CN105593714A - Long optical film, circularly polarizing plate provided with long optical film, and organic electroluminescent display device - Google Patents

Abstract

One embodiment of the present invention is a long optical film containing a cellulose derivative and silica-based fine particles, wherein: the angle between the lengthwise direction thereof and the slow axis thereof is 40-50 degree; the in-plane phase difference (Ro550) at a wavelength of 550nm is 120-160nm, inclusive, and formulas (1)-(3) are satisfied. 1.8<=Y<=2.6 ... (1) 0.3<=XES<=1.5 ... (2) 0.3<=XETH<=2.3 ... (3) (In the formula, XES represents the average degree of ester substitution in the cellulose derivative, XETH represents the average degree of ether substitution in the cellulose derivative, and Y represents the total degree of substitution in the cellulose derivative.)

Description

Long size blooming, possess circular polarizing disk and the organic electroluminescence display device and method of manufacturing same of this length size blooming

Technical field

The present invention relates to long size blooming, possess this length size blooming circular polarizing disk andOrganic electroluminescence display device and method of manufacturing same.

Background technology

In recent years, as general display unit, liquid crystal indicator is universal. For liquid crystalDisplay unit, improves for the requirement of display performance, durability, requires to obtain with wide visual angleTo good contrast, tone balance. In addition, recently, expect for the requirement of saving electric powerImprove, also further improve constantly for the requirement of visual angle and display performance simultaneously. SuchUnder Zhuan Condition, as the display unit of new mode, use organic electroluminescent (to write a Chinese character in simplified form belowFor organic EL. ) receive publicity as OLED display backlight. OLED displayPower consumption is little, can obtain high positive surface contrast, and viewing angle characteristic is also excellent simultaneously.

On the other hand, in OLED display, for the light of spontaneous photosphere in the future expeditiouslyBe fetched into viewable side, use the high metal material of light reflective as the electrode layer that forms negative electrodeMode, by being set in addition, as reflecting member, the reflecting member with minute surface is established metallic platePut the mode of face of taking out the opposition side of face at light and become general mode. Therefore, organicIn EL display, exist outside light takes out the reflecting member of use light to reflect and produce mirror,Under the high environment of illumination, contrast reduces such problem significantly.

In order to solve such problem, for example, have and use the circle of the external light reflection that prevents minute surface inclined to one sideThe shake method (for example,, with reference to patent documentation 1) of element.

But, in such polarizer, there is for white light the polarization under each wavelengthIn state, produce and distribute, be transformed to the such problem of coloured polarised light. This results from formationThe material of polarizer has wavelength dispersibility for phase difference.

In order to solve such problem, for example, having the phase difference of birefringent light is 1/4 wavelengthλ/4 wavelength plate and the phase difference of birefringent light be that λ/2 wavelength plate of 1/2 wavelength is separatelyThe polarizer (for example,, with reference to patent documentation 2) of having fitted under the state that optical axis has intersected.

But such polarizer, except manufacturing process is miscellaneous, also exists and can not realizeThe problem that slimming is such.

Therefore,, as for form the technology that obtains wide band λ/4 phase retardation film with individual layer, grindStudy carefully and will make to have the anisotropic high molecular monomeric unit of positive refractive index and have negative twoRefrangible monomeric unit copolymerization polymeric membrane carry out uniaxial tension and make λ/4 phase placeThe method (for example,, with reference to patent documentation 3) of poor film. In addition, studied and had optical compensation concurrentlyFunction and as the blooming (for example,, with reference to patent documentation 4) of the function of polaroid protective film.In these films, consider from the viewpoint of the manufacture adaptability excellence of polarizer, preferably use fiberElement ester resin. In addition, change in order to suppress humidity the phase difference variation causing, motion has interpolationObstruction water is coordinated in the method as the compound of the ester group of the cellulose ester resin of the principal component of film(for example,, with reference to patent documentation 5).

But the phase retardation film obtaining by the method for recording in patent documentation 3 exists to be made partiallyWhile shaking sheet and the unexcellent such problem of the cementability of polarizer. In addition, passing through patent documentation3,, in the film that the method for recording in 4 obtains, preferably use cellulose ester resin, but cellulose estersOriginally just easily there is phase difference variation in resin, humidity easily occurs and change the phase difference variable causingMoving.

And then, usually, in the case of make the blooming of long size, from suppressing mist degreeThe viewpoint rising is considered, adds delustering agent. But, if containing the cellulose esters of delustering agentIn film, add the additive of recording in patent documentation 5, exist delustering agent cohesion, mist degree to rise thisThe problem of sample. In addition, due to when making λ/4 film and need to be with high magnification stretched film master,Therefore exist the fragility of the film obtaining to reduce such problem.

Prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 8-321381 communique

Patent documentation 2: Japanese kokai publication hei 10-68816 communique

Patent documentation 3: No. 2000/026705th, International Publication

Patent documentation 4: TOHKEMY 2007-47537 communique

Patent documentation 5: TOHKEMY 2012-067218 communique

Summary of the invention

The present invention completes in view of these above-mentioned problems in the past, and object is to provide and shows fullyManifesting property of phase difference, suppress that humidity change the phase difference variation that causes, and polarizer is bondingProperty, fragility excellence, mist degree rise and obtained the long size blooming suppressing, possess this length sizeThe circular polarizing disk of blooming and organic electroluminescence display device and method of manufacturing same.

An aspect of of the present present invention is long size blooming, and it contains cellulose derivative and titanium dioxideSilicon is particulate, and the angle that long dimensional directions becomes with slow axis is 40～50 °, under wavelength 550nmFace in phase difference Ro₅₅₀For more than 120nm and below 160nm, satisfied following formula (1)～(3)。

1.8≤Y≤2.6(1)

0.3≤X_ES≤1.5(2)

0.3≤X_ETH≤2.3(3)

(in formula, X_ESFor the ester average substitution degree of cellulose derivative, X_ETHFor cellulose-derivedThe ether average substitution degree of thing, total substitution value that Y is cellulose derivative. )

Above-mentioned and other object of the present invention, feature and advantage, perhaps by following in detailRecord and accompanying drawing can have a clear understanding of.

Brief description of the drawings

Fig. 1 is the schematic diagram for the contraction multiplying power that tilts to stretch is described.

Fig. 2 represents applicable inclination in the manufacture of blooming of one embodiment of the present inventionThe skeleton diagram of one example of the track pattern of stretching-machine.

Fig. 3 be represent the blooming of manufacturing one embodiment of the present invention method (from long sizePleurodiaphragmatic in terspace roller is extracted the example that laggard line tilt stretches out) skeleton diagram.

Fig. 4 is that the method that represents the blooming of manufacturing one embodiment of the present invention (will not grownSize pleurodiaphragmatic in terspace version batch and continuously tilt stretch example) skeleton diagram.

Fig. 5 is an example that represents the formation of the OLED display of one embodiment of the present inventionSchematic diagram.

Detailed description of the invention

Inventor further investigation, found that and containing silica-based micro-as delustering agentIn grain and the long size blooming of cellulose derivative by making the substituent of cellulose derivativeRatio is the scope of regulation, can solve above-mentioned problem, has completed the present invention described later.

Below, to explaining for implementing mode of the present invention, but the present invention does not limitIn these.

The long size blooming of < >

The long size blooming (below also referred to as blooming, phase retardation film) of present embodimentBe characterised in that, the angle that long dimensional directions becomes with slow axis is 40～50 °. , with regard to long chiVery little blooming, the angle that its length direction becomes with the slow axis in face is 40～50 °. SeparatelyOutward, long size blooming is characterised in that, phase difference Ro in the face under wavelength 550nm₅₅₀ForMore than 120nm and below 160nm. In addition, long size blooming is characterised in that, contains fibreTie up plain derivative and silica-based particulate, cellulose derivative meets following formula (1)～(3).The long size blooming of present embodiment is owing to having phase difference Ro in slow axis, face₅₅₀On becomingState the optical characteristics in scope, therefore, for the light of the wide band of visible ray, can compose in factGive the phase difference of λ/4. In addition, growing size blooming, to contain substituent ratio adjusted with fullThe cellulose derivative of formula (1)～(3) under being enough to is as constituent, therefore with respect toThe variation of the optical property (tinctorial pattern (color and taste) performance, reflection characteristic) of humidity variation obtains pressing downSystem, also fully obtains the inhibition that mist degree rises simultaneously, and gives excellent fragility to film.Below, the order with optical characteristics, constituent for the long size blooming of present embodimentDescribe.

1.8≤Y≤2.6(1)

0.3≤X_ES≤1.5(2)

0.3≤X_ETH≤2.3(3)

In formula, X_ESFor the ester average substitution degree of cellulose derivative, X_ETHFor cellulose derivativeEther average substitution degree, total substitution value that Y is cellulose derivative.

Be explained, in this description, " long size " refers to respect to the width of film, hasLength more than at least 5 times of left and right, preferably refers to and has 10 times or its above length. SeparatelyOutward, " blooming " refers to and has the optics merit of giving desired phase difference for the light seeing throughThe film of energy. In addition, as optical function, for example, can enumerate inclined to one side the straight line of certain specific wavelengthThe light that shakes is transformed to Elliptical circularly polarized light, circularly polarized light or Elliptical circularly polarized light, circularly polarized light is convertedFor function of rectilinearly polarized light etc. Especially, will possess for the light wavelength specifying (conventionallyVisible region), phase difference becomes approximately 1/4 characteristic in the face of film blooming is called " λ/ 4 phase retardation films ". In addition, with regard to the blooming of present embodiment, at visible rayIn the wide region of wavelength, rectilinearly polarized light is transformed to roughly to circularly polarized light completely, is preferablyIn the scope of visible light wavelength, there is wide band λ/4 phase of 1/4 phase difference of wavelength roughlyPotential difference film. Be explained, in this description, " in the scope of visible light wavelength roughly 1/4Phase difference " refer in the region more than wavelength 400nm and below 700nm, to possess wavelength moreThe long dispersing characteristic of head sea long that phase difference value is larger.

(optical characteristics of film)

In face in the blooming of present embodiment, phase difference Ro is defined by following formula.

Ro＝(nx-ny)×d(nm)

(in formula, nx is illustrated in the face of blooming refractive index in direction and becomes maximum slow axisRefractive index on direction x, ny is illustrated in the face of blooming in direction and above-mentioned slow axis directionRefractive index on the orthogonal direction y of x, d (nm) represents the thickness of blooming. )

In addition, Ro can use automatic birefringence meter, at 23 DEG C of temperature, relative humidity 55%RHEnvironment under measure. As automatic birefringence meter, for example, can enumerate Axometrics society and manufactureThe KOBRA-21ADH that manufactures of Axoscan, prince's instrumentation machine (strain) etc.

At this, phase difference in the face of the blooming under wavelength 550nm is made as to Ro₅₅₀Situation under,The blooming of present embodiment is characterised in that, Ro₅₅₀For more than 120nm and below 160nm.Be explained phase difference Ro in the face under this wavelength 550nm₅₅₀It is the flash ranging with wavelength 550nmPhase difference in the face of having determined. Ro₅₅₀As long as for 120nm is above and 160nm below, preferredFor more than 130nm and below 150nm, more preferably more than 135nm and below 148nm. ?Ro₅₅₀(Ro in the situation of the scope more than exceeding 120nm and below 160nm₅₅₀Less than 120nmOr exceed in the situation of 160nm), the phase difference under wavelength 550nm does not become about 1/4Wavelength, uses such film production circular polarizing disk, for example, be applied to the situation of OLED displayUnder, sometimes room lighting the change such as mirror greatly, black can not show in the open.

In addition, phase difference in the face of the blooming under wavelength 450nm is made as to Ro₄₅₀, by wavelengthIn the face of the blooming under 550nm, phase difference is made as Ro₅₅₀Situation under, with respect to Ro₅₅₀Ro₄₅₀Ratio (Ro₄₅₀/Ro₅₅₀) be preferably more than 0.70 and below 0.98 more preferably 0.75Above and below 0.92, more preferably more than 0.80 and below 0.87. Be explained,Phase difference Ro in face under this wavelength 450nm₄₅₀Be with the light measurement of wavelength 450nm face inPhase difference. Ro₄₅₀/Ro₅₅₀Exceed in the situation of the scope more than 0.70 and below 0.98(Ro₄₅₀/Ro₅₅₀Less than 0.70 or exceed in 0.98 situation), blooming does not show phase placeThe poor appropriate long dispersing characteristic of head sea, for example, make existence in the situation of circular polarizing disk and cause form and aspectThe tendency of the form and aspect variation change, humidity environment causing.

