CN107850715A - Phase retardation film, polarizer and vertical orientating type liquid crystal display device - Google Patents

Abstract

The present invention relates to phase retardation film, polarizer and vertical orientating type liquid crystal display device.Phase retardation film includes：Cellulose esters system resin with acetyl group and bytyry, delay rise agent and sugar ester.When the delay in direction in the face of film being set into Ro (nm), the delay of the thickness direction of film being set to Rth (nm), be 50nm≤| Ro |≤80nm, be 200nm≤| Rth |≤300nm.

Description

Phase retardation film, polarizer and vertical orientating type liquid crystal display device

Technical field

The present invention relates to phase retardation film, the polarizer of the phase retardation film is used and has used the vertical orientated of the polarizer Type (VA types；Vertical Alignment) liquid crystal display device.

Background technology

In recent years, the requirement reduced to slimming, lightweight and the cost of Informationization Equipment (particularly display device) exists Increase.Especially in a kind of liquid crystal display device (LCD) of VA types as display device, regarding for LCD is generated Wild angle improves, the improvement of contrast (phase difference) and the filming of phase retardation film that uses and then will be for liquid crystal cell visible Side and the total phase retardation film for employing 2 of backlight side are changed into the demand of 1 grade.

In the LCD of VA types, it is necessary to make side in the face of the phase retardation film when number of the phase retardation film used is 1 To delay Ro and thickness direction delay Rth than using 2 phase retardation films situation it is high.For example, using 2 phase retardation films 2 modes (mode of 2 phase retardation films) in, each phase retardation film Ro and Rth be Ro=50nm, Rth=120nm feelings Under condition, in 1 mode (mode of 1 phase retardation film) of 1 phase retardation film is only used, it is necessary to make phase retardation film Ro and Rth is Ro=65nm, Rth=250nm or so.The LCD of the VA types of 1 phase retardation film has so only been used for example in patent text Offer disclosed in 1.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2005-241794 publications (with reference to claim 1, paragraph [0204]~[0209], [0215], [0221] etc.)

The content of the invention

The invention problem to be solved

But for the phase retardation film of patent document 1, thickness is set to thick (such as 100 μm or so).If film Thickness is thick, then in the film using solution curtain coating film method, becomes difficult from the stripping of the film (casting films) of supporting mass, peel off When drying after striped, fraction defective rise or stretching is produced on film spend time etc., worry that the productivity ratio of film reduces.In addition, If film thickness is thick, the amplitude of fluctuation (difference of the maxima and minima of thickness) of thickness easily becomes big thickness in film surface Fluctuate (inhomogeneity) and easily become big.If the fluctuation of thickness becomes big, the delay Rth of the thickness direction in worry film surface ripple It is dynamic to become display inequality big, that LCD occurs.

The present invention completes to solve the problems, such as above-mentioned, and its object is to provide to improve as 1 phase retardation film to make The productivity ratio of phase retardation film and the uneven phase retardation film of fluctuation is caused in delay Rth face display can be mitigated, made With the polarizer of the phase retardation film and the vertical orientating type liquid crystal display device of the polarizer is used.

Means for solving the problems

The above-mentioned purpose of the present invention is realized by following composition.That is, the phase retardation film bag that an aspect of of the present present invention is related to Contain：Cellulose esters system resin with acetyl group and bytyry, delay rise agent and sugar ester, by the delay in direction in the face of film When being set to Ro (nm), the delay of the thickness direction of film being set to Rth (nm), it is：

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm。

The effect of invention

By phase retardation film include delay rise agent, even if making the thickness of film thinning, can also realize high delay (Ro and Rth).Therefore, it is possible to realize the filming of the phase retardation film used as 1 phase retardation film.In addition, comprising with acetyl group and The film of the cellulose esters system resin of bytyry is compared with the situation comprising other cellulose esters system resins, in the solution curtain coating system of use In the film of embrane method, easily peeled off from supporting mass.Therefore, the filming and specific cellulose esters system resin of phase retardation film are passed through Use, the fissility from supporting mass during the film of phase retardation film can be reliably improved, thus, it is possible to improve phase retardation film Productivity ratio.

In addition, by the filming of phase retardation film, the amplitude of fluctuation (difference of the maxima and minima of thickness) of thickness becomes It is small, therefore the fluctuation (inhomogeneity) of the thickness in film surface can be reduced.Also, sugar ester is included by phase retardation film, due to film Become soft (because sugar ester has the function as plasticizer), more equably mixed in film further, since delay rises agent The ripple of the thickness in film surface when closing (because sugar ester has function as compatilizer), therefore can further mitigate film It is dynamic.So, by the filming of phase retardation film and the use of sugar ester, the fluctuation of the delay Rth in film surface can reliably be mitigated, The display that can mitigate when the phase retardation film that film forms to be applied to liquid crystal display device is uneven.

Brief description of the drawings

Fig. 1 is the composition of the outline for the liquid crystal display device for representing the vertical orientating type that embodiments of the present invention are related to Profile.

Fig. 2 is the device for showing schematically the phase retardation film applied in the polarizer for manufacturing above-mentioned liquid crystal display device The explanation figure of one.

Embodiment

It is as follows if illustrated for one embodiment of the present invention based on accompanying drawing.It should illustrate, this specification In, in the case where number range is expressed as into A~B, it is set to include lower limit A and upper limit B value in its number range.In addition, The present invention is not limited to following content.

[vertical orientating type liquid crystal display device]

Fig. 1 is the composition of the outline for the liquid crystal display device 1 for representing vertical orientating type (VA types) of the present embodiment Profile.Liquid crystal display device 1 has liquid crystal display panel 2 and backlight 3.Backlight 3 is for being carried out to liquid crystal display panel 2 The light source of illumination.

For liquid crystal display panel 2, polarizer 5 is configured at the liquid crystal cell 4 driven in a manner of VA viewable side, The side of backlight 3 configures polarizer 6 and formed.Liquid crystal cell 4 is formed with a pair of transparency carriers clamping liquid crystal layer (not shown).As liquid Brilliant box 4, transparency carrier, i.e. TFT (the Thin Film that colour filter is configured to the side of backlight 3 relative to liquid crystal layer can be used Transistor the liquid crystal cell of substrate, so-called array on color filter (COA) structure of side) is formed but it is also possible to be by colour filter Device is configured at the liquid crystal cell of the transparency carrier of viewable side relative to liquid crystal layer.

Polarizer 5 has polarizer 11 and optical film 1213.Polarizer 11 passes through defined rectilinearly polarized light.Optics Film 12 is the diaphragm that is configured in the viewable side of polarizer 11.Optical film 13 is the side of the backlight 3 (liquid crystal cell 4 in polarizer 11 Side) diaphragm and phase retardation film that are configured.Polarizer 5 is pasted on to the viewable side of liquid crystal cell 4 via adhesive layer 7.I.e., just partially Shake for piece 5, be located at viewable side relative to liquid crystal cell 4 and turn into the side of the side of liquid crystal cell 4 relative to polarizer 11 with optical film 13 Formula fits in liquid crystal cell 4.

Polarizer 6 possesses polarizer 14 and optical film 1516.Polarizer 14 passes through defined rectilinearly polarized light.Optics Film 15 is the diaphragm configured in the viewable side of polarizer 14, can be used as phase retardation film to play function.Optical film 16 For the diaphragm configured in the side of backlight 3 of polarizer 14.Such polarizer 6 is pasted on liquid crystal cell 4 via adhesive layer 8 The side of backlight 3.It is explained, the optical film 15 of viewable side can be omitted and polarizer 14 is directly contacted adhesive layer 8.By polarizer 11 Configured with polarizer 14 in a manner of as cross Nicols state.

The phase retardation film of present embodiment for example can be as the optical film 13 of polarizer 5, the optical film 15 of polarizer 6 Use.But it is the delay Ro and thickness in direction in face as following record for the phase retardation film of present embodiment The delay Rth in direction is than using the high phase retardation film of so-called 1 of each phase retardation film during 2 phase retardation films.Therefore, can be Protected in any one of optical film 13 and optical film 15 using the phase retardation film of present embodiment, in another one using simple Film or the zero phase difference film that phase difference is hardly given to transmitted light.The details of phase retardation film is illustrated below.

[phase retardation film]

The phase retardation film of present embodiment includes the cellulose esters system resin with acetyl group and bytyry, delay rises agent And sugar ester,

When the delay in direction is set to Ro (nm), the delay of the thickness direction of film is set to Rth (nm) in the face by film, it is

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm。

It should illustrate, phase retardation film can include the fiber beyond " the cellulose esters system resin with acetyl group and bytyry " Plain ester system resin (such as cellulose diacetate, cellulose triacetate), can not include yet.

Delay is included by the phase retardation film of present embodiment and rises agent, even if making the thickness of phase retardation film thinning, also can Enough realize high delay.Specifically, even if making the thickness of phase retardation film is thin to reach such as less than 80 μm, also can as Ro and Rth Realize above-mentioned high level (scope).Therefore, for phase retardation film, to require the same of high latency Ro and Rth 1 phase retardation film When being capable of filming.In addition, by making phase retardation film filming, the cost for the material for forming phase retardation film can be also reduced.

In addition, used comprising the film with acetyl group and the cellulose esters system resin (cellulose acetate-butyrate) of bytyry Easily peeled off in the film of solution curtain coating film method from supporting mass (metal support).Its reason is presumed as follows described.It is if fine Tie up that the polarity of the substituent of plain ester system resin is strong, then become big with the interaction on the surface of metal support, the base-material being cast (resin) and the closing force of metal support raise.As a result, film becomes to be difficult to peel off from metal support.With regard to bytyry Speech, is hydrophobic substituent, polarity is weak, therefore includes the cellulose esters substituted with bytyry compared with acetyl group, propiono It is that the film of resin (cellulose acetate-butyrate) and the closing force of metal support reduce, becomes easily to peel off from metal support.

Therefore, by the filming of phase retardation film and the use of specific cellulose esters system resin, be able to can reliably carry The fissility from supporting mass during the film of high phase place difference film.As a result, it can be avoided in film：Produced during stripping in film Drying after striped and fraction defective rise or stretching spends the time, can produce at a high speed and stably film.I.e., it is possible to increase film Productivity ratio.

In addition, the thickness of phase retardation film is thicker, the scope that thickness changes (difference of the maxima and minima of thickness, changes Amount) more become big, therefore the inhomogeneity of the thickness in film surface becomes big.That is, the thickness of phase retardation film is thicker, the thickness in film surface Fluctuation more becomes big.But in present embodiment, in addition to it can make phase retardation film filming as described above, phase retardation film Include sugar ester.Sugar ester is as making film become soft plasticizer and for making delay rise the phase that agent more equably mixes in film Hold agent and play function.Therefore, sugar ester is included by phase retardation film, the thickness in film surface when can further reduce film Fluctuation.Thus, the fluctuation (thickness inhomogeneity) of thickness in film surface, the ripple of the delay Rth in reduction face are reduced in film It is dynamic to be possibly realized.As a result, it is uneven to mitigate display in the liquid crystal display device of the phase retardation film comprising present embodiment Occur.

Especially, the preferred thickness of the phase retardation film of present embodiment is more than 40 μm and less than 70 μm.Pass through phase retardation film For film, the fluctuation for mitigating the thickness in film surface can be reliably obtained and postpone Rth fluctuation and mitigate the upper of display inequality The effect stated.

In addition, cellulose esters system resin contained in the phase retardation film of present embodiment preferably meets following formula (1) simultaneously And (2).

1.8≤X+Y≤2.9··(1)

0.03≤Y≤0.8···(2)

Wherein, X represents the substitution value of acetyl group, and Y represents the substitution value of bytyry.

