CN106353845A

CN106353845A - Phase difference film used for VA, manufacturing method of phase difference film used for VA, polarizing film, and vertical orientation type liquid crystal display device

Info

Publication number: CN106353845A
Application number: CN201610545830.1A
Authority: CN
Inventors: 金子由纪
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Inc; Konica Minolta Opto Inc
Priority date: 2015-07-13
Filing date: 2016-07-12
Publication date: 2017-01-25
Anticipated expiration: 2036-07-12
Also published as: JP2017021236A; KR20170008166A; TW201710348A; CN106353845B

Abstract

The invention discloses a phase difference film used for VA comprising cellulose ester resin and satisfying following conditions (1) and (2). According to the condition (1): smd plus std is smaller than or equal to 0.65%, and smd and std respectively represent the size change rates (5) of the film taking the 55% RH state as the reference during the changing from 20% RH to 80% at 23DEG C in the length direction and the width direction. According to the condition (2):rth 2-rth1 is smaller than or equal to 9nm, and rth 1 represents the measured delay (nm) of the thickness direction, when two transparent substrates are used to clamp the film without using adhesive agent, and rth 2 represents the measured delay (nm) of the thickness direction, when the two transparent substrates are used to clamp the film, and the adhesive agent exists between the film and one of the transparent substrates.

Description

Va phase retardation film, the manufacture method of va phase retardation film, polaroid and vertical orientated Type liquid crystal indicator

Technical field

The present invention relates to one kind is applicable to vertical orientating type (va type；Vertical alignment) liquid crystal indicator Va phase retardation film, the manufacture method of this va phase retardation film, using the polaroid having this va phase retardation film with using having The vertical orientating type liquid crystal display device of this polaroid.

Background technology

As the optical compensation films for va type liquid crystal indicator it is known to the va phase containing cellulose esters resinoid Potential difference film (below, above-mentioned film is also recited as cellulose esters phase retardation film or is only recited as film).Using cellulose esters phase In the case of potential difference film, the phase contrast under high humidity environment changes to become with the tone variations of display image in liquid crystal indicator therewith For problem.As produce tone variations one of the main reasons thus it is speculated that being following main cause.

Cellulose esters phase retardation film, when being loaded on liquid crystal indicator as polarizer group, is fixed on liquid using binding agent Brilliant unit (a piece of glass substrates of such as 2 sheet glass substrates of clamping liquid crystal layer).Cellulose esters phase retardation film is in high humidity ring Aqueous under border, can expand because aqueous.Now, fix film with binding agent, therefore, film can not be in face in thickness direction expansion Direction expands.When the thickness of film increases, the delay rth of the thickness direction of film increases.In film face when aqueous, the size in direction becomes Move bigger, the increase bigger (due to significantly expanding) of this delay rth in thickness direction.As described above, the aqueous of film causes Dimensional variations cause the variation of the delay rth of film through-thickness, as a result, speculating the color of the display image of liquid crystal indicator Tune changes.

On the other hand, as suppressing inhibitor that the delay rth of the aqueous thickness direction leading to changes it is known that Have and contain the delay dose specified in cellulose ester membrane.For example have disclosed in patent documentation 1: can be by pyrimidine will be contained Ring or pyridine ring, and the position specified on ring has the compound group of specified substituent group and make an addition to cellulose ester membrane, suppression with The humidity use environment changes and the variation of the delay rth of generation.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2012-214683 publication (with reference to claim 1,13, paragraph [0006] etc.)

Content of the invention

Invent technical problem to be solved

But, for the composition of film in patent documentation 1 it is known that: in the occupation mode of the reality of liquid crystal indicator, The variation postponing rth can not be adequately suppressed it is impossible to be adequately suppressed the tone variations of display image.Its supposition is because, In patent documentation 1, to the above-mentioned main cause producing tone variations, cause for the aqueous of high humidity environment lower film Dimensional variations and the variation of delay rth that produces is not studied completely, fail to postponing the reason rth changes to be the chi of film Very little variation is suppressed.

In addition, in patent documentation 1, to high humidity and the dimensional variations of film under hot environment or the variation postponing rth Do not studied completely it is believed that not enabling the excellent film of wet heat durability.

The present invention is to complete to solve the problems, such as above-mentioned, it is intended that provide a kind of va phase retardation film and Its manufacture method, use are had the polaroid of this va phase retardation film and are shown using the vertical alignment-type liquid crystal having this polaroid Device, in the occupation mode of the reality of liquid crystal indicator in film to be adopted for the described va phase retardation film, to film during high humidity The aqueous dimensional variations causing are suppressed, and are adequately suppressed the variation of the delay of thickness direction, thus can be adequately suppressed The tone variations of display image, can also enter to the variation of the dimensional variations of film or delay rth under hot and humid environment meanwhile Row suppression, thus improve wet heat durability.

For solving the technical scheme of technical problem

The va phase retardation film of an aspect of of the present present invention contains cellulose esters resinoid, and described va phase retardation film is simultaneously full Enough under condition (1) and (2).

Condition (1)

Smd+std≤0.65%

Wherein, smd and std represents the size changing rate (%) of film length direction and film width respectively,

Smd=(| bm-cm |/am) × 100

Std=(| bt-ct |/at) × 100.

In above formula,

Am, bm and cm refer respectively in same film, when at 23 DEG C of temperature, relative humidity is 55%, 20% and 80%, The size (mm) of the length direction of described film,

At, bt and ct refer respectively in same film, at 23 DEG C of temperature, when relative humidity is 55%, 20% and 80%, The size (mm) of the width of described film.

Condition (2)

rth2-rth1≤9nm

Wherein,

Rth1 refers to clamp this film with two panels transparency carrier and does not use binding agent, at 23 DEG C of temperature, in relative humidity For measuring the delay (nm) of the thickness direction obtaining in the environment of 55%,

Rth2 refers to clamp this film with two panels transparency carrier, and make binding agent be present in this film and a piece of transparency carrier it Between, at 23 DEG C of temperature, it is the delay (nm) measuring the thickness direction obtaining in the environment of 55% in relative humidity.

The effect of invention

In the va phase retardation film containing cellulose esters resinoid, by meeting above-mentioned condition (1), can suppress high The aqueous dimensional variations causing of film when wet, therefore, it is possible to meet condition (2) simultaneously.That is, can with respect to film on-fixed when Variation to the delay of thickness direction when fixing suppresses.

Therefore, by meeting condition (1) and (2) simultaneously, even if adopting above-mentioned film in the liquid crystal indicator of va type In the case of, film when also can be adequately suppressed high humidity in the occupation mode of the reality of the liquid crystal indicator that film is fixed The variation of the delay of the aqueous thickness direction leading to, as a result, the tone variations of display image can be adequately suppressed.

In addition, using at 23 DEG C of temperature, the environment of relative humidity 55% as benchmark, by the dimensional variations of film or thickness The variation of the delay in degree direction is suppressed, even if the environment at more hot and humid than it (such as temperature 60 C relative humidity 90%) Down it is also possible to play its effect in a way, the wet heat durability of film can be improved.

Brief description

Fig. 1 is the profile of the schematic configuration of the vertical orientating type liquid crystal display device illustrating embodiment of the present invention.

Fig. 2 is the device of the phase retardation film adopting in the polaroid schematically showing and manufacturing above-mentioned liquid crystal indicator The explanatory diagram of one example.

Description of symbols

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

4 liquid crystal cells

5 polaroids

11 polarizers

13 bloomings (va phase retardation film)

33 metal support

36 wet films (casting films)

Specific embodiment

An embodiment to the enforcement of the present invention, illustrates if based on accompanying drawing, then as described below.Need explanation , in this specification, in the case that numerical range is marked as a～b, include lower limit a and upper limit b in its numerical range Value, relative humidity sometimes referred to as rh (relative humidity).It should be noted that the present invention be not limited to following Content.

[vertical orientating type liquid crystal display device]

Fig. 1 is the profile of the schematic configuration of vertical orientating type (va type) liquid crystal indicator 1 illustrating present embodiment. Liquid crystal indicator 1 possesses display panels 2 and backlight 3.Backlight 3 is the light source for illuminating display panels 2.

Display panels 2 are constituted as follows: configure polaroid 5 in the visible side of the liquid crystal cells 4 driving in va mode, Backlight 3 side configures polaroid 6.Form liquid crystal cells 4 with a pair of transparency carrier clamping (not shown) liquid crystal layer.As liquid crystal Unit 4, colored filter can use the transparency carrier being configured at backlight 3 side with respect to liquid crystal layer, i.e. tft (thin film Transistor) form the substrate of side, the liquid crystal cells of so-called color filter array (coa) structure, but colour filter can be The liquid crystal cells configuring on the transparency carrier of visible side with respect to liquid crystal layer.

Polaroid 5 possesses: polarizer 11, blooming 12 and blooming 13.Polarizer 11 is through the rectilinearly polarized light specified. Blooming 12 is the protecting film of the viewing side configuration in polarizer 11.Blooming 13 is the backlight 3 side (liquid crystal in polarizer 11 Unit 4 side) protecting film that configures and phase retardation film.Polaroid 5 is attached to the viewing side of liquid crystal cells 4 across adhesive layer 7.That is, Polaroid 5 is to be located at visible side with respect to liquid crystal cells 4, and blooming 13 is fitted so as to respect to polarizer with liquid crystal cells 4 11 become liquid crystal cells 4 side.