With regard to the blooming of present embodiment, the angle that long dimensional directions becomes with slow axis is40～50 °, be preferably 42～48 °, more preferably 43～47 °. The optics of present embodimentFilm is owing to having such slow axis, therefore by by the master film of web-like with have and long sizeThe parallel polarizer film of web-like that sees through axle of direction rolls out respectively, heavy each other to grow dimensional directionsThe mode of closing is fitted with volume to volume, can easily manufacture circular polarizing disk. Thus, can reduceThe cutting loss of film. As making the scope with respect to the slow axis of growing dimensional directions become suchThe method of scope, for example have for by masking stretching before film carry out inclination stretching described laterMethod.

(constituent of film)

Then, the constituent of the blooming to present embodiment describes. Blooming is by becomingFor resinous principle (resin combination that contains cellulose derivative) and the additive of main componentComposition (composition beyond above-mentioned resinous principle, the delustering agent that contains silica-based particulate etc.)Form.

(resin combination that contains cellulose derivative)

Blooming contains cellulose derivative as main component. Be explained, in this description,So-called " main component ", more than referring to and containing 55 quality % in the resinous principle that forms bloomingComposition. Therefore, blooming can be enumerated as the resinous principle forming and use and contained 55 quality %The blooming of the resin combination of above cellulose derivative.

Cellulose derivative has cellulosic hydroxyl and is substituted the structure that base has replaced, particularly,Have by ester bond described later, ehter bond make substituting group and glucose skeleton bonding structure. ThisThe blooming of embodiment, is characterized in that, the substituent substitution value that glucose skeleton hasMeet following formula (1)～(3). Be explained, as " getting of having of glucose skeletonDai Ji ", can enumerate " substituting group " with glucose skeleton ester linkage described later and " with PortugalGrape sugar skeleton ether linking substituting group ".

1.8≤Y≤2.6(1)

0.3≤X_ES≤1.5(2)

0.3≤X_ETH≤2.3(3)

(in formula, X_ESFor the ester average substitution degree of cellulose derivative, X_ETHFor cellulose-derivedThe ether average substitution degree of thing, total substitution value that Y is cellulose derivative. )

In addition, cellulose derivative has the glucose skeleton unit being represented by following general formula.

[changing 1]

(in formula, R²For being positioned at the substituting group of 2 of glucose skeleton, R³For being positioned at glucoseThe substituting group of 3 of skeleton, R⁶For being positioned at the substituting group of 6 of glucose skeleton. With regard to R²、R³And R⁶, select to make substitution value to meet above-mentioned formula (1)～(3),Represent separately hydrogen atom or substituting group. )

Shown in (1), total substitution value Y is more than 1.8 and below 2.6, preferablyBe more than 1.9 and below 2.4, more preferably more than 2.0 and below 2.3. At total substitution valueY is less than in 1.8 situation, and the kind of the solvent dissolving is separately limited, and filmWater imbibition raise, exist due to humidity variation and the tendency that phase difference changes. The opposing partyFace, in the situation that total substitution value Y exceedes 2.6, not only cannot bring into play sufficient phase difference aobviousExisting property, and exist resin to become the tendency of high price, cost cost. In the present embodiment,Total substitution value Y is by ester average substitution degree X_ESWith ether average substitution degree X_ETHSum represents. GiveWith explanation, so-called in this description " total substitution value ", refers to average total substitution value, with formingEsterified or etherfied hydroxyl in 3 hydroxyls (hydroxyl) that cellulosic glucose skeleton hasThe mean value of the number of base represents, gets 0～3.0 value. Therefore be, 1.8 at total substitution value YIn situation above and below 2.6, the ratio of hydroxyl becomes more than 0.4 and below 1.2. ?The ratio of hydroxyl is in the situation of such scope, because the hydrogen bond between cellulose derivative is carriedHeight, the fragility of the blooming therefore obtaining is improved. In addition, if the ratio of hydroxyl is thisThe scope of sample, blooming, in the situation that thickness is for example 20～60 μ m, easily manifests institutePhase difference value Ro in the face of expecting.

Shown in (2), ester average substitution degree X_ESBe more than 0.3 and below 1.5,Be preferably more than 0.5 and below 1.4, more preferably more than 0.7 and below 1.4. Flat at esterAll substitution value X_ESIn 0.3 situation, the tendency that exists the transparency of film to reduce. The opposing partyFace, at ester average substitution degree X_ESExceed in 1.5 situation, the water imbibition of film raises, exist byIn humidity variation and the tendency that phase difference changes.

Shown in (3), ether average substitution degree X_ETHBe more than 0.3 and below 2.3,Be preferably more than 0.5 and below 1.9, more preferably more than 0.5 and below 1.6. Flat at etherAll substitution value X_ETHIn 0.3 situation, based on the scope shown in above-mentioned formula (2), quiltThe total substitution value Y deficiency of the film that ester has replaced, as 1.8 of lower limit, exists because humidity becomesMoving and tendency that phase difference changes. On the other hand, at ether average substitution degree X_ETHExceed 2.3Situation under, in the time making circular polarizing disk by method described later, exist cementability unexcellent,Manufacture the tendency that adaptability worsens, in addition, based on the scope shown in above-mentioned formula (2), got by esterTotal substitution value Y of the film in generation exceedes as 2.6 of higher limit, exists the film obtaining not bring into play and fillThe tendency of the manifesting property of phase difference of dividing.

Below, be used for meeting above-mentioned formula (1)～(3) for the cellulose derivative of present embodiment, substituting group that cellulose derivative possesses describes.

(substituting group) with glucose skeleton ester linkage

The cellulose derivative of present embodiment, the replacement having had with glucose skeleton ester linkageBase, to meet formula (2).

As with glucose skeleton ester linkage substituting group, the general formula of above-mentioned cellulose derivativeIn R²、R³And R⁶Can enumerate aliphatic acyl radical, aromatic group. As aromatic group,Can enumerate aromatic hydrocarbyl, also can enumerate aromatic heterocycle etc. As aromatic group, canTo be aromatic hydrocarbyl, can be also aromatic heterocycle, optimization aromatic alkyl.

As aromatic hydrocarbyl, the aromatic hydrocarbyl that preferably carbon number is 6～24, more preferablyCarbon number is 6～12 aromatic hydrocarbyl, the virtue that further preferably carbon number is 6～10Fragrant family alkyl. As the concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, anthryl, connectionPhenyl, terphenyl etc., preferably phenyl, naphthyl, xenyl, more preferably phenyl.

As aromatic heterocycle, preferably contain in oxygen atom, nitrogen-atoms or sulphur atom at least 1Individual aromatic heterocycle. As the concrete example of heterocycle, can enumerate furans, pyrroles, thiophene,Imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine,Thiazoline, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinolin, phthalazines, naphthalenePyridine, quinoxaline, quinazoline, cinnolines, dish pyridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzeneAnd imidazoles, benzoxazole, benzothiazole, BTA, the purine (テ ト ラ ザ イ Applicationデ Application) etc. As aromatic heterocycle, particularly preferably pyridine radicals, thienyl, triazine radical,Quinolyl.

As passing through ehter bond with glucose skeleton, the concrete example of the aromatic group of bonding, can be listed asLift benzylic ether, 4-benzyl phenyl ether, 4-sulfidomethyl benzylic ether, 4-methoxy-benzyl ether, 2,4,5-trimethyl benzyl ether, 2,4,5-trimethoxy benzylic ether etc. In addition, as with glucoseSkeleton is by other examples of the aromatic group of ehter bond and bonding, can enumerate 2-thienyl ether,3-thienyl ether, 4-thiazolyl ether, 2-thiazolyl ether, 2-furyl ether, 3-furyl ether,4-oxazolyl ether, 2-oxazolyl ether, 2-pyrrole radicals ether, 3-pyrrole radicals ether, 3-imidazole radicals ether,2-triazolyl ether, 1-pyrrole radicals ether, 1-imidazole radicals ether, 1-pyrazolyl ether, 2-pyridyl ethers,3-pyridyl ethers, 4-pyridyl ethers, 2-pyrazinyl ether, 4-pyrimidine radicals ether, 2-pyrimidine radicals ether,2-quinolyl ether, 2-quinoxalinyl ether, 7-quinolyl ether, 9-carbazyl ether, 2-benzothiopheneBase ether, 2-benzofuranyl ether, 2-indyl ether, 2-[4-morpholinodithio base ether, 2-benzoxazoleBase ether, 2-benzimidazolyl ether etc.

As the preferred example of aromatic acyl, can enumerate benzoyl, phenyl benzoyl,4-methyl benzoyl, 4-sulfidomethyl benzoyl, 4-methoxybenzoyl base, 4-heptyl benzeneFormoxyl, 2,4,5-trimethoxy benzoyl, 2,4,5-trimethylbenzoyl, 3,4,5-trimethoxy benzoyl and naphthoyl etc. In addition, as other of aromatic acylExample, can enumerate 2-Thiophene Carboxylic Acid ester, 3-thiophene carboxylate, 4 thiazole carboxylic acid ester, 2-thiopheneTriazole carboxylic acid's ester, pyromucic acid ester, 3-furancarboxylic acid ester, 4-oxazole carboxylate, 2-oxazole carboxylicAcid esters, 2-pyrroles's carboxylate, 3-pyrroles's carboxylate, 3-imidazolyl carboxylic acid ester, 2-triazolylcarboxylic acid ester,1-pyrroles's carboxylate, 1-imidazolyl carboxylic acid ester, 1-pyrazole carboxylate, 2-Pyridinecarboxylic Acid ester, 3-pyrrolePyridine carboxylate, 4-picolinic acid ester, 2-pyrazine carboxylic acid ester, 4-pyrimidine carboxylic ester, 2-pyrimidine carboxylicAcid esters, 2-quinoline carboxylic ester, 2-quinoxaline carboxylic acid ester, 7-quinoline carboxylic ester, 9-carbazole carboxylic acidEster, 2-benzothiophene carboxylate, 2-benzofurancarboxylic acid ester, 2-indoxyl carboxylic acid ester, 2-benzoThiazole carboxylic acid ester, 2-benzoxazole carboxylate, 2-benzimidazole carboxylate etc. These aromatic seriesGroup can further have substituting group, contains carboxyl (C (=O) O-) but preferably do not haveSubstituting group. If these aromatic groups contain carboxyl, the hydrophily of film increases, exists lightLearn the tendency of the humidity dependence deterioration of characteristic. With regard to aromatic group, optimization aromatic portionThe aromatic group of position for not replacing or replaced by alkyl or aryl.

Aliphatic acyl radical refers to-group that (C=O) R of R is aliphatic group. Fatty groupRegiment headquarters position can be any of aliphatic group of straight chain, branch and ring-type. Aliphatic acyl radicalCarbon number preferably 1～20, more preferably 1～12, further preferably 1～6. Aliphatic acyl radical canThere is substituting group at aliphatic group position. Aliphatic acyl radical is not preferably and does not replace, more preferablyAcetyl group, propiono, bytyry.

(substituting group) with glucose skeleton ether linking

The substituting group that the cellulose derivative of present embodiment has had with glucose skeleton ether linkingTo meet formula (3). This carries out getting of bonding at hypothesis and the glucose skeleton of cellulose derivativeThe major part of Dai Ji is in the situation of ester group, and the blooming obtaining is due to the mutual work of ester group and waterWith and easily cause birefringence change. Therefore, contribute to for humidity change tinctorial pattern change,Reflecting properties changes, but by importing ether as substituting group, the hydrophobicity of cellulose derivativeImprove. In addition, ether due to little with the interaction of water, be difficult for causing birefringence change, because ofThis thinks makes the tinctorial pattern variation, the reflecting properties that change for humidity change improvement.