It should illustrate, the substitution value of acetyl group and bytyry can be according to ASTM (American Society for Testing and Materials；Test material association of the U.S.) planning is formulated and the i.e. ASTM-D817-96 of one of standard for issuing Regulation measure.

The cellulose esters system resin for meeting formula (1) and (2) is cellulose acetate-butyrate.Included by phase retardation film such Cellulose acetate-butyrate, the stripping from the film of supporting mass can be reliably improved in the film using solution curtain coating film method Property, reliably improve film productivity ratio.It is explained, the preferred scope of total acyl substitution (X+Y) is

2.4≤X+Y≤2.9···(1’)。

Each composition of the phase retardation film of present embodiment is described in more detail below.

[cellulose esters system resin]

As the cellulose of the raw material of cellulose esters, such as cotton linters, wood pulp, mestha etc. can be included, but it is not special These are not defined in it.In addition, can be by the cellulose esters obtained by these each so that arbitrary ratio mixes and uses.

As cellulose esters system resin, cellulose acetate (cellulose diacetate, cellulose triacetate), second are preferably selected from At least 1 in sour cellulose propionate, cellulose acetate-butyrate, acetic acid cellulose benzoate, cellulose propionate and cellulose butyrate Kind, in these, from the fissility improved from supporting mass, from the viewpoint of the productivity ratio for improving film, cellulose esters system resin is excellent Choosing includes cellulose acetate-butyrate.That is, cellulose esters system resin only can be made up of cellulose acetate-butyrate, also can be by acetic acid fourth The resin that other compositions (such as cellulose diacetate, cellulose triacetate) are mixed with acid cellulose is formed.From reliably carrying From the viewpoint of the productivity ratio of high film, more than the 80% of preferred cellulose ester system resin entirety is cellulose acetate-butyrate, optimal It is cellulose acetate-butyrate to select whole amount.

The weight average molecular weight (Mw) of cellulose esters system resin is preferably more than 75000, more preferably 75000~300000 Scope, in the range of more preferably 100000~240000, particularly preferred 160000~240000.If it is above-mentioned it is heavy divide equally Son amount (Mw) is more than 75000, then play the self film of cellulose esters system resin itself, closely sealed improvement and it is preferred that.

The mean molecule quantity (Mn, Mw) of cellulose esters system resin can be respectively by gel permeation chromatography in following measure Under the conditions of determine.

Solvent：Dichloromethane

Post：Shodex K806, K805, K803G (using 3 connections of Showa electrician (strain) manufacture)

Column temperature：25℃

Sample solution concentration：0.1 mass %

Detector：RI Model 504 (manufacture of GL Science companies)

Pump：L6000 (Hitachi (strain) manufactures)

Flow：1.0ml/min

Calibration curve：Use using polystyrene standard STK standard Polystyrene (East ソ ー (strain) systems Make) the obtained calibration curve of 13 samples in the range of Mw=500~2800000.13 samples are preferably at substantially equal intervals Use.

[delay rises agent]

Delay rises agent and refers to delay (the particularly delay of thickness direction with the film made under measure wavelength 590nm Rth) the compound for the function of increasing compared with delay rises the un-added film of agent.

Delay is contained by phase retardation film and rises agent, delay Ro and the thickness side in direction in the face of phase retardation film can be realized To delay Rth turn into following scope phase retardation film.

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm

For above-mentioned Ro and Rth, such as can be by using automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan Mueller Matrix Polarimeter：ア Network ソ メ ト リ ッ Network ス companies manufacture), in 23 DEG C of temperature, relative humidity The refractive index n obtained by three-dimensional refractive index measure is carried out in the environment of 55%RH, under measure wavelength 590nm_x、n_y、n_z, it is based on down Formula calculates.

Ro=(n_x-n_y)×d(nm)

Rth={ (n_x+n_y)/2-n_z}×d(nm)

(in formula, n_xRepresent that refractive index turns into the refractive index on maximum direction x on direction in the face of film.n_yRepresent in film Face in refractive index on direction y orthogonal with above-mentioned direction x on direction.n_zRepresent the refractive index on the thickness direction z of film.d Represent the thickness (nm) of film.)

In present embodiment, molecular weight can be used to be used as delay for the nitrogen-containing heterocycle compound in the range of 100~800 Rise agent.Wherein, nitrogen-containing heterocycle compound is preferably the compound of the structure represented by following formulas (1).By will have by The compound for the structure that following formulas (1) represent is used together with resin, except that can realize phases of the Ro and Rth for above range Beyond potential difference film, the humidity that can also suppress environment changes the variation of caused delay.

＜ has the compound ＞ of the structure represented by formula (1)

【Change 1】

Formula (1)

A₁-L₁-T₁-L₂-B-(L₃-T₂-L₄-A₂)_n

In above-mentioned formula (1), A₁、A₂And B represents alkyl (methyl, ethyl, n-propyl, isopropyl, tertiary fourth independently of one another Base, n-octyl, 2- ethylhexyls etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyls etc.), aromatic series hydrocarbon ring Or heteroaromatic.Wherein, optimization aromatic hydrocarbon ring or heteroaromatic, particularly preferably 5 yuan or 6 yuan of aromatic series hydrocarbon ring or Heteroaromatic.

The structure of aromatic series hydrocarbon ring or heteroaromatic to 5 yuan or 6 yuan is simultaneously unrestricted, such as can include phenyl ring, pyrrole Cough up ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings, 1,2,4- triazole rings, tetrazole ring, furan nucleus, oxazole ring, isoxazole ring, Evil Diazole ring, Yi oxadiazole rings, thiphene ring, thiazole ring, isothiazole ring, Thiadiazole, different Thiadiazole, carbazole ring, quinoxaline ring, Benzoxazole ring etc..Wherein, nitrogen-containing heterocycle compound is preferably selected from carbazole ring, quinoxaline ring, benzoxazole ring, Evil bis- It is at least any of in the compound of azoles Huan, oxazole rings, triazole ring and pyrazole ring.

By A₁、A₂And 5 yuan or 6 yuan of the aromatic series hydrocarbon ring or heteroaromatic that B is represented can have substituent.Taken as this Dai Ji, such as halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), alkyl (methyl, ethyl, positive third can be included Base, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls etc.), cycloalkyl (the n- dodecyl hexamethylene of cyclohexyl, cyclopenta, 4- Base etc.), alkenyl (vinyl, pi-allyl etc.), cycloalkenyl group (2- cyclopentene -1- bases, 2- cyclohexene -1- bases etc.), alkynyl (acetylene Base, propargyl etc.), aromatic cyclic hydrocarbon group (phenyl, p- tolyl, naphthyl etc.), aromatic heterocycle (2- pyrrole radicals, 2- furans Base, 2- thienyls, pyrrole radicals, imidazole radicals, oxazolyls, thiazolyl, benzimidazolyl, benzoxazolyl, 2-[4-morpholinodithio base, pyrrole Oxazoline ketone group, pyridine radicals, pyriconyl, 2- pyrimidine radicals, triazine radical, pyrazolyl, 1,2,3- triazolyls, 1,2,4- triazolyl, Evil Oxazolyl, isoxazolyls, 1,2,4- oxadiazolyls, 1,3,4- oxadiazolyls, thiazolyl, isothiazolyl, 1,2,4- thiadiazolyl groups, 1, 3,4- thiadiazolyl groups etc.), cyano group, hydroxyl, nitro, carboxyl, alkoxy (methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, just Octyloxy, 2- methoxy ethoxies etc.), aryloxy group (phenoxy group, 2- methylphenoxies, 4- tert-butyls phenoxy group, 3- nitrobenzene Epoxide, 2- myristoyl amino-benzene oxygens etc.), acyloxy (formyloxy, acetoxyl group, new pentane acyloxy, stearoyl-oxy, Benzoyloxy, p- methoxyphenyl carbonyloxy group etc.), amino (amino, methylamino, dimethylamino, anilino-, N- first Base-anilino-, diphenyl amino etc.), acylamino- (formamido group, acetylamino, pivaloyl amino, lauroyl amino, benzoyl Amino etc.), alkyl and Arenesulfonyl amino (sulfonyloxy methyl amino, butyl sulfonamido, phenylsulfonyl-amido, 2,3,5- trichlorines Phenylsulfonyl-amido, p- methylphenyl-sulfonamido etc.), sulfydryl, alkylthio group (methyl mercapto, ethylmercapto group, n- hexadecylthio Deng), arylthio (thiophenyl, p- chlorophenylsulfanyl, m- Methoxv-phenylsulfanvl etc.), sulfamoyl (N- ethylsulfamovls, N- (3- dodecyloxies propyl group) sulfamoyl, N, N- DimethylsuIfamoyls, N- acetylsulfamoyls, N- benzoyl ammonia sulphurs Acyl group, N- (N '-phenylcarbamoyl) sulfamoyl etc.), sulfo group, acyl group (acetyl group, valeryl benzoyl etc.), ammonia Base formyl base class (carbamoyl, N- methylcarbamoyls, N, N- formyl-dimethylaminos, N, N- bis--n- octyl group ammonia Base formoxyl, N- (methyl sulphonyl) carbamoyl etc.) etc. each group.

In above-mentioned formula (1), A₁、A₂And B represents phenyl ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings or 1,2, 4- triazole rings, then obtain optical characteristics changes excellent effect and the cellulose acylate film of excellent in te pins of durability, therefore excellent Choosing.

In above-mentioned formula (1), preferably T₁And T₂Pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazoles are represented independently of one another Ring or 1,2,4- triazole rings.In these, in order to obtain for humidity change delay variation inhibition it is especially excellent and The resin combination of excellent in te pins of durability, preferably pyrazole ring, triazole ring or imidazole ring, particularly preferably pyrazole ring.By T₁And T₂Represent Pyrazole ring, 1,2,3- triazole rings or 1,2,4- triazole rings, imidazole ring can be dynamic isomer.Pyrrole ring described below, Pyrazole ring, imidazole ring, the specific structure of 1,2,3- triazole rings or 1,2,4- triazole rings.

【Change 2】

In formula, ※ marks represent and the L in formula (1)₁、L₂、L₃Or L₄Binding site.R⁵Represent hydrogen atom or non-aromatic Race's substituent.As by R⁵The non-aromatic substituent of expression, it can include and the A in above-mentioned formula (1)₁What can be had takes The same group of Dai Jizhong non-aromatic substituent.By R⁵The substituent of expression is the feelings of the substituent with aromatic group Under condition, A₁With T₁Or B and T₁Easily distortion, A₁, B and T₁The interaction with cellulose acylate can not be formed, therefore, it is difficult to Suppress the variation of optical characteristics.In order to improve the variation inhibition of optical characteristics, R⁵Preferably hydrogen atom, the alkane of carbon number 1~5 The acyl group of base or carbon number 1~5, particularly preferably hydrogen atom.

In above-mentioned formula (1), T₁And T₂There can be substituent, as the substituent, can include and above-mentioned formula (1) In A₁And A₂The same group of the substituent that can have.

In above-mentioned formula (1), L₁、L₂、L₃And L₄The linker of singly-bound or divalent is represented independently of one another, via less than 2 Atom be connected with the aromatic series hydrocarbon ring or heteroaromatic of 5 yuan or 6 yuan.The so-called atom via less than 2, represent the company of composition Connect in the atom of base the existing minimum atomicity between the substituent connected.As the divalent below connection atomicity 2 Linker, there is no particular restriction, for the divalent in alkylidene, alkenylene, alkynylene, O, (C=O), NR, S, (O=S=O) Linker, or represent 2 linkers combined in these.R represents hydrogen atom or substituent.Represented by R Substituent example in, include alkyl (methyl, ethyl, n-propyl, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls Deng), cycloalkyl (n- dodecyl cyclohexyl of cyclohexyl, cyclopenta, 4- etc.), aromatic cyclic hydrocarbon group (phenyl, p- tolyl, Naphthyl etc.), aromatic heterocycle (2- furyls, 2- thienyls, 2- pyrimidine radicals, 2-[4-morpholinodithio base, 2- pyridine radicals etc.), cyano group Deng.By L₁、L₂、L₃And L₄The linker of the divalent of expression can have substituent, and as substituent, there is no particular restriction, such as can To include and the A in above-mentioned formula (1)₁And A₂The same group of the substituent that can have.