Polaroid 6 possesses: polarizer 14, blooming 15 and blooming 16.Polarizer 14 is through the rectilinearly polarized light specified. Blooming 15 is the protecting film of the identification side configuration in polarizer 14, can work as phase retardation film.Blooming 16 be The protecting film of the backlight 3 side configuration of polarizer 14.This polaroid 6 is attached to the backlight of liquid crystal cells 4 across adhesive layer 8 3 sides.It should be noted that omitting the blooming 15 of identification side, polarizer 14 can be directly contacted with adhesive layer 8.To being polarized Mirror 11 and polarizer 14 are configured so as to be become orthogonal Nikkor prism state.

The phase retardation film of the va of present embodiment can serve as the blooming 13 of such as polaroid 5 or the light of polaroid 6 Learn film 15.Hereinafter, the details of phase retardation film is illustrated.

[phase retardation film]

The phase retardation film of present embodiment utilizes solution curtain coating masking method masking described later.As long as phase retardation film is by thermoplastic Property the film that constitutes of resin, any phase retardation film can, but in the case of for optical applications, preferably by with respect to Desired wavelength has the film of the resin formation of transparent property.As the resin constituting this film, can enumerate: Merlon Resinoid, polyether sulfone resin, polyethylene terephthalate resinoid, polyimide based resin, poly-methyl methacrylate Esters resin, polysulfones resinoid, polyarylate resinoid, polythylene resin, polyvinyl chloride resin, there is the alkene of alicyclic structure Hydrocarbon polymer resinoid (ester ring type olefin polymer resinoid), cellulose esters resinoid etc..

Wherein, from the viewpoint, preferably polycarbonate resin, ester ring type olefin polymer such as the transparency or mechanical strength Resinoid, cellulose esters resinoid.Wherein, the fiber further preferably easily phase contrast made during blooming being adjusted Plain esters resin.

(cellulose esters resinoid)

As preferred cellulose esters resinoid, the cellulose acylate meeting following formula (1) and (2) can be enumerated.

Formula (1) 2.0≤z1 ＜ 3.0

Formula (2) 0≤x ＜ 3.0

(in formula (1) and (2), z1 represents total acyl substitution of cellulose acylate, and x represents the third of cellulose acylate Acyl substitution and the summation of bytyry substitution value.)

As the cellulose of the raw material of cellulose esters, such as velveteen, wood pulp, mestha etc. can be enumerated, but not special It is not defined in these.Furthermore it is possible to the cellulose esters being obtained by these materials are used in mixed way with each arbitrary ratio.

From the viewpoint of improving resistance to water, total acyl substitution of preferred cellulose acylate is 2.2～2.9 scope Interior cellulose acylate, in addition, from improve masking when curtain coating and draftability, further raising thickness uniformity sight Point sets out, and total acyl substitution of cellulose acylate is preferably 2.1～2.5.

It should be noted that the substitution value of the substitution value of acetyl group or other acyl group can be according to as astm (american society for testing and materials；Test material association of the U.S.) plan is fixed, the specification of distribution One of the regulation of astm-d817-96 be measured.

As cellulose acylate, particularly preferably it is selected from cellulose ethanoate (cellulose diacetate, cellulose iii second Acid esters), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, fiber At least one in plain butyrate, wherein, preferred cellulose acylate is cellulose ethanoate, cellulose acetate propionate And cellulose acetate butyrate.

Particularly cellulose acetate propionate, compared with other cellulose ethanoates (such as cellulose diacetate), is difficult Aqueous.Speculate this is because: the side chain (propiono) of cellulose acetate propionate and the side chain (acetyl of cellulose diacetate Base) to compare, hydrophobicity is high.In this aspect, as cellulose esters resinoid, preferably use cellulose acetate propionate.

The weight average molecular weight (mw) of cellulose acylate is preferably more than 75000, more preferably 75000～300000 model Enclose, in the range of more preferably 100000～240000, particularly preferred 160000～240000 cellulose acylate.As The weight average molecular weight (mw) of fruit fiber element acylate resin is more than 75000, then can play cellulose acylate layers itself oneself Film property or closely sealed improvement, preferably.In present embodiment, two or more cellulose acylate trees can be used in mixed way Fat.

The mean molecule quantity (mn, mw) of cellulose acylate can be utilized respectively gel permeation chromatography in following mensure Under the conditions of be measured.

Solvent: dichloromethane

Post: shodexk806, k805, k803g (3 connections that Showa Denko K. K is manufactured and use)

Column temperature: 25 DEG C

Sample solution concentration: 0.1 mass %

Detector: ri model 504 (manufacture of gl sciences Co., Ltd.)

Pump: l6000 (Hitachi Co., Ltd's manufacture)

Flow: 1.0ml/min

Calibration trace: using using polystyrene standard stkstandard polystyrene (TOSOH Co., Ltd's manufacture) mw The calibration trace that 13 samples in the range of=500～2800000 obtain.Preferably 13 samples are substantially to use at equal intervals.

(with regard to the characteristic of phase retardation film)

The phase retardation film (below, being only recited as film) of present embodiment is the above-mentioned va phase containing cellulose esters resinoid Potential difference film, meets following condition (1) and (2) simultaneously.

Condition (1)

Smd+std≤0.65%

Wherein, smd and std represents the size changing rate (%) of film length direction and film width respectively, is

Smd=(| bm-cm |/am) × 100

Std=(| bt-ct |/at) × 100.In above formula,

Am, bm and cm refer respectively in same film, at 23 DEG C of temperature, when relative humidity is 55%, 20% and 80%, The size (mm) of the length direction of described film,

Condition (2)

rth2-rth1≤9nm

Wherein,

Above-mentioned condition (1) specifies makes relative humidity from during 20% to 80% change in the environment of 23 DEG C of temperature, with The size changing rate smd in the film length direction on the basis of the state of relative humidity 55% and the size changing rate of film width Smd sum is less than 0.65%.In addition, when condition (2) specifies the on-fixed with respect to film, the prolonging of thickness direction when fixing The amount of change of rth is below 9nm late.

Cellulose esters resinoid compared with other resins (such as ester ring type olefin polymer resinoid), hygroscopicity (moisture-inhibiting Property) high, easily aqueous under high humidity environment.In this phase retardation film containing cellulose esters resinoid, above-mentioned by meeting Condition (1), the aqueous length direction leading to of film and/or the dimensional variations of width can be suppressed.Thus, even if across viscous In the case that film is fixed on transparency carrier by mixture, film also becomes to be difficult to expand in thickness direction when aqueous, film thickness direction Delay rth become to be difficult compared with film is in on-fixed to increase.That is, by suppressing the aqueous dimensional variations causing of film, can To meet above-mentioned condition (2).

So, by meeting condition (1) and (2), even if adopting present embodiment in the liquid crystal indicator of va type In the case of film, it is fixed in the actually used mode of liquid crystal indicator it is also possible to film during fully to high humidity in film The variation of the aqueous delay rth leading to is suppressed.As a result, can fully press down to the tone variations of display image System.

In addition, in the environment of hot and humid (such as 60 DEG C 90%rh), in order to the dimensional variations of film or postpone rth's Variation is suppressed, and under the environment lower than its temperature and humidity, (such as 23 DEG C 55%rh) is to the dimensional variations of film or delay It is minimum needs that the variation of rth carries out suppression.Therefore, by meeting set bar on the basis of the environment of 23 DEG C of 55%rh Part (1) and (2), can realize under the environment more hot and humid than it to dimensional variations or postpone the variation of rth and suppressed Film, is capable of the excellent film of wet heat durability.

The phase retardation film of present embodiment preferably further meets following condition (3).

Condition (3)

W2-w1≤2.4%

Wherein,

W1 and w2 refers respectively to the equilibrium moisture content (%) of this film,

W1={ (wa-wb)/wb } × 100

W2={ (wc-wd)/wd } × 100.In above formula,

Wa refers under 23 DEG C of temperature, relative humidity 20%, the quality (g) of the film after damping 24 hours, and wb refers to phase Same film is adjusted to the quality (g) when parching state,

Wc refers under 23 DEG C of temperature, relative humidity 80%, the quality (g) of the film after damping 24 hours, and wd refers to phase Same film is adjusted to as parching the quality (g) during state.

When condition (3) specifies that relative humidity is 80% at 23 DEG C of temperature equilibrium moisture content w2 of film with 23 DEG C of temperature Lower relative humidity is the difference of equilibrium moisture content w1 of film when 20% is less than 2.4%.It should be noted that equilibrium moisture content is Refer to: in the atmosphere of specified temperature and humidity, the water quantities in material reaches moisture content during poised state.

When big with respect to the change (w2-w1) of the equilibrium moisture content of humidity change, the aqueous dimensional variations causing become big, Thus it is speculated that due to the increase of the aqueous thickness leading to, postponing rth and also become big in the case that film is fixed.By condition (3) will be met , that is, with respect to humidity change equilibrium moisture content change suppress below 2.4%, readily satisfy above-mentioned condition (1) and (2).