As with glucose skeleton ether linking substituting group, can enumerate above-mentioned cellulose derivativeGeneral formula in R²、R³And R⁶For the situation of aliphatic alkyl or aromatic group. At R²、R³And R⁶In situation for aromatic group, R²、R³And R⁶Sometimes there is getting of Multiple Bonds described laterIn Dai Ji (Multiple Bonds group), contain.

In these, as with glucose skeleton ether linking substituting group, owing to obtaining in useBlooming and the tinctorial pattern that changes for humidity in the OLED display made changes, reflectivityCan change and be inhibited, therefore preferably glucose skeleton and aliphatic alkyl have carried out ether linkingSubstituting group. In aliphatic alkyl, be preferably unsubstituted aliphatic alkyl.

So-called unsubstituted aliphatic alkyl, for the atom beyond not carbon atoms and hydrogen atomAliphatic group can be any of group of straight chain, branch and ring-type. This aliphatic hydrocarbonBase is preferably alkyl, more preferably straight chained alkyl. The carbon number of aliphatic alkyl preferably 1～20,More preferably 1～12, further preferably 1～6. Wherein, particularly preferably methyl and ethyl. Pass throughThe aliphatic alkyl of such carbon number and glucose skeleton carry out ether linking, and the blooming obtainingMake as thin thickness, while use in OLED display, the tinctorial pattern under outer light changes, reflectionPerformance change is also inhibited.

Have in substituent situation at aliphatic alkyl, preferably do not there is the carboxyl of containing (C (=O)O-) substituting group. If contain carboxyl, hydrophily increases, and has the humidity of optical characteristicsThe tendency that dependence worsens. As thering is substituent aliphatic alkyl, can enumerate for example hydroxylPropyl group etc.

The substituting group that the cellulose derivative of present embodiment has had with glucose skeleton ester linkageTo meet the ester average substitution degree X of regulation in above-mentioned formula (2)_ESScope, have and glucoseSkeleton ether linking substituting group to meet the ether average substitution degree X of regulation in above-mentioned formula (3)_ETHScope. In addition, cellulose derivative, by have these substituting groups simultaneously, meets above-mentioned formula(1) scope of total substitution value Y of regulation in.

(thering is the substituting group (Multiple Bonds group) of Multiple Bonds)

The cellulose derivative of present embodiment preferably has Multiple Bonds group. As Multiple Bonds baseGroup, as long as have at least 1 two key or triple bond, more than wavelength 220nm and below 350nmHave and absorb greatly, be not particularly limited. In addition, the Multiple Bonds base in cellulose derivativeThe average substitution degree of group is preferably more than 0.3 and below 0.7, more preferably more than 0.3 and 0.6Below, more preferably more than 0.3 and below 0.5. Cellulose derivative is aobvious by havingThe absorption of showing above-mentioned scope greatly and the Multiple Bonds group of average substitution degree, can make the light obtainingThe long dispersing characteristic of head sea of learning film further improves.

As such Multiple Bonds group, for example, can enumerate the substituting group with aromatic structure.Such aromatic group can be the combination of two keys and triple bond. In addition, in aromatic group,The functional group of electrophilic, supplied for electronic is bonding, divides from the wavelength that improves the blooming obtainingThe viewpoint of loose property is considered, preferably supplied for electronic group and aromatic group bonding.

More specifically, the R in the general formula of the preferred above-mentioned cellulose derivative of Multiple Bonds group²、R³And R⁶For-R ,-OC-R ,-OCNH-R ,-(wherein, R are aromatic group) such as OC-O-R.In addition, at R²、R³And R⁶In situation for aromatic group, Multiple Bonds group and glucose boneFrame ether linking, is included in above-mentioned glucose skeleton and has in the substituting group of ehter bond. At Multiple BondsProperty at least a portion of group and glucose skeleton, in the situation of bonding, using by ehter bondIn the OLED display that the blooming that obtains has been made, tinctorial pattern changes, reflecting properties changes and is subject toTo suppressing.

In addition, in the situation that Multiple Bonds group is aromatic group, reach excellent productivity ratio.This be because: be to change large aromatic series knot for the birefringence of wavelength by making Multiple Bonds groupStructure, easily manifests the wavelength dispersion that Multiple Bonds group causes and adjusts effect, even therefore substitution valueLow, also can obtain sufficient wavelength dispersion and adjust effect. Therefore, can shorten Multiple Bonds baseIn reaction time when group imports glucose skeleton, the impact that suppresses other substituent disengagings becomesMay, the stability of production improves. In addition, because the substitution value that can make Multiple Bonds group becomesLittle, therefore can increase the hydroxyl value of every glucose skeleton unit, result, also can improve and carryThe film fragility that hydrogen bond between high resin causes.

Be explained, so-called aromatic series in this description, refers to Physicochemical dictionary (Yan Bo bookstore)The content defining as aromatic compound in the 4th edition 1208 pages. In addition, aromatic group canTo be aromatic hydrocarbyl, can be also aromatic heterocycle, more preferably aromatic hydrocarbyl.

As aromatic hydrocarbyl, the aromatic hydrocarbyl that preferably carbon number is 6～24, more preferably carbon numberBe 6～12 aromatic hydrocarbyl, the aromatic hydrocarbyl that further preferably carbon number is 6～10. DoFor the concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, anthryl, xenyl, terphenylBase etc., wherein preferred phenyl, naphthyl, xenyl, preferably phenyl.

As aromatic heterocycle, preferably comprise in oxygen atom, nitrogen-atoms or sulphur atom at least 1Individual aromatic heterocycle. As the concrete example of such heterocycle, can enumerate furans, pyrroles,Thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole,Purine, thiazoline, thiadiazoles, oxazoline, oxazole, oxadiazole, quinoline, isoquinolin, phthaleinPiperazine, naphthyridines, quinoxaline, quinazoline, cinnolines, dish pyridine, acridine, phenanthroline, azophenlyene, fourAzoles, benzimidazole, benzoxazole, benzothiazole, BTA, the purine etc., whereinPreferably pyridine radicals, thienyl, triazine radical, quinolyl.

As passing through ehter bond with glucose skeleton, the concrete example of the aromatic group of bonding, can be listed asLift benzylic ether, 4-benzyl phenyl ether, 4-sulfidomethyl benzylic ether, 4-methoxy-benzyl ether, 2,4,5-trimethyl benzyl ether, 2,4,5-trimethoxy benzylic ether etc.

In addition, other realities of the aromatic group of bonding as passing through ehter bond with glucose skeletonExample, can enumerate 2-thienyl ether, 3-thienyl ether, 4-thiazolyl ether, 2-thiazolyl ether, 2-Furyl ether, 3-furyl ether, 4-oxazolyl ether, 2-oxazolyl ether, 2-pyrrole radicals ether, 3-Pyrrole radicals ether, 3-imidazole radicals ether, 2-triazolyl ether, 1-pyrrole radicals ether, 1-imidazole radicals ether, 1-Pyrazolyl ether, 2-pyridyl ethers, 3-pyridyl ethers, 4-pyridyl ethers, 2-pyrazinyl ether, 4-Pyrimidine radicals ether, 2-pyrimidine radicals ether, 2-quinolyl ether, 2-quinoxalinyl ether, 7-quinolyl ether,9-carbazyl ether, 2-benzothienyl ether, 2-benzofuranyl ether, 2-indyl ether, 2-benzeneBenzothiazolyl ether, 2-benzoxazolyl ether, 2-benzimidazolyl ether etc.

As the preferred example of aromatic acyl, can enumerate benzoyl, phenyl benzoyl,4-methyl benzoyl, 4-sulfidomethyl benzoyl, 4-methoxybenzoyl base, 4-heptyl benzeneFormoxyl, 2,4,5-trimethoxy benzoyl, 2,4,5-trimethylbenzoyl, 3,4,5-trimethoxy benzoyl, naphthoyl etc.

In addition, as other examples of aromatic acyl, can enumerate 2-Thiophene Carboxylic Acid ester, 3-thiopheneFen carboxylate, 4 thiazole carboxylic acid ester, 2-thiazole carboxylic acid ester, pyromucic acid ester, 3-furans carboxylicAcid esters, 4-oxazole carboxylate, 2-oxazole carboxylate, 2-pyrroles's carboxylate, 3-pyrroles's carboxylate,3-imidazolyl carboxylic acid ester, 2-triazolylcarboxylic acid ester, 1-pyrroles's carboxylate, 1-imidazolyl carboxylic acid ester, 1-pyrroleTriazole carboxylic acid's ester, 2-Pyridinecarboxylic Acid ester, Niacin Nicitinic Acid ester, 4-picolinic acid ester, 2-pyrazine carboxylicAcid esters, 4-pyrimidine carboxylic ester, 2-pyrimidine carboxylic ester, 2-quinoline carboxylic ester, 2-quinoxaline carboxylic acidEster, 7-quinoline carboxylic ester, 9-carbazole carboxylate, 2-benzothiophene carboxylate, 2-benzofuranCarboxylate, 2-indoxyl carboxylic acid ester, 2-[4-morpholinodithio carboxylate, 2-benzoxazole carboxylate, 2-Benzimidazole carboxylate etc.

These aromatic groups can further have substituting group, but preferably do not have the carboxyl of containing (C(=O) O-) substituting group. If contain carboxyl, hydrophily increases, and has optical characteristicsHumidity dependence worsen tendency. Above-mentioned aromatic group optimization aromatic position is not for replacingOr replaced by alkyl or aryl.

The cellulose derivative of present embodiment can be with reference to known method, for example " セ Le ロー ス topical reference book " record in the 131st page～the 164th page (towards storehouse bookstore, 2000) etc.Method is manufactured. Particularly, with regard to the cellulose derivative of present embodiment, can be by makingThe cellulose ether having been replaced by ether by the part of 2,3 and 6 s' hydroxyl is as formerMaterial adds acyl chlorides or acid anhydrides under the alkali of pyridine etc. exists, and imports desired substituting group, esterThe desired substituting group of bonding, manufactures thus.

Be explained, the substituent substitution value of glucose skeleton for example can utilizeCelluloseCommunication6,73-79 (1999) and Chrality12 (9),The method of recording in 670-674, passes through¹H-NMR or¹³C-NMR and determining.

The weight average molecular weight of cellulose ether derivative is preferably 100,000 to 400,000, and more preferably 13Ten thousand to 300,000, more preferably 150,000 to 250,000. In the large situation of molecular weight ratio 400,000Under, not only decline for the solubility of solvent, and the rising of the excess stickiness of the solution obtaining,Be not suitable for solvent cast method, make thermoforming difficulty, have the asking of transparency reduction etc. that produces filmThe tendency of topic. On the other hand, in the situation that molecular weight ratio 100,000 is little, the film that existence obtainsThe tendency that mechanical strength declines.

As cellulose ether derivative, can use the cellulose ether of being manufactured by single raw material derivativeThing, also can be used in combination two or more of cellulose ether derivatives different raw material.

(silica-based particulate)

The blooming of present embodiment contains the silica-based particulate as delustering agent. As thisThe silica-based particulate of sample, can enumerate silica, talcum, clay, burn till kaolin,Burn till calcium silicates, afwillite, alumina silicate, magnesium silicate etc. In these, obtain from inhibitionThe viewpoint that rises of the mist degree of film consider, preferably silica. The particulate of silica is preferably flatAll primary particle size is that 1～20nm and apparent specific gravity are silicon dioxide microparticle more than 70g/L.Wherein, the silicon dioxide microparticle that average primary particle diameter is 5～16nm is due to the light that can make to obtainThe mist degree of learning film reduces well, therefore preferred. In addition, apparent specific gravity be preferably 90～200g/L, more preferably 100～200g/L. The value of apparent specific gravity is larger, and more capable of regulating height is denseThe dispersion liquid of degree, improves mist degree, condensation product, therefore preferred.

As the concrete example of the particulate of silica, can enumerate ア エ ロ ジ Le R972, R972V,R974, R812,200,200V, 300, R202, OX50, TT600 (are Japanese ア aboveエ ロ ジ Le (strain) system) etc. commercially available product. Wherein, ア エ ロ ジ Le 200V and ア エ ロジ Le R972V due to average primary particle diameter be the following and apparent specific gravity of 20nm be 70g/L withUpper, the mist degree of the film obtaining being kept to such an extent that to reduce the effect of coefficient of friction in low large, because ofThis is preferred.

