is installed.In the following embodiments, the integrated-type polaroid that uses optical compensating film is as the downside polaroid, if but formation on the contrary is no problem on the function.Yet, should think use in many cases the integrated-type polaroid as the downside polaroid (because when use integrated-type polaroid during as the upside polaroid, side (above) function film is provided, productive rate reduces thus) must observed, and it is preferred embodiment.

The preparation of liquid crystal cell:

By making the element gap between the matrix is 3.6 μ m, dropwise has anisotropic liquid crystal material of negative permittivity (MLC 6608, and by Merck Ltd., Japan makes) and sealing in matrix, and the preparation liquid crystal cell forms liquid crystal layer thus between matrix.The delay of liquid crystal layer (that is the product Δ nd of thickness d of liquid crystal layer (μ m) and refractive index anisotropy Δ n) is 300nm.This liquid crystal material orientation is vertical orientated thus.

As the upside polaroid (observation side) of the LCD (Fig. 3) of using top vertical alignment-type liquid crystal element, use the superelevation contrast material (for example, HLC2-5618 is made by SANRITZ CORPORATION) of commercially available acquisition.As downside polaroid (on shady face); install and use with among the F3-F10 that makes among the embodiment 1 arbitrarily optical compensating gage embodiment 2＜2-1-1 in the polaroid (A3-A10) that makes, the cellulose acylate film (TAC1-2 that is equivalent to Fig. 3) that makes embodiment 1 make is positioned at the liquid crystal cell side.With bonding agent upside polaroid and downside polaroid are adhered on the liquid crystal.The Nicol that intersects is arranged, and makes that the axis of homology of upside polaroid is that the axis of homology of above-below direction and downside polaroid is a left and right directions.Use is stored in the polaroid of moisture barrier bag and does not nurse one's health the polaroid that just is stored in the moisture barrier bag through humidity after 25 ℃ of 60%RH humidity are nursed one's health 2 hours, the preparation LCD.

Here, use industrial products as the upside polaroid, and use the integrated-type polaroid as the downside polaroid, but observe the result of the LCD that makes, direction and view directions obtain neutral black display in face.Yet, in the LCD of using polaroid A 5 and A10, observe the striped inhomogeneity, although low weight.Use measuring equipment (EZ-contrast 160D, ELDIM Co.), measure the visual angle (the contrast ratio is 10 or bigger and do not have level to put upside down (gradationreversal)) in 8 stages from black display (L1) to white demonstration (L8).

Next, with measuring equipment (EZ-contrast 160D, tone when being the black display of 60 ° of polar angle of standard when ELDIM Co.) to measure with direction in the face of LCDs be the black display at 45 ° at position angle of standard and with the normal direction of display screen, and with it as initial value.Then this plate was left standstill for 1 week, the tone when measuring black display again under normal temperature and humidity (about 25 ℃ of 60%RH, and not controlled humidity).

Following table 3 has shown the measurement result of visual angle and tonal variation.Each sample of the present invention shows that wide visual angle and tone do not change.Use the tonal variation of the LCD of the polaroid of process humidity conditioning before assembling obviously much smaller.

Embodiment 3-2

Downside polaroid as the LCD (Fig. 3) of using the vertical alignment-type liquid crystal element, the optical compensating gage that uses the F3-F10 that makes with embodiment 1 embodiment 2＜2-1-1 the polaroid (A3-A10) that makes, and as the upside polaroid, use embodiment 2＜2-3-1 the polaroid (B0) that makes, and each polaroid is adhered to bonding agent.The Nicol that intersects is arranged, and make that the axis of homology of observing the side polaroid is an above-below direction, and the axis of homology of backlight side polaroid is a left and right directions.At this moment, this workspace is handled through air-conditioning under the humidity of 20-25 ℃ temperature and 50-70%RH.Use is stored in the polaroid of moisture barrier bag and does not nurse one's health the polaroid that just is stored in the moisture barrier bag through humidity after 25 ℃ of 60%RH humidity are nursed one's health 2 hours, the preparation LCD.

The LCD that observation makes, result confirm that direction and view directions obtain neutral black display in face.Yet, in the LCD of using polaroid A 5 and A10, observe the striped inhomogeneity.Also measure visual angle and tonal variation in the mode identical with embodiment 3-1.And will obtain the results are shown in table 3.