In addition, in the case of for example there is space in film, moisture is easily accessible in this space, and the moisture content of film increases. In order to realize the little film of change of the moisture content with respect to humidity change, be difficult aqueous film with respect to humidity change it is necessary to Reduce the space in film.This film can be implemented as described below: by for example in the manufacture of the film with solution curtain coating masking method described later During, set the baking temperature (such as 115～160 DEG C) after stretching higher, make solvent in film (casting films) constantly Volatilization, so that be difficult to form space inside film.That is, it is difficult aqueous film to pass through to be dried under the baking temperature improving And obtain.When baking temperature is high, be chapped from the cold in the surface of film, therefore, even if by the film roll made around in the case of, also become to be difficult to produce Raw adhesion (film attaching each other).I.e., it is possible to say meet condition (3), be difficult aqueous film and can subtract with respect to humidity change Few adhesion.

It is excellent as postponing dose, nitrogen-containing heterocycle compound that the phase retardation film of present embodiment contains nitrogen-containing heterocycle compound Elect following compounds with structure shown in formula (1) as.It should be noted that to after the carrying out in detail of nitrogen-containing heterocycle compound State.

[chemical formula 1]

Formula (1)

(in formula, a₁、a₂And b represents that alkyl, cycloalkyl, aromatic series hydrocarbon ring or heteroaromatic (but remove pyrimidine ring and pyridine Outside ring), t₁And t₂Represent the link group shown in following arbitrary structures formulas, l₁～l₄Represent the concatenating group of singly-bound or divalent respectively Group, n represents 0～5 integer.)

[chemical formula 2]

(in formula, ※ represents and the l in formula (1)₁、l₂、l₃Or l₄Bonding position, r⁵Represent hydrogen atom or non-aromatic Substituent group.)

Under high humidity environment, the phase contrast that cellulose esters resinoid is manifested easily changes.This is because: cellulose esters Resin has the hydrophilic hydroxyl of many displays, and therefore, hygroscopicity is strong.On the other hand, as the nitrogen heterocyclic ring postponing dose Compound does not almost have hygroscopicity, and under high humidity environment, the phase contrast that delay dose is manifested is difficult to change.That is, by phase Potential difference film contains delay dose (nitrogen-containing heterocycle compound), mainly manifests phase contrast using postponing dose, can suppress high The overall phase contrast of wet environment lower film changes (variation of the especially aqueous delay rth leading to).As a result, can improve further The tone variations of the display image of the liquid crystal indicator under high humidity environment.

Particularly from the viewpoint of reliably obtaining the effect above, excellent as the nitrogen-containing heterocycle compound postponing dose Elect as at least any of in the compound with pyrazole ring, triazole ring, imidazole ring.And, from more reliably obtaining From the viewpoint of stating effect, preferably above-mentioned nitrogen-containing heterocycle compound is the compound with structure shown in following formulas.

[chemical formula 3]

Formula (3)

(in formula, a represents pyrazole ring, ar₁And ar₂Represent aromatic series hydrocarbon ring or heteroaromatic respectively, and can have and take Dai Ji.r₁Represent hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl, q represents 1～2 integer, n And m represents 1～3 integer.)

The phase retardation film of present embodiment contains the additive of resistance to water system further, to the aqueous delay rth's leading to Change and suppressed and be readily obtained the phase retardation film aspect meeting above-mentioned condition (1) and (2), be preferred.As this Additive, can enumerate at least one in sugar ester and polycondensation ester.It should be noted that the details to sugar ester and polycondensation ester Carry out aftermentioned.

The phase retardation film of present embodiment for example can be manufactured using solution curtain coating masking method.This solution curtain coating masking method There is following operation: the above-mentioned rubber cement containing cellulose esters resinoid is cast on supporter and is dried, from supporter The upper operation peeling off casting films (wet film)；The operation that casting films after peeling off are stretched；Stretched casting films are made to exist The operation being dried at a temperature of less than more than 115 DEG C 160 DEG C.

As described above, the baking temperature after setting stretching higher, the solvent in casting films can be made constantly to wave Send out, so that being difficult to form space in the inside of manufactured film.Thus, film becomes to be difficult aqueous, can cause to aqueous Dimensional variations are suppressed.Even if in addition, in the state of film is fixed it is also possible to due to aqueous and produce thickness increase Suppressed, the increase of the delay rth of the thickness direction that the increase of thickness leads to can be suppressed.I.e., it is possible to reliably Realize meeting the phase retardation film of above-mentioned condition (1) and (2).Further, since film be difficult aqueous, accordingly it is also possible to easily full The above-mentioned condition (3) itself of foot.And, because baking temperature is high, be chapped from the cold in the surface of film, the film therefore obtaining in winding masking When, it is possible to reduce adhesion produces, and winding situation also becomes good.

[delay dose]

Below, delay dose is described in detail.Delay dose refers to have and makes under mensure wavelength 590nm The change of the delay (the delay rth of special thickness direction) of film function of increase compared with the delay being not added with the film postponing dose Compound.

Delay dose is contained by phase retardation film, it is possible to achieve the delay ro in direction and thickness side in the face of phase retardation film To delay rth become the phase retardation film of following scope.

30nm ＜ ro ＜ 70nm

100nm ＜ rth ＜ 300nm

Above-mentioned ro and rth for example can be by using automatic birefringence meter axoscan (axo scan mueller Matrix polarimeter:axometrics company manufactures), in the environment of 23 DEG C of temperature, relative humidity 55%, measuring Carry out three-dimensional refractive index mensure under wavelength 590nm, and by refractive index n obtaining_x、n_y、n_z, calculated based on following mathematical expression.

Ro=(n_x-n_y)×d(nm)

Rth={ (n_x+n_y)/2-n_z}×d(nm)

(in formula, n_xRepresent that direction refractive index becomes the refractive index on maximum direction x in the face of film.n_yRepresent in film Refractive index on the direction direction y vertical with described direction x in face.n_zRepresent the refractive index on the thickness direction z of film.D represents The thickness (nm) of film.)

In the present embodiment, it is possible to use molecular weight is nitrogen-containing heterocycle compound in the range of 100～800 as prolonging Dose late.Wherein, nitrogen-containing heterocycle compound is preferably the compound of structure shown in following formulas (1).By together with resin Using the compound with the structure shown in following formulas (1), except can realize phase retardation film that ro and rth is above range it Outward, the variation of the delay that the humidity variation of environment causes can also be suppressed.

＜ has the compound ＞ of structure shown in formula (1)

[chemical formula 1]

Formula (1)

In above-mentioned formula (1), a₁、a₂And b separately represents alkyl (methyl, ethyl, n-pro-pyl, isopropyl, uncle Butyl, n-octyl, 2- ethylhexyl etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyl etc.), aromatic hydrocarbon Ring or heteroaromatic (but in addition to pyrimidine ring and pyridine ring).Wherein, optimization aromatic hydrocarbon ring or heteroaromatic, especially excellent Elect five yuan or hexa-atomic aromatic series hydrocarbon ring or heteroaromatic as.

The structure of five yuan or hexa-atomic aromatic series hydrocarbon ring or heteroaromatic is not limited, can enumerate for example: phenyl ring, pyrrole Cough up ring, pyrazole ring, imidazole ring, 1,2,3- triazole ring, 1,2,4- triazole ring, tetrazole ring, furan nucleuss, azoles ring, isoxazole ring, Diazole ring, different diazole ring, thiphene ring, thiazole ring, isothiazole ring, Thiadiazole, different Thiadiazole etc..

a₁、a₂And five shown in b yuan or hexa-atomic aromatic series hydrocarbon ring or heteroaromatic can have substituent group.As this Substituent group, can enumerate for example: halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), alkyl (methyl, ethyl, positive third Base, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyl etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyl Deng), alkenyl (vinyl, pi-allyl etc.), cycloalkenyl (2- cyclopentenes -1- base, 2- cyclohexene -1- base etc.), alkynyl (acetylene Base, propinyl etc.), aromatic cyclic hydrocarbon group (phenyl, p-methylphenyl, naphthyl etc.), aromatic heterocycle (2- pyrrole radicals, 2- furan Base, 2- thienyl, pyrrole radicals, imidazole radicals, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl group, 2-[4-morpholinodithio base, pyrrole Oxazolidine ketone group, pyridine radicals, pyriconyl, 2- pyrimidone, triazine radical, pyrazolyl, 1,2,3- triazolyl, 1,2,4- triazolyl, Oxazolyl, isoxazolyl, 1,2,4- di azoly, 1,3,4- di azoly, thiazolyl, isothiazolyl, 1,2,4- thiadiazolyl group, 1, 3,4- thiadiazolyl group etc.), cyano group, hydroxyl, nitro, carboxyl, alkoxyl (methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, just Octyloxy, 2- methoxy ethoxy etc.), aryloxy group (phenoxy group, 2- methylphenoxy, 4- tert-butyl benzene epoxide, 3- Nitrobenzol oxygen Base, 2- Tetradecanoylamino phenoxy group etc.), acyloxy (formyloxy, acetoxyl group, pivaloyl epoxide, stearoyl-oxy, Benzoyloxy, p-methoxyphenyl carbonyl epoxide etc.), amino (amino, methylamino, dimethylamino, anilino-, n- first Base-anilino-, diphenyl amino etc.), acyl amino (Formylamino, acetyl-amino, pivaloyl group amino, lauroyl Amino, benzoyl-amido etc.), alkyl and arlysulfonylamino (Methylsulfonylamino, butyl sulfuryl amino, phenyl Sulfuryl amino, 2,3,5- trichlorophenyl sulfuryl amino, p-methylphenyl sulfuryl amino etc.), sulfydryl, alkyl sulfenyl (first Base sulfenyl, ethylsulfanyl, n-hexadecyl sulfenyl etc.), artyl sulfo (phenylsulfartyl, rubigan sulfenyl, m-methoxyphenyl Sulfenyl etc.), sulfamoyl (n- ethylsulfamovl, n- (3- dodecyloxy propyl group) sulfamoyl, n, n- Ndimethylsulfamoyl Base, n- acetylsulfamoyl, n- benzoyl sulfamoyl, n- (n '-phenylcarbamoyl) sulfamoyl etc.), sulfo group, acyl Base (acetyl group, pivaloyl group benzoyl etc.), carbamyl (carbamyl, n- methylcarbamoyl, n, n- dimethylamino first Acyl group, n, n- bis--n-octyl carbamyl, n- (methyl sulphonyl) carbamyl etc.) etc. each base.