In above-mentioned formula (1), with regard to L₁、L₂、L₃And L₄For, pass through the chemical combination with the structure represented by above-mentioned formula (1) The flatness rise of thing, so as to the Interaction enhanced of the resin with adsorbing water, suppress the variation of optical characteristics, therefore be preferably Singly-bound or O, (C=O)-O, O- (C=O), (C=O)-NR or NR- (C=O), more preferably singly-bound.

In above-mentioned formula (1), n represents 0~5 integer.It is multiple in above-mentioned formula (1) when n represents more than 2 integer A₂、T₂、L₃、L₄Can be with identical, also can be different.N is bigger, has compound and the absorption of the structure represented by above-mentioned formula (1) The Interaction enhanced of the resin of water, so as to optical characteristics variation inhibition it is excellent, n is smaller, then with adsorb water resin It is excellent in compatibility.Therefore, n is preferably 1~3 integer, more preferably 1~2 integer.

＜ has the compound ＞ of the structure represented by formula (2)

Compound with the structure represented by formula (1) is preferably the compound with the structure represented by formula (2).

【Change 3】

(in formula, A₁、A₂、T₁、T₂、L₁、L₂、L₃And L₄Respectively with the A in above-mentioned formula (1)₁、A₂、T₁、T₂、L₁、L₂、L₃With L₄It is synonymous.A₃And T₃Represent respectively and the A in formula (1)₁And T₁Same group.L₅And L₆Represent and the L in above-mentioned formula (1)₁ Same group.M represents 0~4 integer.)

It is excellent in compatibility with cellulose acylate due to m hours, therefore m is preferably 0~2 integer, more preferably 0 ~1 integer.

＜ has the compound ＞ of the structure represented by formula (1.1)

Compound with the structure represented by formula (1) is preferably with the structure represented by following formulas (1.1) Triazole compounds.

【Change 4】

Formula (1.1)

(in formula, A₁、B、L₁And L₂Represent and the A in above-mentioned formula (1)₁、B、L₁And L₂Same group.K represents 1~4 Integer.T₁Represent 1,2,4- triazole rings.)

And then the triazole compounds with the structure represented by above-mentioned formula (1.1) are preferably with by following formulas (1.2) triazole compounds of the structure represented.

【Change 5】

Formula (1.2)

(in formula, Z represents the structure of following formulas (1.2a).Q represents 2~3 integer.At least two Z are relative in phenyl ring On at least one Z that instead of be incorporated into ortho position or meta.)

【Change 6】

Formula (1.2a)

(in formula, R¹⁰Represent hydrogen atom, alkyl or alkoxy.P represents 1~5 integer.* the bound site with phenyl ring is represented Put.T₁Represent 1,2,4- triazole rings.)

Compound with the structure represented by above-mentioned formula (1), (2), (1.1) or (1.2) can form hydrate, solvent Compound or salt.It should illustrate, in present embodiment, hydrate can contain organic solvent, and solvate can contain water in addition.That is, The mixed solvent compound containing both water and organic solvent is included in " hydrate " and " solvate ".As salt, comprising by nothing The acid-addition salts that machine or organic acid form.As the example of inorganic acid, halogen acids (hydrochloric acid, hydrobromic acid etc.), sulfuric acid, phosphorus are included Acid etc., in addition, being not limited to these.In addition, in the example of organic acid, can include acetic acid, trifluoracetic acid, propionic acid, butyric acid, Oxalic acid, citric acid, benzoic acid, alkyl sulfonic acid (methanesulfonic acid etc.), aryl sulfonic acid (benzene sulfonic acid, 4- toluenesulfonic acids, 1,5- naphthalenedisulfonic acids Deng) etc., in addition, being not limited to these.In these, preferably hydrochloride, acetate, propionate, butyrate.

As the example of salt, can include acidic moiety present in close compound by metal ion (such as alkali metal salt, Such as sodium or sylvite, alkali earth metal salt, such as calcium or magnesium salts, ammonium salt, alkali metal ion, alkaline-earth metal ion or aluminium from Son etc.) salt formed during organic base (monoethanolamine, diethanol amine, triethanolamine, morpholine, piperidines etc.) is replaced or is adjusted to, In addition, it is not limited to these.It is preferably sodium salt, sylvite in these.

In the example for the solvent that solvate includes, also comprising any organic solvent in general organic solvent.Tool Body, alcohol (such as methanol, ethanol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, tert-butyl alcohol), ester (such as vinegar can be included Acetoacetic ester), hydrocarbon (such as toluene, hexane, heptane), ether (such as tetrahydrofuran), nitrile (such as acetonitrile), ketone (acetone) etc..It is preferred that For the solvate of alcohol (such as methanol, ethanol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, tert-butyl alcohol).These solvents can Partial crystallization during being the synthesis of above-claimed cpd after used reaction dissolvent or synthesis is used molten when refined Agent, or can be their mixture.

In addition, solvent of more than two kinds can be contained simultaneously, can be containing water and solvent form (such as water and alcohol (such as Methanol, ethanol, tert-butyl alcohol etc.) etc.).

Should illustrate, can be added in the form of not aqueous, solvent, salt with by above-mentioned formula (1), (2), (1.1) or (1.2) compound of the structure represented, (following " optical film " substantially refers to phase difference to optical film in the present embodiment Film.) in, hydrate, solvate or salt can also be formed.

Spy is had no to the molecular weight of the compound with the structure represented by above-mentioned formula (1), (2), (1.1) or (1.2) Do not limit, due to smaller then more excellent with the compatibility of resin, the variation of the more big then optical value of the change for ambient humidity Inhibition is higher, therefore preferably 150~2000, more preferably 200~1500, more preferably 300~1000.

In addition, nitrogen-containing heterocycle compound of the present embodiment is more preferably with the knot represented by following formulas (3) The compound of structure.

【Change 7】

Formula (3)

(in formula, A represents pyrazole ring, Ar₁And Ar₂Aromatic series hydrocarbon ring or heteroaromatic are each represented, there can be substituent. R₁Hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl are represented, q represents 1~2 integer, n and m tables Show 1~3 integer.)

By Ar₁And Ar₂The aromatic series hydrocarbon ring or heteroaromatic of expression be respectively preferably included in formula (1) 5 yuan or 6 yuan of aromatic series hydrocarbon ring or heteroaromatic.In addition, as Ar₁And Ar₂Substituent, can include with above-mentioned formula (1) the same substituent of substituent shown in the compound of the structure represented.

As R₁Concrete example, halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), alkyl can be included (methyl, ethyl, n-propyl, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls etc.), acyl group (acetyl group, valeryl benzene first Acyl group etc.), sulfonyl (such as methyl sulphonyl, ethylsulfonyl etc.), alkoxy carbonyl (such as methoxycarbonyl), aryloxy group Carbonyl (such as phenyloxycarbonyl etc.) etc..

Q represents 1~2 integer, and n and m represent 1~3 integer.

In the concrete example of the aromatic series hydrocarbon ring with 5 yuan or 6 yuan illustrated below or the compound of heteroaromatic.Above-mentioned tool Have 5 yuan or 6 yuan aromatic series hydrocarbon ring or heteroaromatic compound not by any restriction of following concrete example.Said Bright, as described above, following concrete example can be dynamic isomer, can also form hydrate, solvate or salt.

【Change 8】

Exemplary compounds 1 (carbazole based compound)

The (benzoxazoles based compound of exemplary compounds 2)

As the concrete example of nitrogen-containing heterocycle compound, in addition to above-mentioned shown exemplary compounds 1 and 2, can enumerate Go out the compound described in International Publication sequence number WO2014/109350A1 paragraph [0140]~[0214].

Application method ＞s of the ＜ for the compound with the structure represented by formula (1)

With regard to by above-mentioned formula (1) represent structure compound for, can suitably regulated quantity and in optical film In contain, as addition, relative to the resin for forming optical film, preferably comprise 0.1~10 mass %, particularly preferably contain 0.5~5 mass %.If in the range of this, it can reduce in the case where not damaging the mechanical strength of optical film and depend on ring The variation of the phase difference of the change of border humidity.

In addition, the adding method as the compound with the structure represented by above-mentioned formula (1), can be added with powder To being formed in the resin of optical film, it is added to after can also dissolving in a solvent in the resin to form optical film.

[organic ester]

The optical film (phase retardation film) of present embodiment preferably comprises at least 1 in sugar ester, polycondensation ester, polyol ester Kind is used as organic ester.With regard to above-mentioned polycondensation ester in the structure not for nitrogen atom, liquid during due to being cooled in manufacturing line Change and be attached to filter, the volume size (high high さ) of the filter traps thing of nitrogen-containing heterocycle compound can be made to diminish, because This is preferred.Wherein, for sugar ester and polycondensation ester, due to playing function as plasticizer, it is consequently adapted to reduce film during film The phase retardation film of the present embodiment of the fluctuation of thickness inhomogeneity, reduction delay Rth in face.

(sugar ester)

Sugar ester is at least compound of any one comprising furanose ring or pyranose ring, can be monose or 2 The polysaccharide of~12 sugared structure connections.Moreover, sugar ester is preferably by least one change being esterified for the OH bases that sugared structure has Compound.Average ester substitution value in sugar ester is preferably in the range of 4.0~8.0, in the range of more preferably 5.0~7.5.

As sugar ester, there is no particular restriction, can include the sugar ester represented by following formulas (A).

Formula (A)

(HO)_m- G- (O-C (=O)-R²)_n

In above-mentioned formula (A), G represents monosaccharide or the residue of disaccharides, R²Aliphatic group or aromatic group are represented, M be with monosaccharide or the residue of disaccharides directly in conjunction with hydroxyl number it is total, n is straight with the residue of monosaccharide or disaccharides Binding conjunction-(O-C (=O)-R²) base number it is total, be 3≤m+n≤8, be n ≠ 0.

For the sugar ester with the structure represented by formula (A), it is known that：Number (m) as hydroxyl ,-(O-C (=O)- R²) base the compound of single kind that is secured of number (n) and to carry out isolation be difficult, turning into makes m, n in formula different The several compounds being mixed with of composition.Therefore, the number (m) as hydroxyl ,-(O-C (=O)-R²) base number (n) each change The performance of mixture be important, in the case of the optical film of present embodiment, preferably average ester substitution value be 5.0~ Sugar ester in the range of 7.5.

In above-mentioned formula (A), G represents monosaccharide or the residue of disaccharides.As the concrete example of monosaccharide, such as can enumerate Go out allose, altrose, glucose, mannose, gulose, idose, galactolipin, talose, ribose, arabinose, xylose, Lyxose etc..

In the concrete example of the compound with monosaccharide residue of the sugar ester described below represented by formula (A), but not It is defined in the compound of these illustrations.

【Change 9】

In addition, the concrete example as disaccharides residue, such as trehalose, sucrose, maltose, cellulose two can be included Sugar, gentiobiose, lactose, isotrehalose etc..

In the concrete example of the compound with disaccharides residue of the sugar ester described below represented by formula (A), but not It is defined in the compound of these illustrations.

【Change 10】

In formula (A), R²Represent aliphatic group or aromatic group.Wherein, aliphatic group and aromatic group can There is substituent independently of one another.