Embodiment 3-3

Use vertical alignment-type liquid crystal component fabrication LCD (Fig. 3) in the mode identical with embodiment 3-1, the value that just the element gap is become 2.8mm and Δ nd becomes 230nm.Downside polaroid as LCD, use with embodiment 2＜2-1-1 the polaroid (A13-A14) that makes, and as the upside polaroid, use embodiment 2＜2-5-1 the polaroid (C0) that makes, and each polaroid is adhered to bonding agent.The Nicol that intersects is arranged, and the axis of homology that the feasible axis of homology of observing the side polaroid is above-below direction and backlight side polaroid is a left and right directions.At this moment, this workspace is handled through air-conditioning under the humidity of 20-25 ℃ temperature and 50-70%RH.Use is stored in the polaroid of moisture barrier bag and does not nurse one's health the polaroid that just is stored in the moisture barrier bag through humidity after 25 ℃ of 60%RH humidity are nursed one's health 2 hours, the preparation LCD.

The LCD that observation makes, result confirm that direction and view directions obtain neutral black display in face.Also measure visual angle and tonal variation in the mode identical with embodiment 3-1.And will obtain the results are shown in table 3.

Comparative Examples 3-1

Repeat the step identical, just the downside polaroid is become A1, B1, A2 and B2 with embodiment 3-1.The polaroid that is used for Comparative Examples 3-1 is not through the humidity conditioning.

The LCD that observation makes, result confirm that direction and view directions obtain neutral black display in face.Also measure visual angle and tonal variation in the mode identical with embodiment 3-1.And will obtain the results are shown in table 3.

Table 3

LCD	The visual angle		Variation (the Δ E of 1 all backs black tone is installed *)
				The direction of the axis of homology	Direction apart from 45 ° of the axis of homology
	Embodiment 3-1	＞80°				＞80°	Not humidity conditioning 0.010-0.013 humidity conditioning 0.002
Embodiment 3-2			＞80°	＞80°	The same
	Embodiment 3-3	＞80°				＞80°	The same
Comparative Examples 3-1			＜50°	＜50°	Humidity is not nursed one's health 0.020-0.032

In table 3, all samples of embodiments of the invention 3-1 to 3-3 all has enough wide visual angle and the ageing stability of tone (aging stability), and significantly is better than Comparative Examples.

Embodiment 4

Following composition mixed with 3kg altogether and put into vial, under 25 ℃, 150rpm, stirred 3 hours, make cellulose acylate solution.

Cellulose acylate solution:

Cellulose acylate 17.01 quality % shown in the table 1

Triphenyl phosphate 1.16 quality %

Xenyl diphenyl phosphoester 0.83 quality %

Methylene chloride 0.47 quality %

Methyl alcohol 10.53 quality %

With the cellulose acylate solution process filter paper (aperture: 47 μ m, thickness: 1.32mm, density: 0.32g/m under the flow velocity of 7ml/min that remains on 36 ℃ ³) filter, described filter paper is supported by the ring-type porous plate in the hole that to provide 61 diameters be 3.8mm, and useful area is 12.5cm ²When filter pressure was stablized temporarily, the pressure of observing 3.5-4 hour increased.With the filtration time is transverse axis and PO/P ^0.64For the longitudinal axis is drawn, and find the curve approximation straight line.P and PO are meant filter pressure and inceptive filtering pressure.The slope that filters blockage factor Ks and be by the straight line of finding obtains by equation [Ks=3.5 * slope], and shows the result in table 4.

Table 4

Remarks	The cotton material numbering	The degree of substitution of 6-position/total degree of substitution	The degree of polymerization	Blockage factor Ks (m -3)
					The present invention	CA3	0.327	302	348
The present invention	CA4	0.328	291	298
					The present invention	CA5	0.321	324	420
The present invention	CA6	0.325	287	291
					Comparative Examples	CA7	0.310	369	658
The present invention	CA8	0.323	294	312

Total degree of substitution is the acyl substituted degree sum of 2-position, 3-position and 6-position.

Industrial applicibility

The polarizer of cellulose acylate film of the present invention and this film of use is little in the varied in thickness of width, and surface heterogeneity is little, the increase excellent performance of the delay of direction and thickness direction in the face, and length of delay is little because of the variation of ambient humidity.

And the uneven luminance of liquid crystal display of the present invention is little, and particularly the vertical stripes uneven luminance is little, and variation and the inhomogeneity of tone are little, and the variation of viewing angle characteristic is little.