In above-mentioned formula (1), a₁、a₂And b represents phenyl ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazole ring or 1, 2,4- triazole ring, can get the cellulose acylate film changing excellent effect and excellent in te pins of durability of optical characteristics, therefore excellent Choosing.

In above-mentioned formula (1), t₁And t₂Preferably separately represent pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- tri- Azoles ring or 1,2,4- triazole ring.Wherein, the variation inhibition that can get the delay changing with respect to humidity is especially excellent and resistance to The long excellent resin combination of property, therefore preferably pyrazole ring, triazole ring or imidazole ring, particularly preferably pyrazole ring.t₁And t₂Institute Pyrazole ring, 1,2,3- triazole ring or 1,2,4- triazole ring, the imidazole ring showing can be tautomer.By pyrrole ring, pyrazole ring, The specific structure of imidazole ring, 1,2,3- triazole ring or 1,2,4- triazole ring is shown in following.

[chemical formula 2]

In formula, ※ symbol represents and the l in formula (1)₁、l₂、l₃Or l₄Bonding position.r⁵Represent hydrogen atom or non-aromatic Race's substituent group.As r⁵Shown non-aromatic substituent group, can enumerate and a in above-mentioned formula (1)₁The replacement that can have Non-aromatic substituent group identical group in base.r⁵In the case that shown substituent group is the substituent group with aromatic group, a₁ And t₁Or b and t₁Become easily to distort it is impossible to form a₁, b and t₁With the interaction of cellulose acylate, accordingly, it is difficult to suppression The variation of optical characteristic.In order to improve the variation inhibition of optical characteristic, r⁵It is preferably hydrogen atom, carbon number 1～5 Alkyl or carbon number 1～5 acyl group, particularly preferably hydrogen atom.

In above-mentioned formula (1), t₁And t₂Can have substituent group, as this substituent group, can enumerate and above-mentioned formula (1) a in₁And a₂The substituent group identical group that can have.

In above-mentioned formula (1), l₁、l₂、l₃And l₄Separately represent the link group of singly-bound or divalent, via 2 Following atom is linked with five yuan or hexa-atomic aromatic series hydrocarbon ring or heteroaromatic.Refer to constitute via the atom of less than 2 Minimum atomic number between the substituent group that being present in the atom of concatenating group is concatenated.As the divalent linking below atomic number 2 Concatenating group, be not particularly limited, represent be selected from alkylidene, alkylene group, alkynylene, o, (c=o), nr, s, (o=s=o) In divalent link group, or represent two concatenating groups combining of these groups.R represents hydrogen atom or substituent group. In the example of the substituent group shown in r, comprise alkyl (methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, 2- ethyl Hexyl etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyl etc.), aromatic cyclic hydrocarbon group (phenyl, to toluene Base, naphthyl etc.), aromatic heterocycle (2- furyl, 2- thienyl, 2- pyrimidine radicals, 2-[4-morpholinodithio base, 2- pyridine radicals etc.), Cyano group etc..l₁、l₂、l₃And l₄The concatenating group of shown divalent can have substituent group, as substituent group, is not particularly limited, can With enumerate for example with above-mentioned formula (1) in a₁And a₂The substituent group identical group that can have.

In above-mentioned formula (1), l₁、l₂、l₃And l₄By the above-mentioned plane with the compound of structure shown in formula (1) Property raise, and absorption water resin between Interaction enhanced, the variation of optical characteristics can be suppressed, it is therefore preferable that for 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.When n represents more than 2 integer, many in above-mentioned formula (1) Individual a₂、t₂、l₃、l₄Can identical it is also possible to different.N is bigger, and above-mentioned have the compound of structure shown in formula (1) and absorption water Resin between interaction get over strengthen, thus, the variation inhibition of optical characteristics is excellent, and n is less, with absorption water tree The compatibility between fat is more excellent.Therefore, n is preferably 1～3 integer, more preferably 1～2 integer.

＜ has the compound ＞ of the structure shown in formula (2)

The compound with structure shown in formula (1) preferably has the compound of structure shown in formula (2).

[chemical formula 4]

Formula (2)

(in formula, a₁、a₂、t₁、t₂、l₁、l₂、l₃And l₄Respectively with above-mentioned formula (1) in a₁、a₂、t₁、t₂、l₁、l₂、l₃And l₄Same meaning.a₃And t₃Represent respectively and a in formula (1)₁And t₁Same group.l₅And l₆Represent and above-mentioned formula (1) In l₁Same group.M represents 0～4 integer.)

The little compound of m, the excellent compatibility with cellulose acylate, therefore, m is preferably 0～2 integer, more preferably Integer for 0～1.

＜ has the compound ＞ of structure shown in formula (1.1)

The compound with structure shown in formula (1) preferably has the triazole chemical combination of structure shown in following formulas (1.1) Thing.

[chemical formula 5]

(in formula, a₁、b、l₁And l₂Represent and a in above-mentioned formula (1)₁、b、l₁And l₂Identical group.K represents 1～4 Integer.t₁Represent 1,2,4- triazole ring.)

And, there are the triazole compounds of structure shown in above-mentioned formula (1.1) preferably have shown in following formulas (1.2) The triazole compounds of structure.

[chemical formula 6]

Formula (1.2)

(in formula, z represents the structure of following formulas (1.2a).Q represents 2～3 integer.At least two z are with respect to by phenyl ring At least one z replacing is bonded to ortho position or meta.)

[chemical formula 7]

Formula (1.2a)

(in formula, r¹⁰Represent hydrogen atom, alkyl or alkoxyl.P represents 1～5 integer.* represent with phenyl ring be bonded position Put.t₁Represent 1,2,4- triazole ring.)

There is above-mentioned formula (1), the compound of (2), (1.1) or structure shown in (1.2) can form hydrate, solvent closes Thing or salt.It should be noted that in present embodiment, hydrate can contain organic solvent, in addition, solvate can contain Water.That is, in " hydrate " and " solvate ", the mixed solvent compound that all contains including water and organic solvent.As salt, wrap Containing the acid-addition salts being formed by inorganic or organic acid.As the example of mineral acid, comprise halogenation hydracid (hydrochloric acid, bromination hydracid Deng), sulphuric acid, phosphoric acid etc., in addition, being not limited to these.In addition, the example of organic acid can enumerate acetic acid, trifluoroacetic acid, third Acid, butanoic acid, oxalic acid, citric acid, benzoic acid, alkyl sulfonic acid (Loprazolam etc.), allyl sulphonic acid (benzenesulfonic acid, 4- toluenesulfonic acid, 1,5- naphthalenedisulfonic acid etc.) etc., in addition, being not limited to these.Wherein, preferably hydrochlorate, acetate, propionate, butyrate.

As the example of salt, can enumerate be present in the acidic moiety of parent compound by metal ion (such as alkali metal salt, Such as sodium or potassium salt, alkali salt, such as calcium or magnesium salt, ammonium salt alkali metal ion, alkaline-earth metal ions or aluminium ion etc.) Replace, or with organic base (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidines, etc.) be modulated when the salt that formed, separately Outward, it is not limited to these.Wherein, preferably sodium salt and potassium salt.

In the example containing the solvent of solvate, all include common organic solvent.Specifically, can enumerate: alcohol (such as methanol, ethanol, 2- propanol, n-butyl alcohol, 1- methoxy-2-propanol, the tert-butyl alcohol), ester (such as ethyl acetate), hydrocarbon are (for example Toluene, hexane, heptane), ether (such as oxolane), nitrile (such as acetonitrile), ketone (acetone) etc..It is preferably alcohol (such as methanol, second Alcohol, 2- propanol, n-butyl alcohol, 1- methoxy-2-propanol, the tert-butyl alcohol) solvate.These solvents can close for described compound Carry out the solvent using during partial crystallization purification after the reaction dissolvent using during one-tenth or synthesis, or can be their mixing.

In addition, two or more solvents both can have been contained or contained water and solvent (such as water and alcohol (example simultaneously As methanol, ethanol, tert-butyl alcohol etc.) etc.) form.

It should be noted that can be added in the way of not containing water or solvent, salt have above-mentioned formula (1), (2), (1.1) or the compound of structure shown in (1.2) (below, " blooming " substantially it is also possible to blooming in the present embodiment Refer to phase retardation film.) in form hydrate, solvate or salt.

There is above-mentioned formula (1), (2), (1.1) or the molecular weight of the compound of structure shown in (1.2) be not particularly limited, It is less, the compatibility with resin with excellent, it is bigger, with respect to the variation inhibition of the optical value of the change of ambient humidity Higher, it is therefore preferable that being 150～2000, more preferably 200～1500, more preferably 300～1000.