Silica-based particulate forms the offspring that average grain diameter is 0.05～2.0 μ m conventionally.These offsprings agglomerate as primary particle in blooming exists, on blooming surfaceForm the concavo-convex of 0.05～2.0 μ m. As average aggregate particle size, be preferably 0.05～1.0 μM, more preferably 0.1～0.7 μ m, more preferably 0.1～0.4 μ m. Primary particle size andAggregate particle size for example can by the particulate with in scanning electron microscope viewing optics film, generalThe diameter of a circle external with particle calculates as particle size. Now, can adopt and change fieldAnd observe 200, particle, method with its mean value as average particle size.

As the preparation method of silica-based particulate, be not particularly limited, for example can adoptFollowing method: the particle dispersion liquid that preparation has been uniformly mixed solvent and particulate, uses road mixedThe machine that closes mixes this particle dispersion liquid and the cellulose derivative rubber cement liquid of having prepared in addition etc.Close.

Implement hydrophobization processing on the surface to silica-based particulate, if addedOther hydrophobic additive, this additive is adsorbed on microparticle surfaces, easily produces with itAs the condensation product of the additive of core. Therefore, preferably by by relatively hydrophilic additiveAfter mixing with particle dispersion liquid in advance, hydrophobic additive is mixed to be suppressed at silica-based micro-The cohesion of the surperficial additive of grain. Thus, the mist degree of the film obtaining reduces, and will adopt thisThe circular polarizing disk of the film of sample is assembled in the situation in OLED display, can suppress black demonstrationIn light leak.

In the case of the particulate of silica is mixed with solvent etc. disperseing, silicaConcentration is preferably 5～30 quality %, more preferably 10～25 quality %, more preferably 15～20 quality %. The final addition of the delustering agent in the rubber cement solution of cellulose derivative is preferredThe scope of 0.001～1.0 quality %, the more preferably scope of 0.005～0.5 quality %, furtherThe preferably scope of 0.01～0.1 quality %.

(other additives)

The blooming of present embodiment beyond above-mentioned silica-based particulate, as otherAdditive, for example, can contain the following various additives of enumerating. As such additive,For example can enumerate degradation inhibitor, ultra-violet absorber, the delustring in addition of silica-based particulateAgent, plasticizer etc.

(degradation inhibitor)

In the blooming of present embodiment, can contain for example antioxidant, peroxide breakdownThe degradation inhibitor of agent, radical polymerization inhibitor, matal deactivator, sour capturing agent, amine etc.As degradation inhibitor, can use for example Japanese kokai publication hei 3-199201 communique, Japan spyOpen flat 5-197073 communique, Japanese kokai publication hei 5-194789 communique, Japanese kokai publication heiThe material of recording in 5-271471 communique, Japanese kokai publication hei 6-107854 communique, concreteGround, can use Yoshinox BHT (BHT), tribenzyl amine (TBA). As deterioratedThe content of inhibitor, from suppressing the viewpoint consideration that spills (oozing out) to film surface, is preferablyIn the scope of 0.01～1 quality % of cellulose solution (rubber cement), more preferably 0.01～0.2In the scope of quality %.

(ultra-violet absorber)

The blooming of present embodiment can contain ultra-violet absorber. As ultra-violet absorber,Can enumerate for example dihydroxy benaophenonel based compound, BTA based compound, salicylate systemCompound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt are chemical combinationThing etc. In these, preferably painted few BTA based compound. In addition, also preferably useIn Japanese kokai publication hei 10-182621 communique, Japanese kokai publication hei 8-337574 communique, recordThe macromolecule ultraviolet ray of recording in ultra-violet absorber, Japanese kokai publication hei 6-148430 communique is inhaledReceive agent. Except phase retardation film, the protection using the blooming of present embodiment as polarizerIn the situation that film uses, as ultra-violet absorber, from preventing polarizer, organic ELDeteriorated viewpoint is considered, the ultraviolet absorbability excellence below optimal wavelength 370nm, andAnd consider from the viewpoint of the demonstration of organic EL, preferably have more than wavelength 400nm canSee the few characteristic of absorption of light.

As BTA based compound, for example, can enumerate 2-(2 '-hydroxyl-5 '-methylbenzeneBase) BTA, 2-(2 '-hydroxyl-3 ', 5 '-bis--tert-butyl phenyl) BTA,2-(2 '-hydroxyl-3 '-tert-butyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-bis--tert-butyl phenyl)-5-chlorobenzotriazole, 2-[2 '-hydroxyl-3 '-(3 ", 4 ", 5 " and, 6 " tetrahydrochysene phthalimidomethyl)-5 '-aminomethyl phenyl]BTA, 2,2-di-2-ethylhexylphosphine oxide [4-(1,1,3,3-tetramethyl butyl)-6-(2H-BTA-2-yl) phenol], 2-(2 '-hydroxyl-3 '-tert-butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2H-BTA-2-yl)-6-(straight chain and side chain dodecyl)-4-methylphenol, octyl group-3-[3-tert-butyl-4-hydroxyl-5-(chloro-2H-BTA-2-Base) phenyl] propionic ester and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxyl-5-(chloro-2H-of 5-BTA-2-yl) phenyl] mixture etc. of propionic ester. In addition, as commercially available product, preferablyUse チ ヌ PVC Application (TINUVIN) 109, チ ヌ PVC Application (TINUVIN) 171, チ ヌ PVC Application(TINUVIN) 326, チ ヌ PVC Application (TINUVIN) 328 (is BASF ジ ャ パ Application (strain) aboveManufacture).

With regard to the addition of ultra-violet absorber, with respect to cellulose derivative, be preferablyThe scope of 0.1～5.0 quality %, more preferably in the scope of 0.5～5.0 quality %.

(delustering agent beyond silica-based particulate)

The blooming of present embodiment can contain the delustring beyond above-mentioned silica-based particulateAgent. As such delustering agent, can enumerate titanium dioxide, aluminium oxide, zirconia, calcium carbonate,Calcium carbonate and calcium phosphate etc. With regard to particle size, apparent specific gravity, the preparation method of these delustering agentsAnd addition, due to same with silica-based particulate, therefore description thereof is omitted.

(plasticizer)

With regard to the blooming of present embodiment, to improve mobility, the flexibility of compositionObject, can be used together various plasticizer. As plasticizer, for example, can enumerate polyol ester system and increaseMould agent, ethyl glycolate is that plasticizer, phthalic acid ester are that plasticizer, citrate are plasticisingAgent, fatty acid ester are that plasticizer, phosphate are that plasticizer, multi-carboxylate are plasticizer, thirdOlefin(e) acid is plasticizer etc. By select or also use these plasticizer, Ke Yiying according to purposesFor the wide purposes of scope.

The manufacture method > of < blooming

Then, the manufacture method of above-mentioned blooming is described. The optics of present embodimentFilm can be filmed according to known method. Below, to representational solution casting method and moltenMelting the tape casting describes.

(solution casting method)

The blooming of present embodiment can adopt solution casting method manufacture. At solution casting methodIn, comprise: make thermoplastic resin and the additive etc. of cellulose derivative etc. (contain titanium dioxideSilicon is particulate) in organic solvent heating for dissolving and prepare the operation of rubber cement, by preparation rubber cementCurtain coating to the operation in the metal support of band shape or drum type, by curtain coating rubber cement be dried as netThe operation of shape thing, the operation of peeling off from metal support, the net of having peeled off is stretchedOr the operation of shrinking, further dry operation, operation that the film having completed is batched etc.

(rubber cement preparation section)

In rubber cement preparation section, with regard to the cellulose derivative in rubber cement, concentration Gao ZhekeTo alleviate the drying load of delaying at metal support upper reaches, preferably, if but cellulose-derivedThe excessive concentration of thing, load when filtration increases, and filtering accuracy worsens. Therefore, as taking into accountThe two concentration, in the scope more than being preferably 10 quality % and below 35 quality %, more excellentIn scope more than electing 15 quality % as and below 30 quality %.

(curtain coating operation)

In curtain coating (casting) operation, the preferred effects on surface of metal support of use has carried out minute surfaceAccurately machined product, preferably uses stainless steel band or has carried out plating finishing with casting material effects on surfaceThe drum of work.

Scope more than the width of curtain coating is preferably made as 1m and below 4m. The metal of curtain coating operationThe surface temperature of supporting mass is more than-50 DEG C, in solvent does not seethe with excitement the scope of temperature of foamingSuitably set. The rate of drying of the higher net of temperature can be faster, if but mistake exceedinglyHeight, net foaming sometimes, flatness are deteriorated. The surface temperature of preferred metal support isMore than 0 DEG C and below 100 DEG C, more preferably more than 5 DEG C and below 30 DEG C. In addition, Ke YitongCross and carry out cooling and make net gelation, under the state that contains in a large number residual solvent from drum strippingFrom. Method to the temperature of controlling metal support is not particularly limited, and can adopt and blow temperatureThe method of wind or cold wind, the method that warm water is contacted with the dorsal part of metal support. Use warm waterMethod owing to carrying out expeditiously passage of heat, therefore until the temperature of metal support becomeRegular hour is short and preferred. Use in the method for warm air, consider that the evaporation latent heat of solvent causesThe temperature of net reduce, sometimes in the warm air more than using the boiling point of solvent, limitThe limit that prevents from foaming is used the wind of the temperature higher than the temperature of target. Especially, preferably from curtain coatingDuring peeling off, change the temperature of supporting mass and the temperature of dry wind, be dried expeditiously.

For blooming shows good flatness, when net being peeled off from metal supportIn scope more than residual solvent amount is preferably 10 quality % and below 150 quality %, more preferablyScope more than 20 quality % and below 40 quality % or more than 60 quality % and below 130 quality %In, more preferably 20 quality % above and 30 quality % following or 70 quality % above andIn scope below 120 quality %.

Be explained, in this description, residual solvent amount is defined by following formula.

Residual solvent amount (quality %)={ (M-N)/N} × 100

(in formula, M takes in the moment arbitrarily in the manufacture of net or film or after manufacturingThe quality of sample, N is by the moment arbitrarily in the manufacture of net or film or after manufacturingThe sample of taking has heated the quality after 1 hour at 115 DEG C)

(drying process)

As the drying means adopting in drying process, there is United States Patent (USP) the 2nd, 336, No. 310,The 2nd, 367, No. 603, the 2nd, 492, No. 078, the 2nd, 492, No. 977, the 2nd,492, No. 978, the 2nd, 607, No. 704, the 2nd, 739, No. 069 and the 2nd, 739,070Number each description, BP the 640th, No. 731 and the 736th, each description of No. 892,And Japanese Patent Publication 45-4554 communique, 49-5614 communique, Japanese kokai publication shoIn 60-176834 communique, 60-203430 communique and 62-115035 communique, recordMethod. Dry can the passing through net the non-active gas such as air, nitrogen of rousing or bringingBlow and carry out.

In drying process, preferably net is peeled off from metal support, further dry, makeResidual solvent amount becomes below 1.0 quality %, more preferably becomes below 0.01 quality %.

In drying process, generally can adopt roller drying mode, for example, make net alternately pass throughMultiple rollers of configuration and make its dry mode, carry on one side net in stenter mode up and downCarry out dry mode on one side.

(stretching process)

The blooming of present embodiment, as mentioned above, the face of preferably measuring under wavelength 550nmInterior phase difference Ro₅₅₀For more than 120nm and below 160nm. Such phase difference can pass through filmStretch and give.

Drawing process is not particularly limited, for example, can adopts alone or in combination: make multipleRoller have peripheral speed poor, between them, utilize the poor method longitudinally stretching of roller peripheral speed; WithClip, pin fix, make the interval of clip, pin to expand at direct of travel at the two ends of netThe method of opening up and longitudinally stretching; Similarly extending transversely and laterally stretchingMethod; Or side by side expansion and in two directions stretch in length and breadth method in length and breadth. , phaseFor masking direction, can laterally stretch, also can longitudinally stretch, also canTo stretch in two directions, and then in the situation that two directions stretch, can be to draw simultaneouslyStretching, can be also successively to stretch. Be explained, in the situation of so-called stenter mode, asFruit adopts linear drives mode to drive clip portion, can carry out level and smooth stretching, can reduceThe danger of fracture etc., therefore preferred.