In addition, in formula (A), m be with monosaccharide or the residue of disaccharides directly in conjunction with hydroxyl number it is total, n is With monosaccharide or the residue of disaccharides directly in conjunction with-(O-C (=O)-R²) base number it is total.Moreover, it is necessary for 3≤m+n ≤ 8, preferably 4≤m+n≤8.In addition, it is n ≠ 0.It should illustrate, in the case that n is more than 2 ,-(O-C (=O)-R²) base can , also can be different with mutually the same.

R²Definition in aliphatic group can be straight chain, or branch, can also be ring-type, preferably carbon number 1 The aliphatic group of~25 aliphatic group, more preferably carbon number 1~20, the aliphatic group of particularly preferred carbon number 2~15.Make For the concrete example of aliphatic group, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl can be included Base, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, bicyclooctyl, adamantyl, just Each groups such as decyl, t-octyl, dodecyl, cetyl, octadecyl, didecyl (ジ デ シ Le).

In addition, R²Definition in aromatic group can be aromatic hydrocarbyl or aromatic heterocycle, it is more excellent Elect aromatic hydrocarbyl as.As aromatic hydrocarbyl, preferably carbon number is 6~24 aromatic hydrocarbyl, further preferred carbon number is 6~ 12 aromatic hydrocarbyl.As the concrete example of aromatic hydrocarbyl, such as each of benzene, naphthalene, anthracene, biphenyl, terphenyl etc. can be included Ring.As aromatic hydrocarbyl, particularly preferred phenyl ring, naphthalene nucleus, cyclohexyl biphenyl.As aromatic heterocycle, oxygen atom, nitrogen are preferably comprised At least one ring in atom or sulphur atom.As the concrete example of heterocycle, such as furans, pyrroles, thiophene, miaow can be included Azoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiadiazoles, oxazoline, oxazole, Evil Diazole, quinoline, isoquinolin, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzo Each ring of imidazoles, benzoxazole, benzothiazole, BTA, the purine etc..As aromatic heterocycle, particularly preferred pyrrole Pyridine ring, triazine ring, quinoline ring.

Sugar ester can contain fragrance in a molecule containing the different substituents of more than two in 1 intramolecular Race's substituent and aliphatic substitution, the different aromatic substituents of more than two can be contained in 1 intramolecular, can be 1 Intramolecular contains the different aliphatic substitutions of more than two.

In addition, it is also preferred that sugar ester of more than two kinds is mixed and contained.It is also preferred that contain simultaneously：Contain aromatic substituents Sugar ester and sugar ester containing aliphatic substitution.

Hereinafter, the preferable example of sugar ester represented by formula (A) is shown in following, but is not limited to these illustrations Compound.

【Change 11】

【Change 12】

＜ synthesis examples：The synthesis example ＞ of the sugar ester represented by formula (A)

In the synthesis example of sugar ester described below.

【Change 13】

Filled respectively in the four cephalic flexure neck cucurbits with agitating device, reflux condenser, thermometer and nitrogen ingress pipe Enter sucrose 34.2g (0.1 mole), benzoyl oxide 180.8g (0.8 mole), pyridine 379.7g (4.8 moles), on one side under agitation Make nitrogen bubble from nitrogen ingress pipe while heating, has carried out 5 hours esterifications at 70 DEG C.Then, by bent neck cucurbit Inside it is depressurized to 4 × 10²Below Pa, by after the pyridine distillation of surplus at 60 DEG C, 1.3 × 10Pa will be depressurized in bent neck cucurbit Hereinafter, 120 DEG C are warming up to, by most of distillation of benzoyl oxide, the benzoic acid of generation.Then, toluene 1L, 0.5 are then added Quality % aqueous sodium carbonate 300g, after 30 minutes have been stirred at 50 DEG C, stand, divide and take toluene layer.Finally, point taking Toluene layer in add water 100g, after washing 30 minutes at normal temperatures, point take toluene layer, under reduced pressure (4 × 10²Below Pa), By toluene distillation at 60 DEG C, compound A-1, A-2, A-3, A-4 and A-5 mixture have been obtained.With HPLC and LC-MASS to obtaining To mixture parsed, as a result A-1 is that 7 mass %, A-2 are that 58 mass %, A-3 are that 23 mass %, A-4 are 9 matter % is measured, A-5 is 3 mass %, and the average ester substitution value of sugar ester is 6.57.Should it illustrate, by using silica gel column chromatography to obtaining A part for mixture is refined, and has respectively obtained A-1, A-2, A-3, A-4 and A-5 of purity 100%.

For the addition of the sugar ester, relative to form optical film resin (such as cellulose acylate), preferably with 0.1~20 mass % scope addition, is more preferably added with 1~15 mass % scope.

As sugar ester, preferred hue is 10~300 sugar ester, preferably 10~40 sugar ester.

(polycondensation ester)

In the optical film (phase retardation film) of present embodiment, as organic ester, preferably using with by following formulas (4) table The polycondensation ester for the structure shown.It is excellent relative to the resin for forming optical film from the effect of its plasticising for the polycondensation ester Choosing is contained with 1~30 mass % scope, is more preferably contained with 5~20 mass % scope.

Formula (4)

B₃-(G₂-A)_n-G₂-B₄

In above-mentioned formula (4), B₃And B₄Aliphatic or aromatic monocarboxylate's residue or hydroxyl are represented independently of one another.G₂ Represent the aklylene glycol residue of carbon number 2~12, the aryl-diol residue of carbon number 6~12 or oxyalkylene that carbon number is 4~12 Diol residue.A represents the alkylene dicarboxylic acids residue of carbon number 4~12 or aryl dicarboxylic acid's residue of carbon number 6~12.N represent 1 with On integer.

Polycondensation ester is to be represented comprising the polycondensation ester for making dicarboxylic acids and repeat unit obtained from glycol reaction, A in polycondensation ester Carboxylic acid residues, G₂Represent alcohol residue.

The dicarboxylic acids for forming polycondensation ester is aromatic dicarboxylic acid, aliphatic dicarboxylic acid or ester ring type dicarboxylic acids, is preferably virtue Fragrant race's dicarboxylic acids.Dicarboxylic acids can be a kind or mixture of more than two kinds.Particularly preferably aromatic series, aliphatic are mixed Close.

The glycol for forming polycondensation ester is aromatic diol, aliphatic diol or ester ring type glycol, preferably aliphatic diol, The more preferably glycol of carbon number 1~4.Glycol can be a kind or mixture of more than two kinds.

Wherein, preferably comprising makes to react with the glycol of carbon number 1~8 including at least the dicarboxylic acids of aromatic dicarboxylic acid and obtains Repeat unit, more preferably comprising the glycol for making the dicarboxylic acids comprising aromatic dicarboxylic acid and aliphatic dicarboxylic acid and carbon number 1~8 Repeat unit obtained from reaction.

Two end-cappeds of the molecule of polycondensation ester be able to can not also be blocked.

As the concrete example of the alkylene dicarboxylic acids for the A for forming formula (4), comprising by 1,2- ethane dicarboxylic acids (ambers Acid), 1,3- propane dicarboxylic acids (glutaric acid), 1,4- butane dicarboxylic acids (adipic acid), 1,5- pentanedicarboxylic acids (pimelic acid), 1,8- The group of divalent derived from octane dicarboxylic acid's (decanedioic acid) etc..As the concrete example for the alkenylene dicarboxylic acids for forming A, can include Maleic acid, fumaric acid etc..As the concrete example for the aryl dicarboxylic acid for forming A, 1,2- phthalic acid (O-phthalics can be included Acid), 1,3- phthalic acids, 1,4- phthalic acids, 1,5- naphthalenedicarboxylic acids etc..

A can be a kind, can also combine two or more.Wherein, the alkylene dicarboxylic acids of the preferred carbon numbers 4~12 of A with The combination of the aryl dicarboxylic acid of carbon number 8~12.

G in formula (4)₂Represent as derived from the aklylene glycol of carbon number 2~12 group of divalent, by carbon atom The group of divalent derived from the aryl-diol of number 6~12 or the divalent as derived from the oxyalkylene glycol of carbon number 4~12 Group.

In G₂In the example of the group of divalent as derived from the aklylene glycol of carbon number 2~12 in, comprising by second two Alcohol, 1,2- propane diols, 1,3- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,2- propane diols, 2- methyl-1,3-propanediols, 1,4- butanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propane diols (neopentyl glycol), 2,2- diethyl -1,3- propane diols (3,3- dihydroxymethyls pentane), 2- n-butyl -2- ethyl -1,3- propane diols (3,3- dihydroxymethyls heptane), 3- methyl isophthalic acids, 5- Pentanediol, 1,6-HD, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols, 2- methyl isophthalic acids, 8- pungent two The group of divalent derived from alcohol, 1,9- nonanediols, 1,10- decanediols and 1,12- octacosanols etc..

In G₂In the example of the group of divalent as derived from the aryl-diol of carbon number 6~12 in, comprising by 1,2- bis- The group of divalent derived from hydroxy benzenes (catechol), 1,3- dihydroxy benzenes (resorcinol), Isosorbide-5-Nitrae-dihydroxy benzenes (quinhydrones) etc..In G In the example of the group of divalent as derived from the oxyalkylene glycol that carbon number is 4~12 in, comprising by diethylene glycol (DEG), three sweet The group of divalent derived from alcohol, tetraethylene glycol, DPG, tripropylene glycol etc..

G₂It can be a kind, two or more can also be combined.Wherein, G₂It is preferred that spread out by the aklylene glycol of carbon number 2~12 The group of raw divalent, more preferably 2~5, most preferably 2~4.

B in formula (4)₃And B₄The base of 1 valency respectively as derived from monocarboxylic acid or aliphatic monocarboxylic acid containing aromatic rings Group or hydroxyl.

For the monocarboxylic acid containing aromatic rings in the group of 1 valency as derived from the monocarboxylic acid containing aromatic rings, be Intramolecular contains the carboxylic acid of aromatic rings, not only comprising aromatic rings and carboxyl directly in conjunction with carboxylic acid, also comprising aromatic rings via Asia The carboxylic acid that alkyl etc. is combined with carboxyl.In the example of the group of 1 valency as derived from the monocarboxylic acid containing aromatic rings, comprising by benzene Formic acid, p-tert-butyl benzoic acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethyl 1 valency derived from benzoic acid, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, phenyl acetic acid, 3- phenylpropionic acids etc. Group.Wherein, preferably benzoic acid, p-methylbenzoic acid.

In the example of the group of 1 valency as derived from aliphatic monocarboxylic acid, containing by acetic acid, propionic acid, butyric acid, octanoic acid, oneself The group of 1 valency derived from acid, capric acid, lauric acid/dodecanoic acid, stearic acid, oleic acid etc..Wherein, it is 1 preferably by the carbon number of moieties The group of 1 valency derived from~3 alkyl monocarboxylate, more preferably acetyl group (group of 1 valency as derived from acetic acid).

In present embodiment, the weight average molecular weight of polycondensation ester is preferably 500~3000 scope, more preferably 600~ 2000 scope.Weight average molecular weight can be determined by above-mentioned gel permeation chromatography (GPC).

The concrete example of polycondensation ester described below with the structure represented by formula (4), but it is not limited to it.

【Change 14】

【Change 15】

【Change 16】

Recorded below for the specific synthesis example of the polycondensation ester foregoing described.

＜ polycondensation ester P1 ＞

Using ethylene glycol 180g, phthalic anhydride 278g, adipic acid 91g, benzoic acid 610g, the titanium as esterification catalyst Four isopropyl ester 0.191g of acid be fitted into thermometer, agitator, reflux condensing tube (Slow urgency cooling tube) 2L four-hole boiling flask in, Stirred in nitrogen stream while heating is until as 230 DEG C at leisure.The degree of polymerization is observed while carrying out dehydrating condensation Reaction.React after terminating by the way that unreacted ethylene glycol is depressurized into distillation at 200 DEG C, obtained polycondensation ester P1.Acid number is 0.20, number-average molecular weight 450.