In addition, the nitrogen-containing heterocycle compound of present embodiment more preferably has the chemical combination of structure shown in following formulas (3) Thing.

[chemical formula 8]

Formula (3)

ar₁And ar₂Shown aromatic series hydrocarbon ring or heteroaromatic be respectively preferably five yuan enumerated in formula (1) or Hexa-atomic aromatic series hydrocarbon ring or heteroaromatic.In addition, as ar₁And ar₂Substituent group, can enumerate, with above-mentioned, there is formula (1) Substituent group identical substituent group shown in the compound of shown structure.

As r₁Concrete example, can enumerate: halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), alkyl (first Base, ethyl, n-pro-pyl, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyl etc.), acyl group (acetyl group, pivaloyl group benzoyl Base etc.), sulfonyl (such as methyl sulphonyl, ethylsulfonyl etc.), alkoxy carbonyl (such as methoxycarbonyl), aryloxy group carbonyl Base (such as phenyloxycarbonyl etc.) etc..

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

Hereinafter, illustrate the concrete example of the compound with five yuan or hexa-atomic aromatic series hydrocarbon ring or heteroaromatic.Described There are five yuan or the compound of hexa-atomic aromatic series hydrocarbon ring or heteroaromatic is not subject to any restriction of following concrete example.Need Illustrate, as described above, following concrete example can be for tautomer it is also possible to form hydrate, solvate or salt.

[chemical formula 9]

Exemplary compounds 1 (pyrazole compound)

Exemplary compounds 2 (azoles)

As the concrete example of nitrogen-containing heterocycle compound, in addition to above-mentioned shown exemplary compounds 1～2, state can be enumerated The compound described in paragraph [0140]～[0214] of border publication number wo2014/109350a1.But, remove and there is piperidine ring Or the nitrogen-containing heterocycle compound of pyridine ring.

[there is the synthetic method of the compound of structure shown in formula (1)]

Below, the above-mentioned synthetic method with the compound of structure shown in formula (1) is illustrated.

The above-mentioned compound with structure shown in formula (1) can be synthesized with known method.Above-mentioned, there is formula (1) in the compound of structure shown in, the compound with 1,2,4- triazole ring can use any raw material, but so that nitrile is derived The method that thing or imidoether derivant are reacted with hydrazide derivatives.As the solvent for reaction, as long as not anti-with raw material The solvent answered, any solvent can, can enumerate: esters (such as ethyl acetate, methyl acetate etc.), amide-type (dimethyl Methanamide, dimethyl acetylamide etc.), ethers (ethylene glycol dimethyl ether etc.), alcohols (for example methanol, ethanol, propanol, isopropanol, N-butyl alcohol, 2- butanol, ethylene glycol, ethylene glycol single methyl ether etc.), aromatic hydrocarbon (such as toluene, dimethylbenzene etc.), water.As The solvent using, preferably alcohols solvent.In addition, these solvents can be used in mixed way.

The usage amount of solvent is not particularly limited, with respect to use hydrazide derivatives quality, preferably 0.5～30 times In the range of amount, more preferably 1.0～25 times amount, in the range of particularly preferably 3.0～20 times amount.

In the case of making carbonitrile derivatives and hydrazide derivatives reaction, catalyst can not be used, but in order that reaction accelerates, Preferably use catalyst.As the catalyst using, it is possible to use acid, it is possible to use alkali.As acid, hydrochloric acid, sulfur can be enumerated Acid, nitric acid, acetic acid etc., preferably hydrochloric acid.For acid, can be diluted in water and add it is also possible to being blown into in system The method of gas is added.As alkali, it is possible to use inorganic base (potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, hydroxide Potassium, sodium hydroxide etc.) and organic base (Feldalat NM, Sodium ethylate, Feldalat KM, potassium ethoxide, sodium butoxide, butanol potassium, diisopropyl ethyl Amine, n, n '-dimethyl aminopyridine, 1,4- diazabicyclo [2.2.2] octane, n- methyl morpholine, imidazoles, n- Methylimidazole., Pyridine etc.) any one, as inorganic base, preferably potassium carbonate, as organic base, preferred alcohol sodium, Sodium ethylate, sodium butoxide.No Machine alkali directly can be added it is also possible to add in the state of being scattered in solvent with powder body.In addition, organic base can be dissolved in Add under the state (28% methanol solution of such as Feldalat NM etc.) of solvent.

For the usage amount of catalyst, as long as being by the amount reacted, it is not particularly limited, with respect to formed Triazole ring, in the range of preferably 1.0～5.0 times moles, in the range of further preferred 1.05～3.0 times moles.

Make imidoether derivant and hydrazide derivatives reaction in the case of it is not necessary to use catalyst, by solvent In heated, purpose thing can be obtained.

Adding method for the raw material, solvent and catalyst of reaction is not particularly limited, and finally can add catalyst, Solvent can also finally be added.Additionally, it is preferred that making carbonitrile derivatives be dispersed or dissolved in solvent and add catalyst, then, add The method of hydrazide derivatives.

For the solution temperature in reaction, as long as being by the temperature reacted, any temperature can, but preferably In the range of 0～150 DEG C, in the range of more preferably 20～140 DEG C.Furthermore it is possible to while removing the water generating, one While being reacted.

The processing method of reaction solution can use any method, but when alkali is used as catalyst, is preferably reacting molten The method that acid is neutralized is added in liquid.As the acid for neutralization, such as hydrochloric acid, sulphuric acid, nitric acid or acetic acid etc. can be enumerated, but Particularly preferably acetic acid.As long as the ph of the amount reaction solution of the acid used in neutralization becomes 4～9 scope, do not have Especially limit, with respect to the alkali using, preferably 0.1～3 times mole, in the range of particularly preferably 0.2～1.5 times mole.

As the processing method of reaction solution, in the case of being extracted using suitable organic solvent, preferably after the extraction will The method that organic solvent is concentrated after being cleaned with water.Suitable organic solvent said here is ethyl acetate, toluene, dichloro The non-water-soluble solvent such as methane, ether or the mixed solvent of described non-water-soluble solvent and oxolane or alcohols solvent, excellent Elect ethyl acetate as.

In the case of making there is the compound partial crystallization of structure shown in formula (1), it is not particularly limited, preferably anti-in neutralization Answer and add water in solution and the method that makes its partial crystallization, or to being dissolved with the aqueous solution with the compound of structure shown in formula (1) The method being neutralized and making its partial crystallization.

(synthesis of exemplary compounds 1)

Exemplary compounds 1 can be synthesized using following flow process.

[chemical formula 10]

1-Phenylethanone. 80g (0.67mol), dimethyl isophthalate 52g is added in dehydrogenation oxolane 520ml (0.27mol), under nitrogen atmosphere, stir under frozen water cooling, one side little by little Deca sodium amide 52.3g (1.34mol).After stirring 3 hours under ice water cooling, stir 12 hours under water cooling.Concentrated sulphuric acid is added to carry out in reactant liquor After neutralization, add pure water and ethyl acetate to carry out a point liquid, organic layer is cleaned with pure water.Organic layer is done with magnesium sulfate Dry, solvent is carried out decompression and evaporates.Add methanol and carry out the cleaning that suspends in the coarse crystallization obtaining, thus obtain 55.2g's Intermediate a.

Add the intermediate a (0.15mol) of 55g in oxolane 300ml, ethanol 200ml, stir at room temperature Mix, little by little the hydrazine 1 hydrate (0.37mol) of Deca 18.6g.After completion of dropwise addition, it is heated to reflux 12 hours.In reaction Add pure water and ethyl acetate in liquid and carry out a point liquid, organic layer is cleaned with pure water.Organic layer magnesium sulfate is dried, Solvent under reduced pressure is evaporated.By being purified with silica gel chromatography (ethyl acetate/heptane) to the coarse crystallization obtaining, obtain 27g Exemplary compounds 1.

The exemplary compounds 1 obtaining¹H-nmr spectrum is as described below.It should be noted that depositing due to tautomer In order to avoid chemical shift complicates, few drops trifluoroacetic acid is being added to be measured in measuring solvent.

¹H-nmr (400mhz, solvent: weight dmso, benchmark: tetramethylsilane) δ (ppm): 8.34 (1h, s), 7.87～ 7.81 (6h, m), 7.55～7.51 (1h, m), 7.48-7.44 (4h, m), 7.36-7.33 (2h, m), 7.29 (1h, s)

With regard to other compounds, it is possible to use same method is synthesizing.

＜ is with regard to having using method ＞ of the compound of structure shown in formula (1)

The above-mentioned compound with structure shown in formula (1) can adjust appropriate amount and contain in blooming, as adding Dosage, contains 0.1～10 mass % preferably with respect to the resin constituting blooming, particularly preferably contains 0.5～5 mass %.Only If it is possible to the machinery reducing the variation of phase contrast depending on ambient humidity change and not damaging blooming is strong in the range of being somebody's turn to do Degree.

In addition, as the above-mentioned adding method with the compound of structure shown in formula (1), blooming can be being formed Added with powder body in resin, can add in the resin forming blooming after being dissolved in solvent.