As stretching process, conventionally stretch at width (TD direction), in conveying sideThe situation of shrinking to (MD direction) is many, but in the time that it is shunk, if at incline directionCarry, easily make main chain direction consistent, therefore to manifest effect larger for phase difference. Shrinkage factor canTo be decided by the angle of carrying.

Fig. 1 is the schematic diagram of the contraction multiplying power during explanation tilts to stretch. In Fig. 1, by celluloseAcylate film F is in the time that the direction of Reference numeral 112 tilts to stretch, as throughput directionMajor axis M₁Be punctured into M by carrying out oblique bending₂。

Now, shrinkage factor (%) by

Shrinkage factor (%)=((M₁-M₂)/M₁)×100

Represent. If angle of bend is made as to θ, become

M₂＝M₁×sin(π-θ)，

Shrinkage factor by

Shrinkage factor (%)=(1-sin (π-θ)) × 100

Represent.

In Fig. 1, Reference numeral 111 is draw direction, and Reference numeral 113 is throughput direction(MD direction), Reference numeral 114 represents slow axis.

If consider the productivity ratio of circular polarizing disk, the blooming of present embodiment is with respect to conveying sideTo the angle of orientation be 45 ° ± 2 °, can carry out and the laminating of the volume to volume of polarizing coating, preferably.

(utilizing the stretching of inclination stretching device)

Then, the inclination drawing process stretching in the direction of 45 ° is further saidBright. In the manufacture method of the blooming of present embodiment, as to the blooming stretchingGive the method for the orientation of incline direction, preferably use inclination stretching device.

As applicable inclination stretching device in the present embodiment, be preferably following film and drawStretch device: by track pattern is diversely changed, can freely set the angle of orientation of film,Can make axis of orientation left and right on whole film width of film be orientated accurately equably, andAnd can be with high accuracy control thickness, delay.

Fig. 2 is illustrated in the manufacture of blooming of present embodiment the applicable inclination dress that stretchesThe skeleton diagram of one example of the track pattern of putting. Be explained, figure shown here is an example, canBe not limited thereto with the stretching device of applying in the present embodiment.

Usually, in inclination stretching device, as shown in Figure 2, the pleurodiaphragmatic in terspace of long sizeThe extraction direction D1 of version is different from the take-up direction D2 of the stretched film after stretching, forms and extracts angle outDegree θ i. Angle the drive θ i can be greater than 0 ° and be at random set as less than the scope of 90 °Desired angle.

With regard to the pleurodiaphragmatic in terspace version of long size, in inclination stretching device entrance (position of A in figure)In, its two ends are grasped by the tool (stenter) that grasps of left and right, along with grasping the walking of toolAnd make its walking. In inclination stretching device entrance (position of A in figure), with respect to filmThe relative left and right of the substantially vertical direction of direct of travel (extract out direction D1) grasp tool Ci, CoOn the asymmetrical track Ri in left and right, Ro, walk, the position (B in figure in the time stretching endPosition) film having grasped is discharged.

Now, grasping in the relative left and right of inclination stretching device entrance (position of A in figure)Tool is along with grasping of walking on the asymmetrical track Ri in left and right, Ro, become and walk at Ri skiddingTool Ci is with respect to the position relationship that tool Co advances that grasps of walking at Ro skidding.

That is, at inclination stretching device entrance (utilization of film grasps the starting position that grasps of tool) A,The substantially vertical direction of the extraction direction D1 with respect to film relative grasp tool Ci, Co,Under the state of position B when the stretching that is positioned at film finishes, link this and grasp the straight line of tool Ci, CoWith respect to a roughly orthogonal direction tilt angle theta L of the take-up direction D2 of film.

According to above method, pleurodiaphragmatic in terspace version is tilted to stretch to make the angle of orientation become θ L,Obtain blooming. Substantially vertical in this what is called, be illustrated in the scope of 90 ± 1 °.

In more detail, in the manufacture method of present embodiment, preferably use above-mentioned explanationThe stretching device that can tilt to stretch tilts to stretch. This stretching device can add pleurodiaphragmatic in terspace versionHeat, to the temperature arbitrarily that can stretch, tilts to stretch. This stretching device possess the thermal treatment zone,For delivery of the pair of tracks that grasps the left and right that tool walks of film with walk on this trackMultiple tools that grasp. With grasping tool by the two ends of the film of supplying with successively to the inlet portion of stretching deviceGrasp, film is imported in the thermal treatment zone, film released from grasping tool in the export department of stretching devicePut. To be wound to volume core from grasping the film that tool discharged. Pair of tracks has the company of ring-type separatelyContinuous track, the tool that grasps grasping of film having been discharged in the export department of stretching device is walked in outer rowAnd be back into successively oral area.

Be explained, the track pattern of stretching device becomes the asymmetrical shape in left and right, according to rightThe angle of orientation θ, the stretching ratio etc. that give in the long size stretched film that should manufacture, can be manually orAutomatically adjust its track pattern. The inclination using in the manufacture method of present embodiment stretchesIn device, preferably can freely set the position of each orbit portion and track linking part, at randomChange track pattern (example that in Fig. 2 zero is linking part).

In present embodiment, the tool that grasps that grasps tool and front and back of stretching device keeps certain intervals,Walk with certain speed. The speed of travel that can suitably select to grasp tool, is generally 1～100m/ and dividesClock. It is common below 1%, excellent that the difference of the speed of travel that grasps tool of pair of right and left is the speed of travelSelection of land is below 0.5%, more preferably below 0.1%. This be because, if going out at stretching deviceThe left and right that mouth is in film exists gait of march poor, in the outlet of stretching device, produce gauffer,Assemble, therefore require the speed difference that grasps tool of left and right to be essentially same speed. General drawingStretch in device etc., according to frequency of the cycle of the tooth of the sprocket wheel of chain drive-belt, CD-ROM drive motor etc.,There is the speed inequality producing with the magnitude below second, usually produce the inequality of number %, but these are notBe equivalent to the speed difference described in present embodiment.

In the stretching device of present embodiment, particularly become the position of inclination in the conveying of film,The track that restriction is grasped to the track of tool usually requires the large rate of curving. From avoiding bending sharplyProduce grasp interference between tool or the local concentrated object of stress is considered, preferably existIn bend, make the track that grasps tool depict curve.

In the present embodiment, with regard to long size pleurodiaphragmatic in terspace version, at inclination stretching device entrance (figureThe position of middle A) in, its two ends are grasped successively with the tool that grasps of left and right, along with grasping toolWalk and make its walking. In inclination stretching device entrance (position of A in figure), with respect toIn the substantially vertical direction of film direct of travel (extract out direction D1), the tool that grasps of relative left and right existsOn the asymmetrical track in left and right, walk, by thering is adding of preheating zone, drawing zone, heat fixation districtHot-zone.

So-called preheating zone, refers to the interval guarantor who grasps tool who grasps two ends in the inlet portion of the thermal treatment zoneHold the interval of walking under the state at certain interval.

So-called drawing zone, refers to that the interval that grasps tool that grasps two ends opens until become regulationThe interval at interval. In drawing zone, carry out inclination stretching as described above, can be as requiredBefore and after tilting to stretch, carry out vertical or horizontal stretching. In the situation that tilts to stretch, when bendingWith the contraction in the MD direction (leading phase shaft direction) of the direction as vertical with slow axis.

So-called heat fixation district, refers to that the interval that grasps tool after drawing zone becomes necessarily againDuring in two ends grasp the interval of walking under the state that tool keeps being parallel to each other. Pass through heatAfter fixed area, can be by by the Temperature Setting in district being the vitrifying that forms the thermoplastic resin of filmInterval (cooling zone) below transition temperature Tg. Now, consider the contraction of the cooling film causing,Can be made as the track pattern that tool interval narrows that grasps that makes in advance subtend.

The temperature in Jiu Ge district, with respect to the glass transition temperature Tg of cellulose derivative,Preferably in preheating zone, in the scope of Tg～Tg+30 DEG C, set, in drawing zone Tg～In the scope of Tg+30 DEG C, set, in cooling zone, in the scope of Tg-30 DEG C～Tg, set.

Be explained, in order to control the uneven thickness of width, can be at width in drawing zoneDirection gives temperature difference. For give temperature difference on width in drawing zone time, canUse adjustment makes at width warm air being sent into the aperture of the nozzle in thermostatic chamberGive the method for difference, heater is added to the known of thermal control etc. side by side at widthGimmick.

The length in preheating zone, drawing zone and heat fixation district can suitably be selected, with respect to drawing zoneLength, the length of preheating zone is generally in 100～150% scope, and the length in heat fixation district is logicalBe often in 50～100% scope.

Stretching ratio (W/Wo) in stretching process is preferably in 1.3～3.0 scope, more excellentElect as in 1.5～2.8 scope. If stretching ratio, within the scope of this, can make widthUneven thickness diminishes. In the drawing zone of inclination stretching device, if on width to drawingStretch temperature poor, further improve width uneven thickness and become possibility. Be explained,Wo represents the width of the film before stretching, and W is the width of the film after stretching.

As applicable inclination drawing process in present embodiment, shown in above-mentioned Fig. 2Method beyond, can enumerate Fig. 3 (a)～(c), Fig. 4 (a) and (b) inShown drawing process.

Fig. 3 is that the method that represents the blooming of manufacturing present embodiment is (from long size pleurodiaphragmatic in terspace rollerExtract the example that laggard line tilt stretches out) skeleton diagram, represent the length of temporarily batching as web-likeThe pattern that size pleurodiaphragmatic in terspace version is extracted out, tilted to stretch. Fig. 4 is for representing to manufacture present embodimentThe method of blooming (long size pleurodiaphragmatic in terspace version is not batched and the reality of the stretching of tilting continuouslyExample) skeleton diagram, represent length size pleurodiaphragmatic in terspace version is not batched and continuously tilt stretchingThe pattern of operation.

In Fig. 3 and Fig. 4, Reference numeral 15 represents inclination stretching device, Reference numeral 16Represent film withdrawing device, Reference numeral 17 represents throughput direction change device, Reference numeral 18Represent devices for taking-up, Reference numeral 19 represents film forming apparatus. In each figure, sometimes for tableThe Reference numeral that shows same parts is omitted.

Film withdrawing device 16 preferably with respect to inclination stretching device entrance, with predetermined angular by filmThe mode of sending, can slide and rotate, or can slide, and changes dress by throughput directionPut 17 film is passed out to inclination stretching device entrance. Fig. 3 (a)～(c) represent to change respectivelyThe pattern of configuration of film withdrawing device 16 and throughput direction change device 17. Fig. 4 (a) and(b) represent by by film forming apparatus 19 maskings film be directly retracted to the pattern of stretching device.By making film withdrawing device 16 and throughput direction change device 17 become such formation, exceptCan further make beyond all narrowed width of manufacturing installation, fine controlling diaphragmLaunching position and angle, can obtain the thickness of film, the little long size stretching of fluctuation of optical valueFilm. In addition, by making film withdrawing device 16 and throughput direction change device 17 removable, canMeshing bad with the clip that effectively prevents left and right to film.

With regard to devices for taking-up 18, by export with predetermined angular with respect to inclination stretching deviceThe mode that film is extracted out configures, the fine distracted position of controlling diaphragm and angle. Its knotReally, can obtain the thickness of film, the little long size stretched film of fluctuation of optical value. Therefore, canEffectively prevent the generation of the fold of film, the batching property of film improves, and therefore can incite somebody to action to grow sizeFilm batches. In present embodiment, the drawing tension T (N/m) of the film after stretching is preferably at 100N/m< T < 300N/m, preferably in the scope of 150N/m < T < 250N/m, adjust.

(melting masking method)

Above-mentioned blooming can carry out masking by melting masking method. Melting masking method is to contain fibreTie up the composition heating and melting of plain derivative etc. to the temperature that is mobility, then, by mobilityThe fused mass that contains cellulose derivative carry out the forming method of curtain coating.