＜ polycondensation ester P2 ＞

Using 1,2- propane diols 251g, phthalic anhydride 103g, adipic acid 244g, benzoic acid 610g, as catalyzing esterification The tetraisopropyl titanate 0.191g of agent be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, in nitrogen Stirred in stream while heating is until as 230 DEG C at leisure.The degree of polymerization is observed while making its progress dehydrating condensation anti- Should.React by the way that unreacted 1,2-PD is depressurized into distillation at 200 DEG C after terminating, so as to obtain following polycondensation esters P2.Acid number is 0.10, number-average molecular weight 450.

【Change 17】

＜ polycondensation ester P3 ＞

Using 1,4- butanediols 330g, phthalic anhydride 244g, adipic acid 103g, benzoic acid 610g, as catalyzing esterification The tetraisopropyl titanate 0.191g of agent be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, in nitrogen Stirred in stream while heating is until as 230 DEG C at leisure.The degree of polymerization is observed while making its progress dehydrating condensation anti- Should.After reaction terminates, by the way that unreacted BDO is depressurized into distillation at 200 DEG C, so as to obtain polycondensation ester P3.Acid It is worth for 0.50, number-average molecular weight 2000.

＜ polycondensation ester P4 ＞

Using 1,2- propane diols 251g, terephthalic acid (TPA) 354g, benzoic acid 610g, the isopropyl of metatitanic acid four as esterification catalyst Ester 0.191g be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, while stirring one in nitrogen stream Heat up at leisure until as 230 DEG C on side.The degree of polymerization is observed while making it carry out dehydration condensation.After reaction terminates, By the way that unreacted 1,2-PD is depressurized into distillation at 200 DEG C, so as to obtain polycondensation ester P4.Acid number is 0.10, and number is equal Molecular weight is 400.

＜ polycondensation ester P5 ＞

Using 1,2- propane diols 251g, terephthalic acid (TPA) 354g, p- toluic acid 680g, the metatitanic acid as esterification catalyst Four isopropyl ester 0.191g be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, in nitrogen stream on one side Stirring heats up until as 230 DEG C at leisure on one side.The degree of polymerization is observed while making it carry out dehydration condensation.Reaction knot Shu Hou, by the way that unreacted 1,2-PD is depressurized into distillation at 200 DEG C, so as to obtain following polycondensation ester P5.Acid number is 0.30, number-average molecular weight 400.

【Change 18】

＜ polycondensation ester P6 ＞

Filled using 180g 1,2- propane diols, 292g adipic acid, as the tetraisopropyl titanate 0.191g of esterification catalyst Enter with thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, stirred in nitrogen stream while rising at leisure Temperature is until as 200 DEG C.The degree of polymerization is observed while making it carry out dehydration condensation.After reaction terminates, by 200 DEG C It is lower that unreacted 1,2-PD is depressurized into distillation, so as to obtain polycondensation ester P6.Acid number is 0.10, number-average molecular weight 400.

＜ polycondensation ester P7 ＞

Using 180g 1,2- propane diols, phthalic anhydride 244g, adipic acid 103g, the metatitanic acid four as esterification catalyst Isopropyl ester 0.191g be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, while stirring in nitrogen stream Mix and heat up at leisure on one side until as 200 DEG C.The degree of polymerization is observed while making it carry out dehydration condensation.Reaction terminates Afterwards by the way that unreacted 1,2-PD is depressurized into distillation at 200 DEG C, so as to obtain polycondensation ester P7.Acid number is 0.10, number Average molecular weight is 320.

＜ polycondensation ester P8 ＞

Using ethylene glycol 251g, phthalic anhydride 244g, butanedioic acid 120g, acetic acid 150g, the titanium as esterification catalyst Four isopropyl ester 0.191g of acid be fitted into thermometer, agitator, reflux condensing tube 2L four-hole boiling flask in, one in nitrogen stream Side stirring heats up until as 200 DEG C at leisure on one side.The degree of polymerization is observed while making it carry out dehydration condensation.Reaction After end, by the way that unreacted ethylene glycol is depressurized into distillation at 200 DEG C, so as to obtain polycondensation ester P8.Acid number is 0.50, number Average molecular weight is 1200.

＜ polycondensation ester P9 ＞

With the manufacture method same with above-mentioned polycondensation ester P2, make change in reaction conditions, obtain acid number 0.10, the equal molecule of number The polycondensation ester P9 of amount 315.

＜ polyol esters ＞

It is also preferred that containing polyol ester in the phase retardation film of present embodiment.

Polyol ester is the compound formed by more than 2 yuan of aliphatic polyol and the ester of monocarboxylic acid, preferably in molecule It is interior that there is aromatic rings or cycloalkyl ring.Preferably 2~20 yuan of aliphatic polybasic alcohol ester.

The polyalcohol preferably used in present embodiment is represented by following formula (5).

Formula (5) R₁₁-(OH)_n

Wherein, R₁₁The organic group of n valencys is represented, n represents more than 2 positive integer, OH basis representations alcohol and/or phenol hydroxyl Base.

As the example of preferable polyalcohol, such as following polyalcohol can be included, but be not limited to these.

Adonitol, arabitol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, 1,2- propane diols, 1,3- can be included Propane diols, DPG, tripropylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, dibutylene glycol, 1,2,4- fourths three Alcohol, 1,5- pentanediols, 1,6-HD, hexanetriol, galactitol, mannitol, 3- methylpentane -1,3,5- triols, pinacol, Sorbierite, trimethylolpropane, trimethylolethane, xylitol etc..

Particularly preferred triethylene glycol, tetraethylene glycol, DPG, tripropylene glycol, sorbierite, trimethylolpropane, xylitol.

As the monocarboxylic acid used in polyol ester, there is no particular restriction, can use known aliphatic monocarboxylic acid, fat Ring race monocarboxylic acid, aromatic monocarboxylate etc..If using cycloaliphatic monocarboxylic, aromatic monocarboxylate, make penetrability, retention (retention) improves, in this respect preferably.

As the example of preferable monocarboxylic acid, following such monocarboxylic acid can be included, but be not limited to this.

As aliphatic monocarboxylic acid, the straight chain of carbon number 1~32 or the aliphatic acid with side chain can be preferably used.Carbon number is more Preferably 1~20, particularly preferably 1~10.If containing acetic acid, increase with the compatibility of cellulose acetate, therefore preferably, It is also preferred that acetic acid and other monocarboxylic acids are used in mixed way.

As preferable aliphatic monocarboxylic acid, can include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, N-nonanoic acid, capric acid, 2- ethyl-hexanoics, hendecanoic acid, laurate, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, 17 Alkanoic acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, hexacosoic acid, carboceric acid, lignite The saturated fatty acids such as acid, melissic acid, laccaic acid, undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic Unrighted acids such as acid etc..

As the example of preferable cycloaliphatic monocarboxylic, cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic can be included Acid or their derivative.

As the example of preferable aromatic monocarboxylate, the benzene in benzoic acid such as benzoic acid, toluic acid can be included Product, biphenyl carboxylic acids, naphthoic acid, the tetrahydro-naphthoic acid of the alkoxies such as 1~3 alkyl, methoxy or ethoxy are introduced on ring Deng the aromatic monocarboxylate with more than 2 phenyl ring or their derivative.Particularly preferred benzoic acid.

To the molecular weight of polyol ester, there is no particular restriction, but preferably 300~1500 scope, more preferably 350~ 750 scope.Molecular weight is big, then is difficult to play, therefore preferably, in terms of penetrability, with the compatibility of cellulose acylate Set out, preferred molecular weight is small.

The carboxylic acid used in polyol ester can be a kind or mixing of more than two kinds.In addition, the OH in polyalcohol Base can be all esterified, and a part can also be made to be remained as OH bases.

It is illustrated below go out polyol ester specific compound.

【Change 19】

【Change 20】

【Change 21】

【Change 22】

For polyol ester, relative to phase retardation film (cellulose esters system resin), preferably with 0.5~5 mass % model Enclose containing more preferably being contained with 1~3 mass % scope, particularly preferably contained with 1~2 mass % scope.

Polyol ester can synthesize according to known in general synthetic method.

[other additives]

＜ phosphates ＞

The phase retardation film of present embodiment can also contain phosphate.As phosphate, can include triaryl phosphate, Diaryl phosphate, an aryl phosphate ester, arylphosphonic acid compound, aryl oxidized phosphine compound, condensation aryl phosphate ester, halo Alkyl phosphate, condensed phosphoric acid esters containing halogen, containing halogen condensation phosphonate ester, phosphite ester containing halogen etc..

As specific phosphate, the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of triphenyl phosphate, 9,10- dihydro-9-oxies can be included Compound, phenyl-phosphonic acid, tricresyl phosphate (β-chloroethyl) ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (tribromo neopentyl) ester etc..

The esters ＞ of ＜ glycolics

In addition, a kind as polyalcohol esters, the esters (ethyl glycolate compound) of glycolic can be used.As second Alcoholic acid esterification compound, is not particularly limited, and can preferably use alkyl phthalic acyl alkyl alcohol esters of gallic acid.

As alkyl phthalic acyl alkyl alcohol esters of gallic acid, such as methyl phthalyl methyl ethanol acid can be included Ester, ethyl phthalyl ethyl hexanol acid esters, propyl group phthalyl propyl group ethyl glycolate, butyl phthalyl butyl second Carboxylic ester, octyl phthalyl octyl group ethyl glycolate, methyl phthalyl ethyl hexanol acid esters, ethyl phthalyl first Base ethyl glycolate, ethyl phthalyl propyl group ethyl glycolate, methyl phthalyl butyl alcohol acid esters, ethyl O-phthalic Acyl butyl alcohol acid esters, butyl phthalyl methyl ethanol acid esters, butyl phthalyl ethyl hexanol acid esters, propyl group neighbour's benzene Two formyl butyl alcohol acid esters, butyl phthalyl propyl group ethyl glycolate, methyl phthalyl octyl group ethyl glycolate, ethyl Phthalyl octyl group ethyl glycolate, octyl phthalyl methyl ethanol acid esters, octyl phthalyl ethyl hexanol acid esters Deng preferably ethyl phthalyl ethyl hexanol acid esters.

＜ particulates (delustering agent) ＞

For phase retardation film, in order to improve the sliding on surface, it can further contain particulate (delustering agent) as needed.

Particulate can be inorganic particles or organic fine particles.In the example of inorganic particles, silica is included (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talcum, clay, burn till kaolin, burn till silicic acid Calcium, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc..Wherein, preferably silica, zirconium oxide, in order that obtained film The increase of mist degree diminish, more preferably silica.

In the example of the particulate of silica, comprising ア エ ロ ジ Le R972, R972V, R974, R812,200,200V, 300th, R202, OX50, TT600, NAX50 (be above Japanese ア エ ロ ジ Le (strain) manufacture) , シ ー ホ ス タ ー KE-P10, KE-P30, KE-P50, KE-P100 (being manufactured above for Japanese catalyst (strain)) etc..Wherein, due to ア エ ロ ジ Le R972V, NAX50, シ ー ホ ス タ ー KE-P30 etc. reduce coefficient of friction while the turbidity of obtained film is kept as into low, therefore Particularly preferably.