Have in the compound of structure shown in formula (1) above-mentioned, end has the compound (exemplary compounds 1 of phenyl ring ～3 etc.), its with solution curtain coating masking method described later, with respect to the dissolubility of the dichloromethane using as main solvent, (saturation is molten Xie Du) as little as less than 10%.Therefore, the compound of this slightly solubility is direct plungeed into when the dissolution kettle, produce that to become bright spot different The insoluble matter of thing reason.Therefore, in nitrogen-containing heterocycle compound, in the case of the compound of slightly solubility, preferably will be above-mentioned Compound makes an addition to solvent (dichloromethane simple substance) and is stirred making it disperse, then, together with forming the resin of blooming Devote dissolution kettle.

[organic ester]

The blooming (phase retardation film) of present embodiment, as organic ester, preferably comprises selected from sugar ester, polycondensation ester, polyhydric alcohol At least one in ester, above-mentioned polycondensation ester does not contain nitrogen-atoms in the structure, carries out liquefied when cooled in manufacturing line And it is attached to filter, the big low height in filter traps thing for the nitrogen-containing heterocycle compound can be reduced, therefore preferably.Wherein, Sugar ester and polycondensation ester work as the plasticizer of resistance to water, therefore, are suitable to the variation of the aqueous delay rth leading to is pressed down The phase retardation film of the present embodiment of system.

(sugar ester)

Sugar ester is containing at least any of compound in furanose ring or pyranose ring, can for monosaccharide it is also possible to The polysaccharide being formed by connecting for 2～12 sugared structures.And, at least one of the oh base that the preferably sugared structure of sugar ester has is esterified 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, it is not particularly limited, the sugar ester shown in following formulas (a) can be enumerated.

Formula (a)

(ho)_m- g- (o-c (=o)-r²)_n

In above-mentioned formula (a), g represents the residue of monosaccharide or disaccharides, r²Represent aliphatic group or aromatic group, M is the total of the hydroxyl quantity of Direct Bonding on the residue of monosaccharide or disaccharides, and n is the residue in monosaccharide or disaccharides Upper Direct Bonding-(o-c (=o)-r²) radical amount total, be 3≤m+n≤8, be n ≠ 0.

There is the quantity (m) as hydroxyl for the sugar ester ,-(o-c (=the o)-r of structure shown in formula (a)²) base quantity (n) The compound isolation of fixing single kind difficult it is known to the multiple compound being mixed into of the different composition of m, n in formula. That is, the quantity (m) of hydroxyl, conduct-(o-c (=o)-r²) performance of the respective mixture of change of quantity (n) of base is important, In the case of the blooming of present embodiment, preferably average ester substitution value is the sugar ester in the range of 5.0～7.5.

In above-mentioned formula (a), g represents the residue of monosaccharide or disaccharides.As the concrete example of monosaccharide, example can be enumerated As: allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, wood Sugar, lyxose etc..

Hereinafter, the concrete example with the compound of monosaccharide residue of sugar ester shown in formula (a) is shown, but is not limited to These compounds illustrating.

[chemical formula 11]

In addition, as the concrete example of disaccharides residue, can enumerate for example: trehalose, sucrose, maltose, cellobiose, dragon Gallbladder disaccharide, Lactose, isotrehalose etc..

Hereinafter, the concrete example with the compound of disaccharides residue of sugar ester shown in formula (a) is shown, but is not limited to These compounds illustrating.

[chemical formula 12]

In formula (a), r²Represent aliphatic group or aromatic group.Here, aliphatic group and aromatic group can Separately to have substituent group.

In addition, in formula (a), m is the total of the hydroxyl quantity of Direct Bonding on the residue of monosaccharide or disaccharides, n Be on the residue of monosaccharide or disaccharides Direct Bonding-(o-c (=o)-r²) radix amount total.And it is necessary to for 3≤ M+n≤8, preferably 4≤m+n≤8.In addition, being n ≠ 0.It should be noted that when n is more than 2 ,-(o-c (=o)-r²) base was both Can mutually identical it is also possible to different.

r²Definition in aliphatic group can be straight chain or side chain, can also be ring-type, preferably carbon atom The aliphatic group of number 1～25, more preferably 1～20 aliphatic group, particularly preferred 2～15 aliphatic group.As fat The concrete example of fat race group, can enumerate for example: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, tertiary fourth Base, amyl group, isopentyl, tertiary pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, connection cyclooctyl, adamantyl, positive decyl, uncle Each base such as octyl group, dodecyl, cetyl, octadecyl, eicosyl.

In addition, r²Definition in aromatic group both can be aromatic hydrocarbyl or aromatic heterocycle, more It is preferably aromatic hydrocarbyl.As aromatic hydrocarbyl, preferably carbon number is 6～24 aromatic hydrocarbyl, further preferred 6～ 12 aromatic hydrocarbyl.As the concrete example of aromatic hydrocarbyl, such as each ring such as benzene, naphthalene, anthracene, biphenyl, terphenyl can be enumerated.Make For aromatic hydrocarbyl, particularly preferred phenyl ring, naphthalene nucleus, cyclohexyl biphenyl.As aromatic heterocycle, preferably comprise oxygen atom, nitrogen-atoms Or the ring of at least one of sulphur atom.As the concrete example of heterocycle, can enumerate for example: furan, pyrroles, thiophene, imidazoles, pyrrole Azoles, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazoles, oxazoline, azoles, diazole, Quinoline, isoquinolin, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, Each ring such as benzothiazole, benzothiazole, benzotriazole, purine.As aromatic heterocycle, particularly preferred pyridine ring, three Piperazine ring, quinoline ring.

Sugar ester can contain plural different substituent group in a molecule, can contain fragrance in 1 intramolecular Race's substituent group and aliphatic substitution, contain different plural aromatic substituents in 1 intramolecular, contain in 1 intramolecular There are different plural aliphatic substitution.

Additionally, it is preferred that mixing is containing two or more sugar esters.Preferably comprise simultaneously the sugar ester containing aromatic substituents and Sugar ester containing aliphatic substitution.

Hereinafter, the preferred example of the sugar ester shown in formula (a) is shown in following, but be not limited to these illustration change Compound.

[chemical formula 13]

[chemical formula 14]

＜ synthesis example: synthesis example ＞ of the sugar ester shown in formula (a)

Hereinafter, the synthesis example of sugar ester is shown.

[chemical formula 15]

It is respectively charged into sucrose in the four-hole boiling flask having agitating device, reflux cooler, thermometer and nitrogen ingress pipe 34.2g (0.1 mole), benzoyl oxide 180.8g (0.8 mole), pyridine 379.7g (4.8 moles), under agitation from nitrogen Ingress pipe makes nitrogen bubble, heats up, carries out 5 hours esterifications at 70 DEG C.Then, make to be decompressed to 4 in flask × 10²Below pa, after evaporating excessive pyridine, makes to be decompressed to 1.3 × below 10pa in flask, be warming up to 120 DEG C at 60 DEG C, Evaporate benzoyl oxide and the benzoic major part generating.And, then add toluene 1l, 0.5 mass % sodium carbonate water-soluble Liquid 300g, stirring at 50 DEG C stands for 30 minutes afterwards, divides and takes toluene layer.Finally, add water in point toluene layer taking 100g, washing at normal temperatures point takes toluene layer in 30 minutes afterwards, and under reduced pressure (4 × 10²Below pa), evaporate toluene at 60 DEG C, Obtain the mixture of compound a -1, compound a -2, compound a -3, compound a -4 and compound a -5.By the mixture obtaining It is analyzed with hplc and lc-mass as a result, a-1 is 7 mass %, a-2 is 58 mass %, a-3 is 23 mass %, a-4 is 9 Quality %, a-5 is 3 mass %, and the average ester substitution value of sugar ester is 6.57.It should be noted that by using silica gel column chromatography Method purifies to a part for the mixture obtaining, respectively obtains a-1, a-2, a-3, a-4 and a-5 of purity 100%.

The addition of this sugar ester is being preferably 0.1～20 with respect to the resin (such as cellulose acylate) constituting blooming The scope of quality % is added, and more preferably the scope in 1～15 mass % is added.

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

(polycondensation ester)

In the blooming (phase retardation film) of present embodiment, as organic ester, preferably use and there is following formulas (4) institute Show the polycondensation ester of structure.From the aspect of the effect of its plasticising, this polycondensation ester is being preferably 1 with respect to the resin constituting blooming The scope of～30 mass % contains, and more preferably the scope in 5～20 mass % contains.

Formula (4)

b₃-(g₂-a)_n-g₂-b₄

In above-mentioned formula (4), b₃And b₄Separately represent aliphatic or aromatic monocarboxylate's residue or hydroxyl.g₂Table Show that the aklylene glycol residue of carbon number 2～12, the aryl-diol residue of carbon number 6～12 or carbon number are 4～12 Oxyalkylene diol residue.A represents the alkylene dicarboxylic acids residue of carbon number 4～12 or the aryl of carbon number 6～12 Dicarboxylic acid residue.N represents more than 1 integer.

Polycondensation ester is containing the polycondensation ester making dicarboxylic acids and repetitives obtained from glycol reaction, and a represents in polycondensation ester Carboxylic acid residues, g₂Represent alcohol residue.

The dicarboxylic acids constituting polycondensation ester are aromatic dicarboxylic acid, aliphatic dicarboxylic acid or ester ring type dicarboxylic acids, preferably virtue Fragrant race dicarboxylic acids.Dicarboxylic acids can be a kind of or two or more mixture.Particularly preferably make aromatic series, aliphatic Mixing.