The method of forming of carrying out heating and melting for example can be categorized as and melt extrude the method for forming, is molded intoType method, inflation method, injection moulding, blow molding method, drawing and forming method etc. These one-tenthIn type method, from the viewpoint of mechanical strength and surface accuracy etc., preferred molten extrusion molding.

The multiple raw material that use in extrusion by melting preferably carry out mixing and pellet conventionally in advanceChange. Pelletization can be undertaken by known method, for example, can pass through dried fibres elementDerivative, additive are supplied to extruder with feeder, use single screw rod, double screw extruderCarry out mixingly, be extruded into tow shape from die head, carry out water-cooled or air cooling, cut to obtain.

Additive can mix before being supplied to extruder, or can use respectively feeder separatelySupply with. Be explained, with regard to a small amount of additive of particulate, antioxidant etc., for allMix evenly, preferably mix in advance.

With regard to the extruder using in pellet, in order to suppress shearing force, to make resin not badChange (molecular weight reduces, painted, gel generation etc.), preferably can pellet as much as possibleThe mode of processing under low temperature. For example, the in the situation that of double screw extruder, preferably useThe screw rod of shallow/deep groove type, make it in equidirectional rotation. Consider from mixing uniformity, preferably meshingType.

Use the above pellet obtaining like that to carry out film masking. Not pellet, willRaw-material powder drops into as former state and in feeder, is supplied to extruder, heating and melting after,Carry out as former state film masking.

For above-mentioned pellet, use the extruder of single-bolt type, double-screw type, while making to extrudeMelt temperature is in 200 DEG C of above and 300 DEG C of following scopes, waits with the filter of leaf dish-typeFilter and after impurity is removed, be membranaceous from T-shaped die head curtain coating, with chill roll and Elastic Contact rollerClamping film makes it solidify on chill roll.

While importing to extruder from feeding hopper, preferably under vacuum or decompression under, nonactive gasUnder body atmosphere, prevent oxidation Decomposition etc.

Extruding flow preferably imports gear pump etc. and stably carries out. In addition, removing with regard to impurityThe filter of middle use, preferably uses stainless steel fibre sintered filter. Stainless steel fibreSintered filter be make after the state that stainless steel fibre body intricately tangled compress,By contact site sintering and integrated product, can come by the thickness of its fiber and decrementChange density, adjust filtering accuracy.

The additive of plasticizer, particulate etc. can be in advance and mixed with resin, also can be in extruderWay is mixing. In order to add equably, preferably use the mixing arrangement of static mixer etc.

The film temperature of touch roll side when film clamping with chill roll and Elastic Contact roller is preferably made asIn the scope more than Tg of film and below (Tg+110 DEG C). Use as the object with suchThere is the Elastic Contact roller of surface of elastomer, can use known Elastic Contact roller. Elastic connectingTouch roller also referred to as clamping rotary body, also can use commercially available product.

When film being peeled off from chill roll, preferably control tension force and prevent the distortion of film.

The film obtaining as described above after the operation of joining with chill roll, can pass through having passed throughStretched operation is implemented to stretch and shrink process. The method stretching and shrink can preferably be used above-mentionedKnown roller stretching device, inclination stretching device etc. Draft temperature is preferably forming film conventionallyAbove and (Tg+60 DEG C) the following temperature range of the Tg of resin carry out.

Before batching, end is cut and cut the width that becomes goods, or in order to preventAttaching in coiling, scratch and can implement at two ends annular knurl processing (embossing processing). With regard to annular knurlThe method of processing, can be by heating, pressurization to having the gold of the pattern of convex-concave in sideBelonging to ring processes. Be explained, with regard to the grip portion of the clip at film both ends, conventionallyBecause deforming, film can not use as goods, and therefore cut and recycle.

With regard to above-mentioned blooming, by stacked to make slow axis and polarizer described laterThe angle that sees through axle becomes in fact 45 °, can make circular polarizing disk. Be explained this theoryIn bright book, so-called " 45 ° in fact ", refer to be 40 ° of above and 50 ° of following scopesIn.

The angle that sees through axle of the slow axis in the face of above-mentioned blooming and polarizer is preferablyMore than 41 ° and in 49 ° of following scopes, more preferably 42 ° of above and 48 ° of following modelsIn enclosing, more preferably, more than 43 ° and in 47 ° of following scopes, be particularly preferably 44 °In scopes above and below 46 °.

< circular polarizing disk >

The circular polarizing disk of present embodiment is by having successively the diaphragm of long size shape, long chiThe long size of the blooming (phase retardation film) of the polarizer of very little shape and above-mentioned long size shape involves inRow severing and making. With regard to circular polarizing disk, owing to using above-mentioned blooming to make, thereforeBy being applied to OLED display described later etc., in the all-wave length of visible ray, can manifest and coverThe effect of the mirror-reflection of the metal electrode of organic EL. Its result, can prevent from observing timeMirror, and can make black table now improve.

In addition, the circular polarizing disk of present embodiment preferably possesses ultraviolet radiation absorption function. VisibleThe diaphragm of side possesses in the situation of ultraviolet radiation absorption function, can be at polarizer and organic ELThe two manifests element for ultraviolet protection effect. In addition, if the phase place on luminous sidePoor film also possesses ultraviolet radiation absorption function, for OLED display described later in the situation that,Can further suppress the deteriorated of organic EL.

In addition, with regard to the circular polarizing disk of present embodiment, by using the angle to slow axis(, angle of orientation θ) carried out adjusting and become " in fact with respect to length direction making45 ° " above-mentioned phase retardation film, can adopt consistent manufacturing line to carry out bond layerThe laminating of formation and polarizer and phase retardation film. Particularly, stretching polarizing coating and make polarizerOperation finish after, in the drying process then carrying out or after drying process, can introduce will riseThe operation of polariscope and phase retardation film laminating, can supply with them continuously separately, and pass throughAfter laminating, also batch with volume state, can be with consistent manufacturing line and subsequent processingBe connected. Be explained, during by polarizer and phase retardation film laminating, can be simultaneously also with volume stateSupply with diaphragm, fit continuously. Consider from the viewpoint of performance and production efficiency, preferablyPhase retardation film and diaphragm are fitted in to polarizer simultaneously. , polarizing coating stretched and makeAfter the operation of polariscope finishes, in the drying process then carrying out or after drying process, with bondingAgent is fitted diaphragm and phase retardation film respectively at the face of both sides, and the circle that can obtain volume state is inclined to one sideSheet shakes.

The circular polarizing disk of present embodiment preferably passes through above-mentioned phase retardation film and diaphragm by polarizerClamp, preferably cured layer is laminated in to the viewable side of this diaphragm.

(diaphragm)

As the diaphragm using in circular polarizing disk, preferably use the film that contains cellulose esters, exampleCellulose ester membrane as commercially available in preferred use (for example, コ ニ カ ミ ノ Le タ タ ッ Network KC8UX,KC5UX、KC4UX、KC8UCR3、KC4SR、KC4BR、KC4CR、KC4DR、KC4FR、KC4KR、 KC8UY、KC6UY、KC4UY、KC4UE、KC8UE、KC8UY-HA、KC2UA、KC4UA、KC6UAKC, 2UAH, KC4UAH, KC6UAH, be above コ ニ カ ミ ノ Le タ (strain) manufacture,フジタックT40UZ、フジタックT60UZ、フジタックT80UZ、フジタックTD80UL、フジタックTD60UL、フジタックTD40UL、フジタックR02、Off ジ タ ッ Network R06, be above the Off イ of Fuji Le system (strain) manufacture). Thick to diaphragmDegree is not particularly limited, and can be made as 10～200 μ m left and right, is preferably 10～100 μ m,More preferably 10～70 μ m.

(polarizer)

Polarizer is the element that only makes the light of the plane of polarization of certain orientation pass through, for example, have polyethyleneAlcohol is polarizing coating. In polyethenol series polarizing coating, useful iodine has dyeed polyvinyl alcohol mesenteryPolarizing coating and the polarizing coating that polyvinyl alcohol mesentery has been dyeed with dichroic dye.

Polarizer can be by polyvinyl alcohol film is carried out dyeing after uniaxial tension, or willAfter polyvinyl alcohol film dyeing, carry out uniaxial tension, preferably further carry out resistance to boron compoundProperty is processed and is made for a long time. The thickness of polarizer is the scope of 5～30 μ m preferably, more preferably 5～The scope of 15 μ m.

As polyvinyl alcohol film, preferably use TOHKEMY 2003-248123 communique, JapanThe content of the ethylidene unit of recording in JP 2003-342322 communique etc. be 1～4 % by mole,The ethylidene modified poly ethylene that the degree of polymerization 2000～4000, saponification degree are 99.0～99.99 % by moleAlcohol. In addition, can adopt TOHKEMY 2011-100161 communique, Japan Patent the 4691205thThe method of recording in number communique, No. 4804589 communique of Japan Patent is made.

< organic electroluminescence display device and method of manufacturing same (OLED display) >

The OLED display of present embodiment uses above-mentioned circular polarizing disk and makes. In more detailSay, the OLED display of present embodiment possesses the circular polarizing disk that has used above-mentioned phase retardation filmAnd organic EL. Picture dimension to OLED display is not particularly limited, Ke YiweiMore than 20 inches.

Fig. 5 is the skeleton diagram of the formation of the OLED display of present embodiment. Be explained,The formation of the OLED display 100 shown in Fig. 5 is an example, organic to present embodimentThe formation of EL display there is no any restriction.

As shown in Figure 5, on the transparency carrier 1 that has used glass, polyimides etc. successivelyThere is metal electrode 2, TFT (thin film transistor (TFT)) 3, organic luminous layer 4, transparency electrode (ITO(tin indium oxide) etc.) 5, organic EL of insulating barrier 6, sealant 7 and film 8 (can omit)On element 200, arrange and clamped polarizer by above-mentioned phase retardation film 9 and diaphragm 1110 above-mentioned circular polarizing disk 300, forms OLED display 100. Preferably by cured layer 12Be laminated in diaphragm 11. Cured layer 12 not only prevents the surperficial damage of OLED display,And there is the effect of the warpage that prevents that circular polarizing disk from causing. And then, on cured layer, can haveAnti-reflection layer 13. The thickness of above-mentioned organic EL self is 1 μ m left and right.

Usually, with regard to OLED display, on transparency carrier by metal electrode and organicLuminescent layer and transparency electrode stack gradually and form the element (organic EL) as illuminator.At this, the duplexer that organic luminous layer is various organic films, is for example knownly spread out by triphenylamineThe biological luminescent layer that waits the hole injection layer of formation and formed by the epipolic organic solid of anthracene etc.Duplexer or such luminescent layer Yu the layer of the electron injecting layer that You perylene derivative etc. formHaving of the duplexer of folded body or these hole injection layers, luminescent layer and electron injecting layer etc.The formation of various combinations.

OLED display is luminous with principle as follows: by transparency electrode and metal electricThe utmost point applies voltage, and hole and electronics are injected into organic luminous layer, by these holes and electronicsEnergy compound and that produce fluorescent material is excited, the fluorescent material being excited returns to substrateUtilizing emitted light when state. Compound mechanism is same with general diode, electric current and luminous intensity pairShow the strong non-linear with rectification in applying voltage.

In OLED display, for by the luminous taking-up in organic luminous layer, need at leastThe electrode of one is transparent, conventionally, preferably uses transparent the leading by tin indium oxide (ITO) etc.The transparency electrode that electricity body has formed is as anode. On the other hand, in order to make electronic injection easilyImprove luminous efficiency, importantly use the material that work function is little, conventionally by Mg-Ag, Al-LiDeng metal electrode use as negative electrode.

It is 20 inches that the circular polarizing disk with above-mentioned phase retardation film can be applied to picture dimensionAbove, diagonal distance is the OLED display that large-scale picture more than 50.8cm forms.

In the OLED display of such formation, organic luminous layer is by thick 10nm left and rightFilm as thin as a wafer forms. Therefore, organic luminous layer also with transparency electrode similarly, make light almost completeEntirely see through. Its result, non-when luminous from the surperficial incident of transparency carrier, see through transparency electrodeThe face side of again coming transparency carrier with organic luminous layer and at the light that metal electrode has reflected,Therefore, while watching from outside, the display surface of OLED display seems as minute surface.