The primary particle size of particulate is preferably 5~50nm scope, more preferably 7~20nm scope.Primary particle size is big, then It is big to improve the effect of the sliding of obtained film, but the transparency is easily reduced.Therefore, for particulate, particle diameter 0.05 can be used as The secondary aggregation body of~0.3 μm of scope and contain.The primary particle of particulate or its secondary agglomerate are sized to transmission Type electron microscope observes primary particle or secondary aggregation body using multiplying power 50~2,000,000 times, is used as primary particle or secondary aggregation The average value for the particle diameter that body is 100 and obtain.

For the content of particulate, relative to the model for the resin, preferably 0.05~1.0 mass % for forming phase retardation film Enclose, more preferably 0.1~0.8 mass % scope.

＜ retardation controlling agents ＞

For the raising of the display quality of the image display devices such as liquid crystal display device, phase difference is added in phase retardation film Controlling agent or formed alignment films and set liquid crystal layer, by from polaroid protective film and liquid crystal layer phase difference carry out it is compound Change, thus, it is possible to assign optical compensation ability to phase retardation film.

As retardation controlling agent, European Patent 911 can be included, it is described in 656A2 specifications, have 2 with On the aromatic compounds of aromatic ring, rod-shaped compound described in Japanese Unexamined Patent Publication 2006-2025 publications etc..In addition, it can incite somebody to action More than two kinds of aromatic compounds is used in combination.Preferably also contain in addition to aromatics hydrocarbon ring in the aromatic ring of the aromatic compounds The aromatic heterocycle of aromatic heterocycle.Aromatic heterocycle is generally unsaturated heterocycle.Wherein, preferably Japanese Unexamined Patent Publication 2006-2026 1,3,5- triazine rings described in number publication.

It is explained, the compound with the structure represented by formula (1) also serves as retardation controlling agent and plays function.

For the addition of retardation controlling agent, relative to as the mass % of resin used in film base material 100, preferably In the range of 0.5~20 mass %, in the range of more preferably 1~10 mass %.

[manufacture method of phase retardation film]

For the phase retardation film of present embodiment, such as method, melting casting film method can be film-made by solution curtain coating To manufacture.But in the case of the phase retardation film of manufacture film, in order to suppress delay Rth reduction, it is necessary to make as delay The addition for rising the nitrogen-containing heterocycle compound of agent increases.In the case of more than the addition of nitrogen-containing heterocycle compound, for molten For melting casting film method, incipient scorch etc. occurs in film-forming process because nitrogen-containing heterocycle compound does not melt, therefore preferably Method is film-made using solution curtain coating to be film-made.The phase retardation film of present embodiment is manufactured below for using solution curtain coating film method Example illustrate.

(solution curtain coating film method)

Fig. 2 shows schematically is film-made method to manufacture the one of the device of phase retardation film by solution curtain coating.Solution curtain coating system In embrane method, carry out successively：(1) at least cellulose esters system resin, delay is made to rise agent (such as nitrogen-containing heterocycle compound) and organic The process that the additives such as ester (such as sugar ester) are dissolved in solvent and prepare rubber cement；(2) rubber cement is cast to banding or rotary drum shape Process in metal support；(3) solvent for the rubber cement for making to be cast in metal support evaporates and obtains the work of mesh Sequence；(4) process for peeling off mesh from metal support；(5) by the mesh peeled off (film) stretching, the work for drying it Sequence；(6) process batched after film is cooled down.

(1) rubber cement preparation section

In the process, in the organic solvent based on the good solvent for cellulose esters system resin, in dissolution kettle 31 It is middle by cellulose esters system resin, nitrogen-containing heterocycle compound according to circumstances, sugar ester, polycondensation ester, polyol ester or the othersization Compound is stirred while dissolving, formation rubber cement.Or in the cellulose esters system resin solution by nitrogen-containing heterocycle compound, Sugar ester, polycondensation ester, polyol ester or the mixing of other compound solutions, form the rubber cement as main lysate.

It is just workable organic molten in rubber cement is formed in the case where making phase retardation film using solution curtain coating film legal system For agent, as long as dissolve cellulose esters system resin and other compounds simultaneously, then can unrestrictedly it use.

For example, as chlorine-based organic solvent, dichloromethane can be included, as chlorine-free organic solvent, can be enumerated Go out methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3- dioxolanes, 1,4- dioxanes, cyclohexanone, first Acetoacetic ester, 2,2,2 tfifluoroethyl alcohol, 2,2,3,3- hexafluoro -1- propyl alcohol, the fluoro- 2- propyl alcohol of 1,3- bis-, 1,1,1,3,3,3- hexafluoros -2- Methyl-2-propanol, HFIP, 2,2,3,3,3- five fluoro- 1- propyl alcohol, nitroethane etc., can be preferred Use dichloromethane, methyl acetate, ethyl acetate, acetone.

In rubber cement, in addition to above-mentioned organic solvent, the carbon number 1~4 of 1~40 mass % scope is preferably comprised Straight chain or branch's chain state aliphatic alcohol.If the ratio rise of the alcohol in rubber cement, mesh gelation, from metal support The stripping of body becomes easy, in addition, the ratio hour of alcohol, it may have promotes cellulose esters system's resin and other compounds in non-chlorine It is the effect of the dissolving in organic solvent system.In the film of phase retardation film, from the flatness for improving obtained phase retardation film Aspect is set out, the method that can be filmed using rubber cement of the determining alcohol in the range of 0.5~15.0 mass %.

Particularly preferably in the solvent of the straight chain containing dichloromethane and carbon number 1~4 or the aliphatic alcohol of branch's chain state Make cellulose acylate and other compounds to add up to 15~45 mass % lysed composition of colloidal slurry of scope.

As the straight chain of carbon number 1~4 or the aliphatic alcohol of branch's chain state, methanol, ethanol, positive third can be included Alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol.In these, stability, boiling point from rubber cement also might as well than relatively low, drying property Etc. setting out, preferably methanol and ethanol.

For cellulose esters system resin, nitrogen-containing heterocycle compound, sugar ester, polycondensation ester and polyol ester or other chemical combination The dissolving of thing, the method carried out at ambient pressure, the method carried out below the boiling point of main solvent, the boiling in main solvent can be used The method of more than point pressurization progress, such as Japanese Unexamined Patent Publication 9-95544 publications, Japanese Unexamined Patent Publication 9-95557 publications or Japan Method, the Japanese Unexamined Patent Publication 11-21379 public affairs carried out like that using hot-cold lysis method described in Unexamined Patent 9-95538 publications The various dissolving methods such as the method carried out under the high pressure described in report, the pressurization progress particularly preferably more than the boiling point of main solvent Method.

The concentration of cellulose esters system resin in rubber cement is preferably 10~40 mass % scope.In dissolving or after dissolving Rubber cement in add compound after dissolving and being scattered, filtered with filtering material, deaeration, subsequent processing be pumped into liquor charging.

The filter material that filtering is preferably 0.5~5 μm using trapping particle diameter and drainage time is 10~25 seconds/100ml Material.

In the method, caused condensation product when the condensation product of remaining, the addition of main rubber cement, passes through when disperseing for particle The filtering material that using trapping particle diameter be 0.5~5 μm and drainage time is 10~25 seconds/100ml, can be only by condensation product Remove.For main rubber cement, the concentration of particle is also thin enough compared with annex solution, therefore also will not condensation product during filtering Between stick together and steeply rise filter pressure.

(2) it is cast process

In the process, by the rubber cement in dissolution kettle 31 by liquid-feeding pump (such as compression type quantitative gear pump) and liquor charging extremely Pressurize die head 32, the casting position in the annular metal support 33 ad infinitum transferred, from pressurization die head 32 by rubber cement stream Prolong.For the die head 32 that pressurizes, shape of slit in the mouth mold part that can adjust die head, easily thickness is set to become homogeneous side Face is preferred.There are rack type die, T-shaped mould first-class in pressurization die head 32, all preferably use., can be in gold in order to improve film speed The pressurization die head 32 of more than 2 is set on category supporting mass 33, rubber cement amount is split and lamination.

Metal support 33 is made up of the stainless steel band hung by 2 framves of roller 3434.As metal support 33, preferred pair Surface has carried out the product of minute surface finishing, in addition to above-mentioned stainless steel band, can also use to enter surface with moulding Metal drum of plating of having gone finishing etc..

Curtain coating (cast) width can be set to 1~4m scope, preferably 1.5~3m scope, more preferably 2~ 2.8m scope.The surface temperature of metal support 33 in curtain coating process is set as that -50 DEG C~solvent does not seethe with excitement foaming Temperature, it is highly preferred that being set as -30~0 DEG C of scope.Temperature is high, then the rate of drying of mesh can accelerate, therefore excellent Choosing, but if exceedingly high, mesh foams sometimes, or flatness deterioration.As preferable supporting temperature, 0~100 Suitably determined in DEG C, more preferably 5~30 DEG C of scope.Or make mesh gelation by being cooled down, largely containing Have in the state of residual solvent and to be peeled off from supporting mass and preferable method.

To the method for temperature that controls metal support 33, there is no particular restriction, has the method for warm air or cold wind that blows, makes The method of warm water and the backside contact of metal support 33.During using warm water, due to effectively carrying out passage of heat, therefore until The temperature of metal support 33 is short as the regular hour, preferably.In the case of using warm air, the evaporation latent heat of solvent is considered The temperature of caused mesh reduces, sometimes using the warm air more than boiling point of solvent, be simultaneously used in and prevent the same of foaming Wind also higher than target temperature Shi Wendu.In particular it is preferred to from be cast to peel off during change the temperature of supporting mass and dry The temperature of dry wind, is efficiently dried.

(3) solvent evaporization process

In the process, the film (mesh) formd by the rubber cement being cast in metal support 33 is heated, Evaporate solvent.In order that solvent evaporate, have from the surface of mesh (side opposite with metal support 33) blowing method, From the back side of metal support 33 (face of side opposite with mesh) by liquid come conducted heat method, pass through radiant heat From method etc. of table back pass heat, the drying efficiency of rear surface liquid heat-transferring method it is good and it is preferred that.In addition, it is also preferred that using by these groups The method of conjunction.It is preferred that make the net in the metal support 33 after curtain coating under 40~100 DEG C of atmosphere, in metal support 33 Shape thing is dried.In order to maintain under 40~100 DEG C of atmosphere, the warm air of the temperature is preferably blown into mesh upper surface, or Heated by the means of infrared ray etc..

From the viewpoint of face quality, penetrability, fissility, by the mesh from metal preferably within 30~120 seconds Supporting mass 33 is peeled off.

(4) stripping process

In the process, by stripper roll 35 it is defined stripping position will in metal support 33 solvent it is vaporized Mesh is peeled off.Afterwards, using the mesh after stripping as mesh 36.Mesh 36 is sent to subsequent processing.

The temperature of stripping opening position in metal support 33 is preferably 10~40 DEG C of scope, more preferably 11~30 DEG C Scope.

It should illustrate, for the residual solvent amount of the mesh in the metal support 33 for peeling off the moment, according to drying The power of condition, the length of metal support 33 etc., preferably peeled off in the range of 50~120 mass %.Remaining In the case of being peeled off at the time of quantity of solvent is more, if mesh is excessively soft, flatness is damaged when peeling off, easily production Reeled off raw silk from cocoons caused by raw stripping tension force, vertical stripe, therefore take into account economic pace with quality to determine residual solvent amount when peeling off.Should Explanation is given, the residual solvent amount of mesh is defined with following formula.

Residual solvent amount (%)=(quality after the heating of quality-mesh before the heating of mesh)/(netted Quality after the heating of thing) × 100

Wherein, heating during so-called measure residual solvent amount, represents to carry out the heating of 1 hour at 115 DEG C.

In the range of stripping tension force when mesh is peeled off from metal support 33 is usually 196~245N/m, but In the case of easily producing fold during stripping, preferably peeled off with below 190N/m tension force.