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

Wherein, preferably comprise so that the glycol of at least dicarboxylic acids containing aromatic dicarboxylic acid and carbon number 1～8 is reacted and The repetitives obtaining, more preferably comprise to make the dicarboxylic acids containing aromatic dicarboxylic acid and aliphatic dicarboxylic acid and carbon number 1 ～8 repetitives obtained from glycol reaction.

Two ends of the molecule of polycondensation ester can be blocked it is also possible to not blocked.

As the concrete example of the alkylene dicarboxylic acids of a constituting formula (4), comprise by 1,2- ethane dicarboxylic acids (succinum Acid), 1,3- propane dicarboxylic acids (1,3-propanedicarboxylic acid), 1,4- butane dicarboxylic acid (adipic acid), 1,5- pentanedicarboxylic acid (1,5-pentanedicarboxylic acid .), 1,8- Octane dicarboxylic acid's (decanedioic acid) etc. derived from divalent group.As the concrete example of the alkenylene dicarboxylic acids constituting a, can lift Go out maleic acid, fumaric acid etc..As the concrete example of the aryl dicarboxylic acid constituting a, 1,2-benzenedicarboxylic acid (O-phthalic can be enumerated Acid), 1,3- benzene dicarboxylic acid, 1,4- benzene dicarboxylic acid, 1,5- naphthalene dicarboxylic acids etc..

A can be for a kind of it is also possible to combination be two or more.Wherein, the alkylene dicarboxylic acids of the preferred carbon number of a 4～12 Combination with the aryl dicarboxylic acid of carbon number 8～12.

G in formula (4)₂Represent aklylene glycol by carbon number 2～12 derived from divalent group, former by carbon The aryl-diol of subnumber 6～12 derived from the group of divalent or the oxyalkylene glycol institute derivative 2 by carbon number 4～12 The group of valency.

By g₂In the aklylene glycol of carbon number 2～12 derived from divalent the example of group in, comprise by second Glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,2- propylene glycol, 2- methyl isophthalic acid, 3- the third two Alcohol, 1,4- butanediol, 1,5- pentanediol, 2,2- dimethyl -1,3- propylene glycol (neopentyl glycol), 2,2- diethyl -1,3- the third two Alcohol (3,3- dihydroxymethyl pentane), 2- normal-butyl -2- ethyl -1,3- propylene glycol (3,3- dihydroxymethyl heptane), 3- methyl isophthalic acid, 5- Pentanediol, 1,6-HD, 2,2,4- trimethyl -1,3- pentanediol, 2- ethyl -1,3- hexanediol, 2- methyl isophthalic acid, 8- pungent two Alcohol, 1,9- nonanediol, 1,10- decanediol and 1,12- octacosanol etc. derived from divalent group.

By g₂In the aryl-diol of carbon number 6～12 derived from divalent the example of group in, comprise by 1,2- Divalent derived from the institute such as dihydroxy benzenes (catechol), 1,3- dihydroxy benzenes (resorcinol), 1,4- dihydroxy benzenes (hydroquinone) Group.The oxyalkylene glycol being 4～12 by the carbon number in g derived from divalent group example in, comprise by Diethylene glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol etc. derived from divalent group.

g₂Can be for a kind it is also possible to combine two or more.Wherein, g₂Preferably by the aklylene glycol institute of carbon number 2～12 The group of derivative divalent, further preferred 2～5, most preferably 2～4.

B in formula (4)₃And b₄Be by the monocarboxylic acid of each self-contained aromatic rings or aliphatic monocarboxylic acid derivative 1 valency base Group or hydroxyl.

By the monocarboxylic acid containing aromatic rings derivative 1 valency group in the monocarboxylic acid containing aromatic rings contain virtue for intramolecular The carboxylic acid of fragrant ring, not only comprises the carboxylic acid of aromatic rings and the synthesis of carboxyl direct key, and comprises aromatic rings via alkylidene etc. And the carboxylic acid becoming with carboxylic-bond.By the monocarboxylic acid containing aromatic rings derivative 1 valency group example in, comprise by benzene first Acid, p-tert-butyl benzoic acid, adjacent toluic acid, a toluic acid, to toluic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene Formic acid, amino benzoic Acid, acetoxy-benzoic acid, phenylacetic acid, 3- phenylpropionic acid etc. derivative 1 valency group.Wherein, excellent Select benzoic acid, to toluic acid.

By aliphatic monocarboxylic acid derivative 1 valency group example in, comprise by acetic acid, propanoic acid, butanoic acid, octanoic acid, Caproic acid, capric acid, dodecylic acid, stearic acid, Oleic acid etc. derivative 1 valency group.Wherein, preferably by the carbon atom of moieties Number for 1～3 alkyl monocarboxylates institute derived from 1 valency group, more preferably acetyl group (by acetic acid derived from 1 valency group).

In present embodiment, the scope of the weight average molecular weight preferably 500～3000 of polycondensation ester, more preferably 600～ 2000 scope.Weight average molecular weight can be measured using described gel permeation chromatography (gpc).

Hereinafter, the concrete example with the polycondensation ester of structure shown in formula (4) is shown, but is not limited to this.

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

Hereinafter, the specific synthesis example of the polycondensation ester of described above is recorded.

＜ polycondensation ester p1 ＞

Using ethylene glycol 180g, phthalic anhydride 278g, adipic acid 91g, benzoic acid 610g, as the four of esterification catalyst Isopropyl titanate esters 0.191g load and have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stir, Lentamente heat up, until becoming 230 DEG C in nitrogen stream on one side.While observing the degree of polymerization, carry out dehydration condensation.Instead After should terminating, decompression at 200 DEG C evaporates unreacted ethylene glycol, thus obtains polycondensation ester p1.Acid number is 0.20, the equal molecule of number Measure as 450.

＜ polycondensation ester p2 ＞

Using 1,2- propylene glycol 251g, phthalic anhydride 103g, adipic acid 244g, benzoic acid 610g, as catalyzing esterification The tetra isopropyl titanate 0.191g of agent load have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, Stirring, lentamente heats up, until becoming 230 DEG C in nitrogen stream.While observing the degree of polymerization, carry out dehydrating condensation anti- Should.After reaction terminates, decompression at 200 DEG C evaporates unreacted 1,2-PD, thus obtains following polycondensation ester p2.Acid number is 0.10, number-average molecular weight is 450.

[chemical formula 19]

＜ polycondensation ester p3 ＞

Using 1,4- butanediol 330g, phthalic anhydride 244g, adipic acid 103g, benzoic acid 610g, as catalyzing esterification The tetra isopropyl titanate 0.191g of agent load have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, Stirring, lentamente heats up, until becoming 230 DEG C in nitrogen stream.While observing the degree of polymerization, carry out dehydrating condensation anti- Should.After reaction terminates, decompression at 200 DEG C evaporates unreacted BDO, thus obtains polycondensation ester p3.Acid number is 0.50, number-average molecular weight is 2000.

＜ polycondensation ester p4 ＞

Using 1,2- propylene glycol 251g, p-phthalic acid 354g, benzoic acid 610g, the tetra isopropyl titanium as esterification catalyst Acid esters 0.191g load have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stirring, on one side slowly Ground heats up, until becoming 230 DEG C in nitrogen stream.While observing the degree of polymerization, carry out dehydration condensation.Reaction terminates Afterwards, at 200 DEG C, decompression evaporates unreacted 1,2-PD, thus obtains polycondensation ester p4.Acid number is 0.10, number-average molecular weight For 400.

＜ polycondensation ester p5 ＞

Using 1,2- propylene glycol 251g, p-phthalic acid 354g, paratolunitrile 680g, four isopropyls as esterification catalyst Base titanate esters 0.191g load and have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stir, on one side Lentamente heat up, until becoming 230 DEG C in nitrogen stream.While observing the degree of polymerization, carry out dehydration condensation.Reaction knot Shu Hou, decompression at 200 DEG C evaporates unreacted 1,2-PD, thus obtains following polycondensation ester p5.Acid number is 0.30, and number is all Molecular weight is 400.

[chemical formula 20]

＜ polycondensation ester p6 ＞

Using the 1,2- propylene glycol of 180g, the adipic acid of 292g, the tetra isopropyl titanate 0.191g as esterification catalyst Load have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stirring, lentamente heat up, in nitrogen in one side To becoming 200 DEG C in air-flow.While observing the degree of polymerization, carry out dehydration condensation.After reaction terminates, subtract at 200 DEG C Pressure evaporates unreacted 1,2-PD, thus obtains polycondensation ester p6.Acid number is 0.10, and number-average molecular weight is 400.

＜ polycondensation ester p7 ＞

Using the 1,2- propylene glycol of 180g, phthalic anhydride 244g, adipic acid 103g, four isopropyls as esterification catalyst Base titanate esters 0.191g load and have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stir, on one side Lentamente heat up, until in nitrogen stream to becoming 200 DEG C.While observing the degree of polymerization, carry out dehydration condensation.Reaction After end, decompression at 200 DEG C evaporates unreacted 1,2-PD, thus obtains polycondensation ester p7.Acid number is 0.10, and number is divided equally Son is measured as 320.

＜ polycondensation ester p8 ＞

Using ethylene glycol 251g, phthalic anhydride 244g, succinic acid 120g, acetic acid 150g, as the four of esterification catalyst Isopropyl titanate esters 0.191g load and have thermometer, agitator, in the four-hole boiling flask of 2l of pipe ball cooling tube, stir, Lentamente heat up on one side, until in nitrogen stream to becoming 200 DEG C.While observing the degree of polymerization, carry out dehydration condensation. After reaction terminates, decompression at 200 DEG C evaporates unreacted ethylene glycol, thus obtains polycondensation ester p8.Acid number is 0.50, and number is divided equally Son is measured as 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, number-average molecular weight 315 polycondensation ester p9.