The face side of carrying out luminous organic luminous layer containing logical superpotential applying possessesPrescribed electrode and possess organic EL organic of metal electrode in the rear side of organic luminous layerIn EL display, can the face side of transparency electrode (viewable side) arrange polarizer andBetween these transparency electrodes and polarizer, polarizer is set.

Phase retardation film and polarizer make from outside incident and have reflected at metal electrode owing to havingThe effect of light polarization, therefore has and utilizes its polarization and make the minute surface of metal electrode from outsideSightless effect. Especially, if with 1/4 phase retardation film formation phase retardation film and by inclined to one sideThe shake Suo Cheng angle, polarization direction of sheet and phase retardation film is adjusted to π/4, can be by metal electrodeMinute surface fully cover.

,, with regard to inciding the exterior light of this OLED display, by polarizer, only haveRectilinearly polarized light composition sees through, and this rectilinearly polarized light generally becomes Elliptical circle partially by polarizerLight shakes. Especially, phase retardation film is λ/4 phase retardation film, and polarizer and phase retardation film is inclined to one sideThe angle that the direction of shaking becomes is π/4 o'clock, becomes circularly polarized light.

This circularly polarized light sees through transparency carrier, transparency electrode, organic film, enters at metal electrodeRow reflection, sees through organic film, transparency electrode, transparency carrier again, in phase retardation film againThe inferior rectilinearly polarized light that becomes. And, this rectilinearly polarized light due to the polarization direction of polarizer justHand over, therefore can not see through polarizer. Its result, can fully hide the minute surface of metal electrodeCover. Therefore,, according to the OLED display of present embodiment, suppress external light reflection, daylight pairThan degree, black repeatability excellence.

This description, as described above, discloses the technology of variety of way, below sums up whereinMain technology.

An aspect of of the present present invention is long size blooming, and it contains cellulose derivative and titanium dioxideSilicon is particulate, and the angle that long dimensional directions becomes with slow axis is 40～50 °, under wavelength 550nmFace in phase difference Ro₅₅₀For more than 120nm and below 160nm, satisfied following formula (1)～(3)。

1.8≤Y≤2.6(1)

0.3≤X_ES≤1.5(2)

0.3≤X_ETH≤2.3(3)

In formula, X_ESFor the ester average substitution degree of cellulose derivative, X_ETHFor cellulose derivativeEther average substitution degree, total substitution value that Y is cellulose derivative.

In the long size blooming relating in one aspect of the invention, not by adding additiveSuppress to be coordinated in cellulose derivative and the phase difference that causes changes by water, but by adjustingWith the substituent ratio of cellulose derivative suppress. Its result, the optics just obtainingFilm, the variation of the optical property (tinctorial pattern performance, reflection characteristic) changing for humidity is subject toTo suppressing. In addition, because the delustering agent (silica-based particulate) having added is difficult for cohesion,Therefore also obtain fully the inhibition of the mist degree rising of this delustering agent generation. And then, thisBright long size blooming can be given in fact λ/4 for the light of the wide band of visible rayPhase difference shows excellent fragility simultaneously.

In addition, in above-mentioned long size blooming, with respect to Ro₅₅₀Wavelength 450nm under faceInterior phase difference Ro₄₅₀Ratio (Ro₄₅₀/Ro₅₅₀) be preferably more than 0.70 and below 0.98. ByThis, show the long dispersing characteristic of excellent head sea.

In addition, in above-mentioned long size blooming, above-mentioned cellulose derivative preferably has at rippleAbove and the 350nm of long 220nm has the great Multiple Bonds group of absorption, above-mentioned cellulose belowThe average substitution degree of the above-mentioned Multiple Bonds group in derivative is more than 0.3 and below 0.7. ByThis, can further improve the long dispersing characteristic of head sea.

In addition, in above-mentioned long size blooming, preferably thickness is in the scope of 20～60 μ m.Thus, easily manifest phase difference value Ro in desired face.

In addition, another aspect of the invention is the laminating of above-mentioned long size blooming and polarizerCircular polarizing disk.

According to such formation, by being applied to OLED display etc., in the all-wave of visible rayIn length, can manifest the effect that the mirror-reflection of the metal electrode of organic EL is covered. ItsAs a result, mirroring can prevent from observing time, and can make black table now improve.

In addition, another aspect of the invention is that to possess the organic electroluminescent of above-mentioned circular polarizing disk aobviousShowing device.

By such formation, external light reflection is suppressed, daylight contrast, black repeatabilityExcellent.

According to the present invention, can provide and show that sufficient manifesting property of phase difference, humidity variation causePhase difference variation be suppressed, rise with cementability, fragility excellence, the mist degree of polarizerTo the long size blooming having suppressed, possess the circular polarizing disk of this length size blooming and organicEl display device.

Embodiment

Below, enumerates embodiment the present invention is specifically described, but the present invention is not limited toThese. Be explained, in embodiment, use the expression of " part " or " % ", as long as without saying especiallyBright, represent " mass parts " or " quality % ". In addition, in substitution value shown below, replacementRadix all represents mean value.

< embodiment 1 >

Make phase retardation film 1 by following method.

(synthesizing of cellulose derivative 1)

(the 1st operation: cellulose ether synthetic)

First, before broad leaf tree, be hydrolyzed sulfate process paper pulp (chemical cellulose content 98.4%)In 100g, add 60% sodium hydroxide solution 140g, mix. Then, add bromination fourthAlkane 400g, stirs while keeps, after approximately 1 hour, being heated to the temperature range of 0～5 DEG CThe temperature range of 30～40 DEG C and make its reaction 6 hours. By content isolated by filtration, will precipitateAfter thing is removed, add wherein warm water. With in 1% phosphate aqueous solution and after, splash in acetone,Reaction product is separated out. Separate by isolated by filtration, anti-with acetone/water (9:1) solutionMultiple cleaning for several times carried out vacuum drying at 60 DEG C, obtained butyl cellulose. With regard to productThe substitution value (MS) of butyl bromide, the result of the mensuration of NMR, is 1.1, by its workFor cellulose ether.

(the 2nd operation: acetyl group is to the importing of cellulose ether)

Three mouthfuls of burnings of 3L of mechanical agitator, thermometer, cooling tube and dropping funel are being installedIn bottle, add the cellulose ether 200g, the acetone 2000mL that in the 1st operation, obtain, at room temperature stirMix. The chloroacetic chloride that splashes at leisure wherein 350g further stirs 8 after interpolation at 50 DEG CHour. After reaction, naturally cooling until turn back to room temperature, stirring tempestuously on one side on one side will be anti-Answer solution to put in methyl alcohol 20L, white solid is separated out. By suction strainer, white solid is filteredSeparate, carry out 3 times with a large amount of methyl alcohol and clean. The white solid obtaining is dry at 60 DEG CWhole night, by vacuum drying at 90 DEG C 6 hours, obtain cellulose derivative 1. RightIn the substituent substitution value of the glucose skeleton of the cellulose derivative 1 obtaining, according toCelluloseCommunication6,73-79 (1999) and Chrality12 (9),The method of recording in 670-674, passes through¹H-NMR and¹³C-NMR measures, and obtains that it is averageValue. Its result, is 2.1 as the replacement radix of the substituent butoxy with ehter bond, secondThe replacement radix of acyl group is 0.3, and total substitution value is 2.4.

(making of phase retardation film 1)

(preparation of particle dispersion liquid)

Particulate (ア エ ロ ジ Le R812 Japan's ア エ ロ ジ Le (strain) system) 11 mass parts

Ethanol 89 mass parts

To be uniformly mixed after 50 minutes with dissolvers above, use マ Application ト ン ゴ ー リ Application to disperseMachine disperses, and has prepared particle dispersion liquid.

(preparation of particulate annex solution 1)

In dissolving tank, pack the carrene of 50 mass parts into, on one side carrene is stirred fullyMix and on one side add at leisure above-mentioned particle dispersion liquid 50 mass parts of having prepared. And then, with grindingMachine disperses to make the particle diameter of offspring to become the size of regulation. Used Japanese smart lineThe Off ァ イ Application メ ッ ト NF of (strain) system filters, and has prepared particulate annex solution 1.

(preparation of rubber cement)

First, in dissolved under pressure tank, be added on carrene and the ethanol shown in following. At dressHave and in the dissolved under pressure tank of organic solvent, stir while drop into the above-mentioned cellulose having synthesized and spread outBiological 1. Be heated, stir while fully dissolving. Then, adding particulate addsAfter liquid 1, use the long-pending filter paper No.244 of peace of long-pending filter paper (strain) system of peace to filter, prepare glueSlurry.

The composition > of < rubber cement

(masking)

By the above-mentioned rubber cement of having prepared on stainless steel band supporting mass after curtain coating (casting), neverOn rust steel band supporting mass, film is peeled off. The master film of having peeled off is heated while use stretchingDevice only carries out uniaxial tension at width (TD direction), regulates conveyance tension to makeThroughput direction (MD direction) does not shrink. Then, in dry section, carry out on one side via multiple rollersCarry one side to complete dry, make the master film of roller shape.

(stretching process)

This master film is used by formed inclination stretching device, the phase of forming of recording in Fig. 2For throughput direction, become the incline direction of 45 ° at the optics slow axis of film and stretch, byThis makes the phase retardation film 1 of roller shape. Be explained, as stretching condition, suitably adjust masterThickness, draft temperature, width (TD direction) and the throughput direction (MD direction) of filmStretching ratio is with phase difference Ro in the face that makes to measure under optical wavelength 550nm₅₅₀Become138nm, thickness become 50 μ m, Ro₄₅₀/Ro₅₅₀Become 0.9.

Be explained above-mentioned Ro₅₅₀And Ro₄₅₀/Ro₅₅₀To use under 23 DEG C, 55%RH environmentThe Axoscan of Axometrics society system, phase in the face under the wavelength of mensuration 450nm, 550nmPotential difference Ro₄₅₀、Ro₅₅₀, calculate Ro simultaneously₄₅₀/Ro₅₅₀。

< comparative example 1～6, embodiment 2 >

(synthesizing of cellulose derivative 2～8)

In above-mentioned cellulose derivative 1 synthetic, suitably select the 1st operation～2nd operationIn ratio and the reaction condition of each constituent material, synthesize to make to become in table 1 to recordGlucose skeleton substituting group form, obtained cellulose derivative 1～8.

(making of phase retardation film 2～8)

In the making of above-mentioned phase retardation film 1, replace cellulose derivative 1 and having used respectivelyCellulose derivative 2～8, similarly makes phase retardation film 2～8 in addition. Be explained,As stretching condition, suitably regulate thickness, draft temperature, the width (TD of master filmDirection) and the stretching ratio of throughput direction (MD direction) under optical wavelength 550nm, measure makingFace in phase difference value Ro₅₅₀Become 140nm, thickness becomes 50 μ m, Ro₄₅₀/Ro₅₅₀BecomeFor the value of recording in table 1.

< embodiment 3 >

(synthesizing of cellulose derivative 9)

(the 1st operation)

Adopt method similarly to Example 1, make cellulose ether.

(the 2nd operation)

Three mouthfuls of burnings of 3L of machine mixer, thermometer, cooling tube and dropping funel are being installedIn bottle, add cellulose ether 200g, the pyridine 120mL, the acetone 2000mL that in the 1st operation, obtain,At room temperature stir. The chloroacetic chloride that splashes into lentamente wherein 1650g, further exists after interpolationAt 50 DEG C, stir 8 hours. After reaction, naturally cooling until turn back to room temperature, acutely stir on one sideMix one reaction solution is dropped in methyl alcohol 20L, white solid is separated out. By suction strainer, white is solidBody isolated by filtration, carries out 3 times with a large amount of methyl alcohol and cleans. By the white solid obtaining at 60 DEG CAfter being dried down whole night, vacuum drying 6 hours at 90 DEG C, has obtained cellulose derivative thus9。

For the substituent replacement of the glucose skeleton of above-mentioned cellulose derivative 9 of having preparedDegree, according to CelluloseCommunication6,73-79 (1999) and Chrality12(9), the method for recording in 670-674, passes through¹H-NMR and¹³C-NMR measures, and obtainsIts mean value. Its result, as the replacement radix of the substituent butoxy with ehter bond is0.7, the replacement radix of acetyl group is 1.4, in degree of substitution with acetyl group, as contain acetyl group andThe replacement radix with the substituent benzoic acid ester group of Multiple Bonds is 0.4, and total substitution value is 2.1.