This application has requires each foreign patent application of foreign priority and the whole content of each foreign patent application all to add by reference this paper, as described in fully.

Claims (35)

1, a kind of optics cellulose acylate film; has the delay Rth (λ) that postpones the film thickness direction of Re (λ), 70≤Rth (630)≤350 in the face of 46≤Re (630)≤200; and Width is 0.6 μ m or littler every the variation in thickness of 10mm; wherein Re (λ) postpones the Re value (unit: nm), Rth (λ) is the delay Rth value (unit: nm) of film thickness direction under the wavelength X nm in the face under the wavelength X nm.

2, cellulose acylate film as claimed in claim 1, it is to obtain by the dope that 33 ℃ of following viscosity coefficients of curtain coating are 10-70Pas.

3, as the cellulose acylate film of claim 1 or 2,

The degree of polymerization of wherein said cellulose acylate is 265-380.

4, as the cellulose acylate film of claim 1 or 2,

The bulk density of wherein said cellulose acylate is 0.30-0.80.

5, as the cellulose acylate film of claim 1 or 2, it is the film that comprises cellulose acylate, and described cellulose acylate obtains with the hydroxyl that the acyl substituted with two or more carbon atoms constitutes cellulosic glucose unit,

Wherein this film satisfies equation (I) and (II):

2.0≤DS2+DS3+DS6≤2.85 (I)

DS6/(DS2+DS3+DS6)≥0.315 (II)

Wherein DS2 represents the degree of substitution with the hydroxyl on the 2-position of the described glucose unit of acyl substituted;

The DS3 representative degree of substitution of the hydroxyl on the acyl substituted 3-position; With

The DS6 representative degree of substitution of the hydroxyl on the acyl substituted 6-position.

6, as the cellulose acylate film of claim 1 or 2, it comprises at least a delay dose that contains bar-shaped or cylindrical compound.

7, as the cellulose acylate film of claim 1 or 2, it comprises plastifier, ultraviolet light absorber and peels off at least a in the promoter.

8, as the cellulose acylate film of claim 1 or 2,

The thickness of wherein said film is 40-180 μ m.

9, as the cellulose acylate film of claim 1 or 2,

Wherein based on the film gross mass, the content of additive that joins in the described cellulose acylate is 10 quality % or bigger to 30 quality % or littler.

10, as the cellulose acylate film of claim 1 or 2,

The difference Δ Re (=Re 10%RH-Re80%RH) of Re (Re80%RH) value of wherein said film under (Re 10%RH) value of the Re under 25 ℃ of 10%RH and 25 ℃ of 80%RH is 12nm or littler, and the difference Δ Rth of Rth (Rth 80%RH) value under Rth (Rth10%RH) value under 25 ℃ of 10%RH and the 25 ℃ of 80%RH (=Rth10%RH-Rth80%RH) be 32nm or littler.

11, as the cellulose acylate film of claim 1 or 2,

The equilibrium moisture content of wherein said film under 25 ℃ of 80%RH is 3.4% or littler.

12, as the cellulose acylate film of claim 1 or 2,

Seepage rate (based on the thickness of 80 μ m) wherein said film leaves standstill 24 hours under 60 ℃ of 95%RH after is 400-2,300g/m ²24hr.

13, as the cellulose acylate film of claim 1 or 2,

Wherein said film is 0-5% in the mass change that leaves standstill under 80 ℃ of 90%RH under 48 hours the situation.

14, as the cellulose acylate film of claim 1 or 2,

Wherein said film is leaving standstill under 24 hours the situation and is leaving standstill change in size under 24 hours the situation under 90 ℃ of 3%RH all within ± 2% under 60 ℃ of 90%RH.

15, as the cellulose acylate film of claim 1 or 2,

Wherein glass temperature Tg is 80-180 ℃.

16, as the cellulose acylate film of claim 1 or 2,

Its Elastic Modulus is 1,500-5,000MPa.

17, as the cellulose acylate film of claim 1 or 2,

Wherein the photoelasticity modulus is 50 * 10 ^-13Cm ²/ dyn (5 * 10 ^-11Pa-1) or littler.

18, as the cellulose acylate film of claim 1 or 2,

Wherein haze value is 0.01-2%.

19, as the cellulose acylate film of claim 1 or 2, it comprises that the mean grain size of secondary granule is 0.2 μ m or bigger to 1.5 μ m or littler fine particles of silica.