In present embodiment, scope that the temperature that preferably makes stripping opening position in metal support 33 is -50~40 DEG C It is interior, in the range of more preferably 10~40 DEG C, most preferably it is in the range of 15~30 DEG C.

(5) stretching, drying process

In the process, predry drying process, stretching process, trunk drying process are carried out successively.It is predrying to enter as needed OK.

＜ predry drying process ＞

Make to dry from mesh 36 obtained from the stripping of metal support 33., can be on one side for the drying of mesh 36 Its drying is made using multiple rollers conveying mesh 36 one side being configured with up and down, also can be as drying tenter while using fixture The both ends of mesh 36 are fixed and conveyed, while making its drying.

To making the means that mesh 36 dries, there is no particular restriction, can typically use hot blast, infrared ray, heating roller, micro- Ripple etc. is carried out, in terms of simplicity, it is preferred to use hot blast is carried out.

For the drying temperature in the drying process of mesh 36, preferably film -5 DEG C of glass transition temperature with Under, more than 100 DEG C to carry out the heat treatments of more than 10 minutes and less than 60 minutes be effective.Drying temperature is preferably 100~200 In the range of DEG C, in the range of more preferably 110~160 DEG C.

＜ stretching process ＞

In the process, for being peeled off from metal support 33, as needed and by predrying mesh 36, MD is carried out Stretching on direction and/or TD directions.Now, preferably at least stretched using tentering stretching device 37, on TD directions.

Stretching in stretching process can be set to be stretched uniaxially or biaxially.It is biaxial stretch-formed that to be also contained in a direction enterprising Row stretching, the mode for making the tension force of other direction relax and shrink it.

For the phase retardation film of present embodiment, preferably in a manner of the thickness after stretching turns into desired scope, Stretched on MD directions and/or TD directions, preferably on TD directions, in (Tg+15)~(Tg+50) DEG C of temperature range. It should illustrate, Tg is the glass transition temperature (DEG C) of film.If stretched in said temperature scope, easily postponed Adjustment, additionally be able to reduce tensile stress, therefore mist degree reduce.In addition, suppressing the generation of rupture, flatness, film are obtained certainly The phase retardation film of the excellent polarizer of the coloring of body.Draft temperature is preferably (Tg+20)~(Tg+40) DEG C of scope.

Should illustrate, glass transition temperature Tg mentioned here be using commercially available Differential Scanning Calorimetry analyzer, with 20 DEG C/min of measure of programming rate, the intermediate point glass transition temperature (Tmg) obtained according to JIS K7121 (1987).Just For the assay method of the glass transition temperature Tg of specific phase retardation film, according to JIS K7121 (1987), Seiko instrument is used The differential scanning calorimeter DSC220 of device (strain) manufacture is determined.

For the phase retardation film of present embodiment, mesh 36 is at least preferably pulled up more than 1.1 times in TD side. For the scope of stretching, relative to former wide, preferably 1.1~1.5 times, more preferably 1.05~1.3 times.If above-mentioned model In enclosing, then not only the movement of the molecule in film is big, obtains desired length of delay, and can be by the behavior of the change in size of film Control is in desired scope.

And then for should stretching, for the film in MD when residual solvent amount is more than 40 mass % preferably after film Start to stretch on direction, preferably stretched when residual solvent amount is less than 40 mass % on TD directions.

In order to be stretched in the MD direction, stripping tension force is preferably set to be peeled off for more than 130N/m, particularly preferably 150~170N/m.Because the mesh after stripping is high residue solvent state, therefore by maintaining same with peeling off tension force Power, the stretching on MD directions can be carried out.As mesh is dry, residual solvent amount is reduced, extensibility drop in the MD direction It is low.

It should illustrate, the stretching ratio in MD directions can be calculated by the rotary speed with supporting mass and stenter running speed Go out.

In order to be stretched on TD directions, such as made using such shown in Japanese Unexamined Patent Application 62-46625 publications Full process or a part of process is dried to protect to enter the width both ends of mesh line width with fixture or needle plate in the direction of the width The method (being referred to as stenter mode) that it is dried is held while makes, wherein it is preferred that using the stenter mode using fixture, using pin The pin stenter mode of plate.

For the phase retardation film of present embodiment, necessarily there is delay due to being stretched, but with regard to postponing Ro in face And for the delay Rt of thickness direction each value, automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan can be used Mueller Matrix Polarimeter：ア Network ソ メ ト リ ッ Network ス companies manufacture), in the environment of 23 DEG C of 55%RH, Three-dimensional refractive index measure is carried out under 590nm wavelength, is calculated by obtained refractive index nx, ny, nz.

For the phase retardation film of present embodiment, with 1 in the case of possessing from VA mode-type liquid crystal display devices From the viewpoint of the composition of phase retardation film can just improve observability, direction prolongs in the face that is preferably defined by following formula (i) The delay Rth of slow Ro and the thickness direction defined by following formula (ii) is in following scope.For phase retardation film, by extremely It is few to adjust stretching ratio while stretching on TD directions, delay Ro, Rth can be adjusted in above range.

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm

Formula (i)：Ro=(nx-ny) × d (nm)

Formula (ii)：Rt={ (nx+ny)/2-nz } × d (nm)

[in formula (i) and formula (ii), nx represents that refractive index turns into the refraction on maximum direction x on direction in the face of film Rate.Ny represents the refractive index on direction y orthogonal with above-mentioned direction x on direction in the face of film.Nz represents the thickness direction z of film On refractive index.D represents the thickness (nm) of film.]

＜ trunk drying process ＞

For the mesh 36 after stretching, drying device 38 is delivered to as film F, use herein with it is above-mentioned predrying Same gimmick is dried.It should illustrate, the drying condition in trunk drying process can be different from predry drying process.Trunk is dry In process, from making the orientating deviation of cellulose esters system resin and additive be difficult to produce, suppress aqueous and drying thereafter and wet It it is 100 DEG C preferably after the stretch, in the temperature lower than draft temperature from the viewpoint of delay Rth variation caused by thermal change is dynamic The drying of more than 5 minutes is carried out above, and the drying of 10~20 minutes is carried out more preferably at 110~150 DEG C.

＜ annular knurls process ＞

Due to obtaining good volume appearance, therefore rip cutting is set preferably after the dry end of above-mentioned trunk, before the batching of film F Machine cuts away film F end.And then annular knurl processing is implemented at preferred pair film width both ends.

For annular knurl processing, it can be pressed against by the knurling rolls for making to be heated to be formed.In knurling rolls formed with Tiny bumps, by pressing it against, bumps can be formed in film, end is become fluffy.The rolling at film F width both ends Colored highly preferred 4~20 μm, width preferably 5~20mm.

(6) coiling process

It is the process for being batched film F with devices for taking-up 39 after residual solvent amount is as below 2 mass % in the process. By making residual solvent amount turn into below 0.4 mass %, the good film of dimensional stability can be obtained.

For film F method for coiling, the method for coiling that typically uses can be used, is had and is determined Torque method, determines tensammetry, gradually Certain program tension control method of varied tention method, internal stress etc., these all can be used.

[physical property of phase retardation film]

(mist degree)

The preferred mist degree of phase retardation film of present embodiment is less than 1%, more preferably less than 0.5%.By making mist degree not To 1%, have the following advantages that：The further rise of the transparency of film, becomes easier to use as the film of optical applications.

(equilibrium moisture content)

Equilibrium moisture content under preferably 25 DEG C of the phase retardation film of present embodiment, relative humidity 60% is less than 4%, more excellent Elect less than 3% as.By making equilibrium moisture content turn into less than 4%, humidity change is easily tackled, optical characteristics, size are more difficult to Change and it is preferred that.

(film length and width degree, thickness)

The phase retardation film of present embodiment is preferably long size shape, and specifically, it is preferable to the length for 100~10000m or so Degree, is wound into web-like.In addition, the width of the phase retardation film of present embodiment is preferably more than 1m, more preferably more than 1.4m, Particularly preferably 1.4~4m.

For the thickness of phase retardation film, from the viewpoint of the slimming, productivity ratio from display device, preferably 10~ In the range of 100 μm, for being formed to realize above-mentioned Ro and Rth with 1 phase retardation film, the thickness of phase retardation film is preferably 40~70 μm (if the thickness of phase retardation film is excessively thin, desired Ro and Rth can not be realized with 1 phase retardation film).

The thickness inequality of phase retardation film is in the range of all preferably 0~5 μm of thickness direction or width, and more preferably 0 In the range of~3 μm, in the range of more preferably 0~2 μm.

[embodiment]

It is exemplified below embodiment to specifically describe the present invention, but the present invention is not limited to these embodiments.It should say It is bright, the expression of " part " or " % " is used in embodiment, as long as no special instructions, then it represents that " mass parts " or " quality % ".

The making ＞ of ＜ phase retardation films 1

The ＞ of ＜ particle dispersion liquids 1

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

The mass parts of ethanol 89

After being stirred 50 minutes with dissolvers by more than, disperseed with マ Application ト ン ゴ ー リ Application, be prepared for micro- Grain dispersion liquid 1.

The ＞ of ＜ particulate annex solutions 1

In the dissolving tank equipped with dichloromethane, fully particle dispersion liquid 1 is slowly added in stirring on one side on one side.Enter And carry out scattered with grater so that the particle diameter of offspring turns into defined size.The Off manufactured with the smart line (strain) of Japan ァ イ Application メ ッ ト NF are filtered, and are prepared for particulate annex solution 1.

The mass parts of dichloromethane 99

The mass parts of particle dispersion liquid 15

The preparation ＞ of ＜ rubber cements

Then, dichloromethane and ethanol be with the addition of in dissolved under pressure tank.Then, in the dissolved under pressure tank equipped with solvent Stir while putting into the cellulose acetate-butyrate of total acyl substitution 2.4.It is heated, stirs while fully molten Solution, the peace product filter paper No.244 manufactured using peace product filter paper (strain) are filtered, and are prepared for main rubber cement.Then, by following thing Matter puts into closed dissolution kettle, stirs while dissolve, is prepared for rubber cement.

《The composition of rubber cement》

It should illustrate, as above-mentioned sugar ester S, use BzSc (benzoyl sucrose：Saccharide residue is B-2, substituent is Change mixture, average ester substitution value=5.5 of a1~a4 described in 11).

The film ＞ of ＜ films

Then, in stainless steel band supporting mass, make solvent be evaporated up to by be cast the rubber cement (cast) formed it is netted Residual solvent amount in thing turns into 75 mass %, then, with peel off tension force 130N/m peeled off from stainless steel band supporting mass it is netted Thing.Then, the mesh of stripping is stretched 30% in the direction of the width using stenter.Stretching residual solvent when starting is 15%.It is explained, the draft temperature at stenter is 160 DEG C.

Then, while being conveyed with multiple rollers in dry section while completing drying.Drying temperature after stretching is 100 DEG C, drying time is 5 minutes.The phase retardation film 1 of 60 μm of dry film thickness has been obtained as described above.

The making ＞ of ＜ phase retardation films 2

Except rising agent as delay nitrogen-containing heterocycle compound B (exemplary compounds are used instead of nitrogen-containing heterocycle compound A 2nd, benzoxazole based compound) beyond preparing rubber cement, being film-made using the rubber cement, made in the same manner as the making with phase retardation film 1 Phase retardation film 2 is made.

The making ＞ of ＜ phase retardation films 3

In addition to being film-made in a manner of turning into 80 μm by dry film thickness, made in the same manner as the making with phase retardation film 1 Phase retardation film 3 is made.

The making ＞ of ＜ phase retardation films 4

Except using degree of substitution with acetyl group 1.9, bytyry substitution value 0.5, the substitution of total acyl group as cellulose esters system resin The cellulose acetate-butyrate of degree 2.4 is come beyond preparing rubber cement, being film-made using the rubber cement, in the same manner as the making with phase retardation film 3 Phase retardation film 4 is made.