(making of phase retardation film 9)

In the making of above-mentioned phase retardation film 1, replace cellulose derivative 1 and used fiberElement derivative 9, in addition similarly makes phase retardation film 9.

< embodiment 4 >

(synthesizing of cellulose derivative 10)

(the 1st operation)

By method similarly to Example 1, make cellulose ether.

(the 2nd operation)

Three mouthfuls of burnings of 3L of machine mixer, thermometer, cooling tube and dropping funel are being installedIn bottle, add cellulose ether 200g, the pyridine 120mL, the acetone 2000mL that in the 1st operation, obtain,At room temperature stir. Splash into lentamente after thiophene-2-phosgene of 42g, and then at 50 DEG CStir 8 hours. After reaction, naturally cooling until return to room temperature, stir tempestuously on one side on one sideReaction solution is dropped in methyl alcohol 20L, and white solid is separated out. By suction strainer by white solid mistakeFilter separates, and carries out 3 times clean with a large amount of methyl alcohol. The white solid obtaining is dry at 60 DEG CDry whole night after, at 90 DEG C, vacuum drying 6 hours, has obtained cellulose derivative 10 thus.

Glucose skeleton substituent for above-mentioned cellulose derivative 10 of having prepared gotDai Du, according to CelluloseCommunication6,73-79 (1999) and Chrality12 (9), the method for recording in 670-674, adopts¹H-NMR and¹³C-NMR measures, and asksGo out its mean value. Its result, as the replacement radix of the substituent butoxy with ehter bond is0.7, the replacement radix of acetyl group is 1.4, in degree of substitution with acetyl group, as comprising acetyl groupAnd the replacement radix with the substituent thiophene carbonyl of Multiple Bonds is 0.4, total substitution value is2.1。

(making of phase retardation film 10)

In the making of above-mentioned phase retardation film 1, replace cellulose derivative 1 and used fiberElement derivative 10, in addition similarly makes phase retardation film 10.

< comparative example 7 >

Use Supreme Being people to change into " ピ ュ ア エ ー ス " WR-W142 of (strain) system, make phase differenceFilm 11.

For phase retardation film 1～11, carry out following evaluation. Show the result in table 2.

(mist degree evaluation)

Mist degree uses haze meter (Japanese electric look industry (strain) system under 23 DEG C, 55%RH environmentNDH2000) measure.

(metewand)

◎: mist degree is less than 0.1.

Zero: mist degree is more than 0.1 and less than 0.5.

×: mist degree is more than 0.5.

(brittleness evaluation)

Make circular polarizing disk by following method, the circular polarizing disk of having made is cut into 5cm tetra-Square, in water, flood after 30 minutes, from circular polarizing disk, film is peeled off, evaluate thus fragility.

(preparation method of circular polarizing disk)

The polyvinyl alcohol film of thick 120 μ m is carried out to uniaxial tension (110 DEG C of temperature, stretching ratio5 times). It is soaked in the aqueous solution being made up of iodine 0.075g, KI 5g, water 100gSteep 60 seconds, then, at 68 DEG C that are formed by KI 6g, boric acid 7.5g, water 100gIn the aqueous solution, flood. Washed, dry and obtained polarizer. With phase retardation film 1～11Slow axis and the absorption axes of polarizer become the mode of 45 ° and use adhesive laminating, rising partiallyThe rear side of mirror is stuck with paste diaphragm (コ ニ カ ミ ノ Le タ タ ッ Network KC4UY, thick 40 by waterμ m, コ ニ カ ミ ノ Le タ (strain) system) fit, make respectively circular polarizing disk.

(metewand)

Zero: while peeling off, film does not split at all.

×: while peeling off, film splits.

(with the cementability of polarizer)

Above-mentioned each polarizer of having made is preserved 24 hours under the atmosphere of 23 DEG C of 80%RH, soAfter, under this atmosphere, measure fissility with hand, be confirmed whether to peel off.

(metewand)

Zero: can not peel off with hand. Or only end is peeled off, if by its above peeling off, structurePart is destroyed.

×: the part beyond end is also peeled off with hand.

(making of organic EL unit)

Use 50 inches (127cm) that 3mm is thick to use alkali-free glass, according to JP 2010-20925The method of recording in the embodiment of number communique, makes the Fig. 8 by JP 2010-20925 communiqueOrganic EL unit of the formation composition of middle record.

(making of OLED display)

At the surface-coated bonding agent of the phase retardation film 1～11 of above-mentioned each circular polarizing disk of having madeAfter, fit in the viewable side of organic EL unit, make respectively thus OLED display.

(evaluation of OLED display)

For above-mentioned each OLED display of having made, carry out following evaluation.

(black tinctorial pattern humidity stability)

Under 23 DEG C, the low wet environment of 20%RH, in the most surface from each OLED displayThe illumination of the position that 5cm is high becomes under the condition of 1000Lx, in OLED display, showsPicture black. Then,, under 23 DEG C, the high humidity environment of 80%RH, similarly show picture black.Under above-mentioned two environment, to the front position from each OLED display (with respect to face normal,Be 0 °), being the picture black at the angle of inclination of 40 ° with respect to face normal, tinctorial pattern comparesObserve, have or not according to following benchmark evaluation that humidity causes by general human observer 10 people to blackThe impact of tinctorial pattern. Be explained, if more than zero, as the humidity stability of black sample,Being judged as can be practical.

(metewand)

◎: more than 9 people human observer judgement does not exist the black humidity effect having shown.

There is not the black humidity effect having shown in zero: 5～8 people's human observer judgement.

×: judge that not having the human observer of the black humidity effect having shown is below 4 people.

(antireflection property humidity stability)

In the making of above-mentioned OLED display, in the stage of having made organic EL unit,Give red, blue, green line on viewable side surface with magic ink, in addition similarly madeEvaluate the OLED display of use. There is red, blue, green line organic for what madeEL display, under 23 DEG C, the low wet environment of 20%RH, from each OLED displayThe illumination of the position that most surface 5cm is high becomes under the condition of 1000Lx, aobvious to giving organic ELShow that the observability (reflecting properties) of the line of the magic ink of device evaluates. Then, 23 DEG C,Under the high humidity environment of 80%RH, similarly by general human observer 10 people according to following benchmark pairThe observability (reflecting properties) of the line of magic ink is evaluated. Be explained if zeroAbove, as the humidity stability of reflecting properties, being judged as can be practical. Be explained, hereSaid reflecting properties is not the surperficial reflection of circular polarizing disk, but fingering has entered circular polarizing diskOrganic EL unit of inside in reflection.

(metewand)

◎: human observer more than 9 people be judged to be not exist the magic ink that humidity causes line canThe impact of opinion property.

Zero: 5～8 people's human observer is judged to be not exist line visible of the magic ink that humidity causesProperty affects.

×: the visible sex human observer that is judged to be not exist the line of the magic ink that humidity causesBe below 4 people.

As shown in table 1 and table 2, substitution value meets the numerical value model of formula (1)～(3)The mist degree of the blooming (phase retardation film 1,8～10) of the embodiment 1～4 enclosing is little, and fragility is excellentDifferent. In addition, the cementability of these bloomings and polarizer is also excellent, uses it and has madeBlack tinctorial pattern, the antireflection property of OLED display are also excellent.

On the other hand, ester average substitution degree is less than the blooming of the comparative example 1 of the lower limit of formula (2)The mist degree of (phase retardation film 2) is large. Exceeded the ratio of the upper limit of formula (2) with regard to ester average substitution degreeThe blooming of example 2, comparative example 3 (phase retardation film 3 and phase retardation film 4), uses itAnd black tinctorial pattern, the antireflection property of the OLED display of having made are unexcellent. In addition, etherAverage substitution degree exceedes the upper limit of formula (3), always substitution value has exceeded the ratio of the upper limit of formula (1)The fragility of the blooming of example 4 (phase retardation film 5) is unexcellent, uses it and having of having madeThe antireflection property of machine EL display is unexcellent. And then total substitution value is less than under formula (1)The mist degree of blooming (phase retardation film 6) of the comparative example 5 of limit is large, uses it and madeBlack tinctorial pattern, the antireflection property of OLED display are unexcellent. Ether average substitution degree is less than formula(3) blooming (phase retardation film 5) of the comparative example 6 of lower limit and the cementability of polarizer are notExcellent. In addition, do not use cellulose derivative as resin but used modification to gather carbonic acidThe blooming (phase retardation film 11) of the comparative example 7 of ester is poor with the cementability of polarizer.

The application is to be willing in the Japanese patent application laid of application on September 19th, 2013Be for No. 2013-193688 basis, its content comprises in this application.

In order to show the present invention, above-mentioned middle suitable to the present invention by embodiment with reference to accompanying drawingAnd be illustrated fully, those skilled in the art will recognize that can be easily to above-mentioned realityThe mode of executing changes and/or improves. It is therefore to be understood that the change that those skilled in the art implementMode or improved procedure are so long as not the right model that departs from the claim of recording in claimsThe level of enclosing, this alter mode or this improved procedure are included in the interest field of this claimIn.

Utilizability in industry

According to the present invention, can obtain showing that sufficient manifesting property of phase difference, inhibition humidity change and drawsThe phase difference variation, the cementability with polarizer, fragility excellence, the mist degree that rise rise and have obtained pressing downThe long size blooming of system. Therefore, the present invention can obtain well with wide viewing angle for example requiringThe field of contrast, the image display device of tone balance etc. in utilize suitably. In addition,According to the present invention, can provide the circular polarizing disk and the organic electroluminescence that possess above-mentioned long size bloomingLuminous display unit.

The explanation of symbol

A inclination stretching device entrance

Position when B stretches end

Ci, Co grasp tool

D1 extracts direction out

D2 take-up direction

F cellulose acylate film

Ri, Ro track

100 OLED displays

200 organic ELs

300 circular polarizing disks

1 transparency carrier

2 metal electrodes

3TFT

4 organic luminous layers

5 transparency electrodes

6 insulating barriers

7 sealants

8 films

9 phase retardation films

10 polarizers

11 diaphragms

12 cured layers

13 anti-reflection layers

15 inclination stretching devices

16 film withdrawing devices

17 throughput direction change devices

18 devices for taking-ups

19 film forming apparatus

111,112 draw directions

113 throughput directions

114 slow axis

Claims (6)

1. a long size blooming, it contains cellulose derivative and silica-based particulate,

The angle that long dimensional directions becomes with slow axis is 40～50 °,

Phase difference Ro in the face of wavelength 550nm₅₅₀For more than 120nm and below 160nm,

Meet following formula (1)～(3):

1.8≤Y≤2.6(1)

0.3≤X_ES≤1.5(2)

0.3≤X_ETH≤2.3(3)

In formula, X_ESFor the ester average substitution degree of cellulose derivative, X_ETHFor cellulose derivativeEther average substitution degree, total substitution value that Y is cellulose derivative.

2. long size blooming claimed in claim 1, wherein, in the face of wavelength 450nmPhase difference Ro₄₅₀With respect to Ro₅₅₀Ratio (Ro₄₅₀/Ro₅₅₀) be more than 0.70 and below 0.98.

3. the long size blooming described in claim 1 or 2, wherein, described cellulose-derivedThing has and more than wavelength 220nm and below 350nm, has the great Multiple Bonds group of absorption,

The average substitution degree of the described Multiple Bonds group in described cellulose derivative is more than 0.3And below 0.7.

4. the long size blooming described in any one of claim 1～3, wherein, thickness isIn the scope of 20～60 μ m.

5. a circular polarizing disk, wherein, the long size described in any one of claim 1～4Blooming and polarizer laminating.

6. an organic electroluminescence display device and method of manufacturing same, it possesses circular polarization claimed in claim 5Sheet.