20, as the cellulose acylate film of claim 1 or 2,

Wherein Re that measures under the ambient humidity of 25 ℃ of 60%RH (630) and Rth (630) satisfy equation (A), (B) and (C):

46≤Re(630)≤100 (A)

Rth(630)＝a-5.9Re(630)(B)

520≤a≤600 (C)。

21, as the cellulose acylate film of claim 1 or 2,

Wherein Re value by changing wavelength measurement and Rth value satisfy equation (D) and (E) under the ambient humidity of 25 ℃ of 60%RH:

0.90≤Re (450)/Re (550)≤1.10 and 0.90≤Re (650)/Re (550)≤1.10 (D)

0.90≤Rth (450)/Rth (550)≤1.25 and 0.90≤Rth (650)/Rth (550)≤1.10 (E).

22, as the cellulose acylate film of claim 1 or 2,

Wherein major axis is that 20 μ m or bigger bright spot inclusion number are 20 or still less in any 2.16mm * 1.72mm zone of described cellulose acylate film.

23, a kind of polaroid comprises:

Polarizer; With

Protective film,

Wherein this protective film comprises at least one cellulose acylate film as claimed in claim 1.

24, as the polaroid of claim 23,

The independent transmissivity TT (%) that wherein said polaroid is measured under 25 ℃ of 60%RH, parallel transmissivity PT (%), intersect transmissivity CT (%) and degree of polarization P and satisfy at least a in the equation (a) to (d):

40.0≤TT≤45.0 (a)

30.0≤PT≤40.0 (b)

CT≤2.0 (c)

95.0≤P (d)。

25, as the polaroid of claim 23 or 24,

Wherein CT (380) (%), CT (410) (%) and CT (700) (%) satisfy in the equation (e) to (g) at least aly, prerequisite is that CT (λ) (%) is meant intersection transmissivity under wavelength X:

CT(380)≤2.0 (e)

CT(410)≤0.1 (f)

CT(700)≤0.5 (g)。

26, as the polaroid of claim 23 or 24, wherein when this polaroid is left standstill 500 hours under 60 ℃ of 90%RH, the changes delta P of the changes delta CT (%) of transmissivity and degree of polarization of intersecting satisfy equation (h) and (i) at least a:

-3.0≤ΔCT≤3.0 (h)

-5.0≤ΔP≤0.0 (i)

Wherein said variation is meant that the measured value after test deducts the test value that measured value obtained before.

27, as the polaroid of claim 23 or 24, wherein when this polaroid is left standstill 500 hours under 60 ℃ of 95%RH, the changes delta P of the changes delta CT (%) of transmissivity and degree of polarization of intersecting satisfy equation (j) and (k) at least a:

-6.0≤ΔCT≤6.0 (j)

-10.0≤ΔP≤0.0 (k)

Wherein said variation is meant that the measured value after test deducts the test value that measured value obtained before.

28, as the polaroid of claim 23 or 24, when wherein this polaroid being left standstill 500 hours under 80 ℃, the changes delta P of the changes delta CT of transmissivity and degree of polarization of intersecting satisfy equation (l) and (m) at least a:

-3.0≤ΔCT≤3.0 (1)

-2.0≤ΔP≤0.0 (m)。

29, as the polaroid of claim 23 or 24, wherein provide the one deck at least in hard conating, anti-dazzle photosphere and the anti-reflecting layer on the protective film surface that on the face relative of described polaroid, provides with liquid crystal cell.

30, as the polaroid of claim 23 or 24, it is packaged in the moisture barrier bag, and the humidity in the bag of 25 ℃ of following packed states is 43%RH to 70%RH.

31, as the polaroid of claim 23 or 24, it is packaged in the moisture barrier bag, and the difference of humidity in the bag of packed state and the humidity when sticking to described polaroid on the liquid crystal board is 15%RH or littler.

32, a kind of OCB type LCD comprises as the cellulose acylate film of claim 1 or 2 and at least a as in the polaroid of claim 23 or 24.

33, a kind of VA type LCD comprises as the cellulose acylate film of claim 1 or 2 and at least a as in the polaroid of claim 23 or 24.

34, a kind of VA type LCD only comprises as the cellulose acylate film of claim 1 or 2 and a kind of as in the polaroid of claim 23 or 24.

35, a kind of VA type LCD only comprises as the cellulose acylate film of claim 1 or 2 and a kind of as in the polaroid of claim 23 or 24 at shady face.

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