The making ＞ of ＜ phase retardation films 5

In addition to preparing rubber cement except no addition delay rises agent, be film-made using the rubber cement, the system with phase retardation film 1 Phase retardation film 5 is similarly made.It is explained, as delay Ro and Rth, in order to realize the value of table 1, with dry film thickness 100 μm have made phase retardation film 5.

The making ＞ of ＜ phase retardation films 6

It is same with the making of phase retardation film 3 in addition to no addition sugar ester is prepared rubber cement, is film-made using the rubber cement Ground has made phase retardation film 6.

The making ＞ of ＜ phase retardation films 7

Prepare rubber cement except using the cellulose diacetate of degree of substitution with acetyl group 2.4 as cellulose esters system resin, make Beyond being film-made with the rubber cement, phase retardation film 7 has been made in the same manner as the making with phase retardation film 3.

The making ＞ of ＜ phase retardation films 8

Except the tri acetic acid fiber that degree of substitution with acetyl group 2.8 is used as cellulose esters system resin usually prepares rubber cement, makes Beyond being film-made with the rubber cement, phase retardation film 8 is made in the same manner as the making with phase retardation film 3.It is explained, makes phase retardation film 8 Dry film thickness be 100 μm.

The making ＞ of ＜ phase retardation films 9~12

In addition to the substitution value of bytyry and the thickness of film that cellulose esters system resin is changed as table 2, with phase The making of potential difference film 1 has similarly made phase retardation film 9~12.

＜ Ro and Rth measure ＞

Use automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan Mueller Matrix Polarimeter： ア Network ソ メ ト リ ッ Network ス companies manufacture) the delay Ro and thickness in direction in the face of the phase retardation film 1~12 that determines above-mentioned making The delay Rth in direction.For Ro and Rth, by the environment of 23 DEG C of temperature, relative humidity 55%RH, under wavelength 590nm Carry out the refractive index n obtained by three-dimensional refractive index measure_x、n_y、n_z, calculated based on following formula.

Ro=(n_x-n_y)×d(nm)

Rth={ (n_x+n_y)/2-n_z}×d(nm)

(in formula, n_xRepresent that refractive index turns into the refractive index on maximum direction x on direction in the face of film.n_yRepresent in film Face in refractive index on direction y orthogonal with above-mentioned direction x on direction.n_zRepresent the refractive index on the thickness direction z of film.d Represent the thickness (nm) of film.)

The making ＞ of ＜ viewable side polarizers

(making of polarizer)

Make thick 70 μm polyvinyl alcohol membrane swelling with 35 DEG C of water.By obtained film by iodine 0.075g, KI 5g and Impregnated 60 seconds in the aqueous solution of water 100g compositions, and then in 45 DEG C of water being made up of KI 3g, boric acid 7.5g and water 100g Impregnated in solution.Uniaxial tension is carried out to obtained film under conditions of 55 DEG C of draft temperature, 5 times of stretching ratio.To the single shaft After stretched film is washed, make its drying, obtain thick 15 μm polarizer.

(making of polarizer)

As the cellulose acylate film for the side for fitting in polarizer, prepare as commercially available polaroid protective film Thick 60 μm U ニ カ ミ ノ Le タ KC6UA.

Process 1：Phase retardation film and KC6UA are impregnated 90 seconds in 60 DEG C of 2 moles/L sodium hydroxide solution respectively, connect Washing, drying, pair side being bonded with polarizer implements saponification process.

Process 2：By polarizer in the mass % of solid constituent 2 polyvinyl alcohol bonding agent groove impregnated of 1~2 second.

Process 3：The superfluous bonding agent that polarizer is attached in process 2 is lightly wiped, process 1 is placed in its one side The middle phase retardation film handled, place KC6UA in the face of opposite side and configure.

Process 4：By the phase retardation film, polarizer, KC6UA that are laminated in process 3 with 20~30N/cm of pressure², transporting velocity About 2m/ minutes are bonded.

Process 5：In 80 DEG C of drying machine, the layered product being bonded in process 4 is dried 2 minutes, makes polarizer.

The process for carrying out the above respectively for the phase retardation film 1~12 made, has made the polarizer of viewable side.

The making ＞ of ＜ backlight side polarizers

Except the one side of polarizer paste zero phase difference film (manufacture of U ニ カ ミ ノ Le タ Co., Ltd., KC4CZ), Another side has been pasted beyond above-mentioned polaroid protective film (KC6UA), and backlight has been made in the same manner as the making with viewable side polarizer Side polarizer.It is explained, the delay Ro in direction is 4nm in the face of zero phase difference film, and the delay Rth of thickness direction is 6nm.

＜ panels evaluate ＞

By in SAMSUNG VA type liquid crystal display device (models：UN55HU-8500 paste in advance on the two sides of liquid crystal cell) The polarizer of conjunction is peeled off, by the viewable side polarizer of above-mentioned making and backlight side polarizer respectively for liquid crystal cell in viewable side and The glass surface of backlight side is bonded using acrylic adhesive.Now, liquid is turned into the phase retardation film of viewable side polarizer Brilliant box side, the zero phase difference film of backlight side polarizer turn into the mode of liquid crystal cell side, and each polarizer is bonded.Then, in drying The backlight of liquid crystal display device is continuously lighted 1 hour afterwards, picture is turned into black come visual valuation based on following metewand Show and whether observe uneven and striped.And carried out for each liquid crystal display device with phase retardation film 1~12 Such evaluation.

＜ metewands ＞

◎：Uneven and striped is not observed completely by visual observation.

○：According to visual angle, it was observed that slightly weak inequality and striped, but be unchallenged level.

△：Independent of visual angle, it was observed that weak inequality and striped, are the levels as problem.

×：Strong inequality and striped are clearly observed in picture by visual observation.

Table 1 and table 2 show the result of the evaluation for each phase retardation film 1~12.In addition, for embodiment and comparative example Corresponding relation, be also shown in the lump in table 1 and table 2.

As shown in Table 1:It is uneven that display is clearly observed in the liquid crystal display device for having used phase retardation film 5.Think This is due to rise agent without delay in phase retardation film 5, therefore (is particularly thickness direction to obtain desired delay Postpone Rth), it has to make thickness thickness up to 100 μm, because film thickness is thick, therefore the inhomogeneity increase of the thickness in film surface, knot Fruit postpones Rth fluctuations in film surface, and it is uneven to generate display.

In the liquid crystal display device for having used phase retardation film 6, the liquid crystal display device phase with having used phase retardation film 5 Than that although display inequality obtains some improvement, can not say and fully be improved.It is thought that because：Due in phase In poor film 6 containing delay rise agent, therefore with 80 μm of the thickness thinner than phase retardation film 5 just obtained desired delay Ro and Rth, but due to without sugar ester, therefore in film film can not be made to become soft and delay can not be made to rise agent in film equably Mixing, it is impossible to fully improve thickness inhomogeneity.

In the liquid crystal display device for having used phase retardation film 7 and 8 respectively, striped is clearly observed by visual observation.Recognize It is due to that cellulose esters system resin contained in phase retardation film 7 and 8 is the fiber without the substituent beyond acetyl group for this Plain acylate (cellulose diacetate, cellulose triacetate), therefore fissility during film from supporting mass is poor, does not enter well Row is peeled off, and produces striped on the width of film when as a result peeling off, the striped generates to the display in liquid crystal display device Influence.Additionally, it is believed that the display in visually does not produce by the striped.

Relative to above-mentioned, in the liquid crystal display device for having used phase retardation film 1~4 respectively, it is not observed completely aobvious Show uneven and striped or even if it was observed that and no problem level.Think due to having used acetic acid in phase retardation film 1~4 Cellulose butyrate is as cellulose esters system resin, the film for being also less than 80 μm for thickness, therefore is carried out well in film From the stripping of supporting mass, as a result, striped is almost not observed.Additionally, it is believed that the uneven original of display is almost not observed Because being：Phase retardation film 1~4 includes delay and rises both agent and sugar ester, thus using the film below 80 μm of thickness, be used as 1 Necessary high latency Ro and Rth is realized in the case of opening phase retardation film use, while can fully improve the thickness in film surface Inhomogeneity, thereby, it is possible to reduce the fluctuation of the delay Rth in film surface.

In addition, as shown in Table 2：In the range of the substitution value of bytyry is 0.03~0.8, bar is not observed completely Line, or even if it was observed that and the level that has no problem, it can be said that the fissility from supporting mass when film is film-made is good.

Phase retardation film, polarizer and the vertical orientating type liquid crystal display device of present embodiment described above can be as follows Show describedly.

1. phase retardation film, it is characterised in that include：On cellulose esters system resin, delay with acetyl group and bytyry Agent and sugar ester are risen,

When the delay in direction is set to Ro (nm), the delay of the thickness direction of film is set to Rth (nm) in the face by film, For：

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm。

2. the phase retardation film described in above-mentioned 1, it is characterised in that thickness is more than 40 μm and less than 70 μm.

3. the phase retardation film described in above-mentioned 1 or 2, it is characterised in that above-mentioned cellulose esters system resin meets following formula simultaneously And (2) (1).

1.8≤X+Y≤2.9···(1)

0.03≤Y≤0.8···(2)

Wherein, X represents the substitution value of acetyl group, and Y represents the substitution value of bytyry.

4. polarizer, it is characterised in that have：

Phase retardation film any one of above-mentioned 1-3 and

It is bonded the polarizer of above-mentioned phase retardation film.

5. vertical orientating type liquid crystal display device, it is characterised in that have：

Polarizer described in above-mentioned 4 and

It is bonded the liquid crystal cell of above-mentioned polarizer.

6. the vertical orientating type liquid crystal display device described in above-mentioned 5, it is characterised in that for above-mentioned polarizer, relatively It is located at viewable side in above-mentioned liquid crystal cell, and in a manner of above-mentioned phase retardation film turns into above-mentioned liquid crystal cell side relative to above-mentioned polarizer Fit in above-mentioned liquid crystal cell.

Industrial applicability

The phase retardation film of the present invention can utilize in the liquid crystal display device of polarizer and VA types.

The explanation of symbol

1 liquid crystal display device (vertical orientating type liquid crystal display device)

4 liquid crystal cells

5 polarizers

11 polarizers

13 optical films (phase retardation film)

Claims (6)

1. a kind of phase retardation film, it is characterised in that include：On cellulose esters system resin, delay with acetyl group and bytyry Agent and sugar ester are risen,

When the delay in direction is set to Ro (nm), the delay of the thickness direction of film is set to Rth (nm) in the face by film, it is：

50nm≤|Ro|≤80nm

200nm≤|Rth|≤300nm。

2. the phase retardation film described in claim 1, it is characterised in that thickness is more than 40 μm and less than 70 μm.

3. the phase retardation film described in claim 1 or 2, it is characterised in that cellulose esters system resin meets following formula simultaneously And (2) (1)：

1.8≤X+Y≤2.9···(1)

0.03≤Y≤0.8···(2)

Wherein, X represents the substitution value of acetyl group, and Y represents the substitution value of bytyry.

4. a kind of polarizer, it is characterised in that have：

Phase retardation film described in any one of claim 1-3 and

It is bonded the polarizer of the phase retardation film.

5. a kind of vertical orientating type liquid crystal display device, it is characterised in that have：

Polarizer described in claim 4 and

It is bonded the liquid crystal cell of the polarizer.

6. the vertical orientating type liquid crystal display device described in claim 5, it is characterised in that for the polarizer, relatively It is located at viewable side in the liquid crystal cell, and in a manner of the phase retardation film turns into the liquid crystal cell side relative to the polarizer Fit in the liquid crystal cell.