＜ polyol ester ＞

The phase retardation film of present embodiment is it is also preferred that contain polyol ester.Polyol ester be by two-spot more than aliphatic many The compound that the ester of first alcohol and monocarboxylic acid is constituted, preferably intramolecular has aromatic rings or cycloalkyl ring.It is preferably 2～20 yuan of fat Fat race polyol ester.

The polyhydric alcohol preferably using in present embodiment is represented with following formula (5).

Formula (5) r₁₁-(oh)_n

Wherein, r₁₁Represent positive integer, oh basis representation alcoholic extract hydroxyl group and/or phenol that the organic group of n valency, n represent more than 2 Hydroxyl.

As the example of preferred polyhydric alcohol, for example following polyhydric alcohol can be enumerated, but be not limited to these.

Can enumerate: ribitol, 1,2,3,4,5-pentanepentol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, 1,2- the third two Alcohol, 1,3- propylene glycol, dipropylene glycol, tripropylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, dibutylene glycol, 1, 2,4- butantriol, 1,5- pentanediol, 1,6-HD, hexanetriol, galactose, Mannitol, 3- methylpentane -1,3,5- triol, Pinacol, Sorbitol, trimethylolpropane, trimethylolethane, xylitol etc..

Particularly preferably triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, Sorbitol, trimethylolpropane, wood Sugar alcohol.

As the monocarboxylic acid used in polyol ester, it is not particularly limited, it is possible to use known aliphatic monocarboxylic acid, Cycloaliphatic monocarboxylic, aromatic monocarboxylate etc..During using cycloaliphatic monocarboxylic, aromatic monocarboxylate, improving poisture-penetrability, reservation Property aspect, preferably.

As the example of preferred monocarboxylic acid, following monocarboxylic acid can be enumerated, but be not limited to this.

It may be preferred to use, there is the straight chain of carbon number 1～32 or the fatty acid of side chain as aliphatic monocarboxylic acid.Carbon Atomic number more preferably 1～20, particularly preferably 1～10.During containing acetic acid, the compatibility with cellulose ethanoate increases Plus, therefore preferably, it is also preferred that being used in mixed way acetic acid and other monocarboxylic acid.

As preferred aliphatic monocarboxylic acid, can enumerate: acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, nonyl Acid, capric acid, 2- ethyl-hexanoic, hendecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 18 Alkanoic acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, carboceric acid, montanic acid, Herba leucadis ciliatae The insatiable hungers such as the satisfied fatty acid such as acid, lacceroic acid, 9-undecylenic acid, Oleic acid, sorbic acid, linoleic acid, linolenic acid, Ara With fatty acid etc..

As the example of preferred cycloaliphatic monocarboxylic, Cyclopentane carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic can be enumerated Acid or their derivant.

As the example of preferred aromatic monocarboxylate, phenyl ring benzoic in benzoic acid, toluic acid etc. can be enumerated On be imported with the monocarboxylic acid of the alkoxyls such as 1～3 alkyl, methoxy or ethoxy, biphenyl carboxylic acids, naphthalene-carboxylic acid, tetrahydronaphthalene carboxylic Acid etc. has aromatic monocarboxylate or their derivant of more than 2 phenyl ring.Particularly preferably benzoic acid.

The molecular weight of polyol ester is not particularly limited, but preferably 300～1500 scope, more preferably 350 ～750 scope.The big polyol ester of molecular weight is it becomes difficult to volatilize, therefore preferably, in poisture-penetrability and cellulose acylate Compatibility aspect, the little polyol ester of preferred molecular weight.

Used in polyol ester, carboxylic acid can be both a kind of or two or more mixed acid.In addition, polyhydric alcohol In oh base both can be to be all esterified it is also possible to remain a part in the way of with oh base.

Hereinafter, illustrate the specific compound of polyol ester.

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

Polyol ester preferably containing with respect to the scope that phase retardation film (cellulose esters resinoid) is 0.5～5 mass %, More preferably the scope in 1～3 mass % contains, and particularly preferably the scope in 1～2 mass % contains.

Polyol ester can synthesize according to known common synthetic method.

[other additive]

＜ phosphate ester ＞

The phase retardation film of present embodiment can contain phosphate ester.As phosphate ester, can enumerate: triaryl phosphate, two Aryl phosphate ester, aryl phosphate, aryl phosphine oxide compound, aryl oxidized phosphine compound, condensation aryl phosphate ester, alkyl halide Base phosphate ester, halogen condensed phosphoric acid esters, halogen condensation phosphonate ester, halogen phosphite ester etc..

As specific phosphate ester, can enumerate: Triphenyl phosphate, 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxygen Compound, phenyl-phosphonic acid, three (β-chloroethyl) phosphate ester, three (two chloropropyls) phosphate ester, three (tribromo neopentyl) phosphate ester etc..

The esters ＞ of ＜ alkyd

In addition, the one kind as polyhydric alcohol esters, it is possible to use the esters (ethyl glycolate compound) of glycolic.As second Alcoholic acid esterification compound, is not particularly limited it may be preferred to use alkyl phthalic acyl alkyl glycolate esters.

As alkyl phthalic acyl alkyl glycolate esters, can enumerate for example: methyl phthalyl methyl glycollate, Ethyl phthalyl ethyl glycolate, propyl group phthalyl alcohol propyl propionate, butyl phthalyl alcohol acid butyl ester, octyl group are adjacent Phenyl-diformyl alkyd monooctyl ester, methyl phthalyl ethyl glycolate, ethyl phthalyl methyl glycollate, ethyl neighbour's benzene two Formylglycollic acid propyl ester, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl O-phthalic Acyl methyl glycollate, butyl methyl phthallyl ethyl glycollate, propyl group phthalyl butyl glycolate, butyl phthalyl Propyl glycolate, methyl phthalyl glycolic monooctyl ester, ethyl phthalyl glycolic monooctyl ester, octyl phthalyl second Alkyd methyl ester, octyl phthalyl ethyl glycolate etc., preferably ethyl phthalyl ethyl glycolate.

＜ microgranule (delustering agent) ＞

In order to improve the lubricity on surface, phase retardation film can contain microgranule (delustering agent) as needed further.

Microgranule can be inorganic particles or organic fine particles.Silicon dioxide (two is comprised in the example of inorganic particles Silicon oxide), titanium dioxide, aluminium oxide, zirconium oxide, Calcium Carbonate, Calcium Carbonate, Talcum, clay, roasting kaolin, roasting calcium silicates, Afwillite, aluminium silicate, magnesium silicate and calcium phosphate etc..Wherein, preferably silicon dioxide or zirconium oxide, in order to reduce the film obtaining The increase of mist degree, more preferably silicon dioxide.

In the example of the microgranule of silicon dioxide, comprise aerosil r972, aerosil r972v, aerosil r974, aerosil r812、aerosil 200、aerosil 200v、aerosil300、aerosil r202、aerosil ox50、 Aerosil tt600, aerosil nax50 (above Japanese aerosil Co., Ltd. manufacture), seahostar ke-p10, Seahostar ke-p30, seahostar ke-p50, seahostar ke-p100 (above Nippon Shokubai Co., Ltd manufactures) Deng.Wherein, the film that aerosil r972v, aerosil nax50, seahostar ke-p30 etc. lower keep obtaining muddy Turbidity, and reduce coefficient of friction, therefore particularly preferably.

The primary particle size of microgranule is preferably the scope of 5～50nm, the more preferably scope of 7～20nm.Primary particle size is big Microgranule, the effect improving the lubricity of film obtaining is good, but the transparency is easily reduced.Therefore, microgranule as particle diameter can be The secondary aggregation body of 0.05～0.3 μm of scope and contain.The size of the primary particle of microgranule or its secondary aggregation body can be used Transmission electron microscope observes primary particle or secondary aggregation body for 50～2,000,000 times with multiplying power, and as primary particle or two The meansigma methodss of secondary 100 particle diameters of agglutination body are obtained.

With respect to the resin forming phase retardation film, the content of microgranule is preferably the scope of 0.05～1.0 mass %, more preferably Scope for 0.1～0.8 mass %.

＜ retardation controlling agent ＞

In order to improve the display quality of the image display devices such as liquid crystal indicator, phase retardation film adds phase contrast control Preparation, or form alignment films and liquid crystal layer is set, carry out Composite to polaroid protective film with from the phase contrast of liquid crystal layer, by This can give optical compensation energy to phase retardation film.

As retardation controlling agent, European Patent 911 can be enumerated, described in 656a2 description have more than 2 Rod-shaped compound described in the aromatic compound of aromatic ring, Japanese Unexamined Patent Publication 2006-2025 publication etc..In addition, also may be used To be applied in combination two or more aromatic compounds.On the aromatic ring of this aromatic compound, except aromatic series hydrocarbon ring it Outward, the aromatic series heterocycle preferably containing aromatic series heterocycle.Aromatic series heterocycle is generally unsaturated heterocycle.Wherein, excellent Select the 1,3,5- triazine ring described in Japanese Unexamined Patent Publication 2006-2026 publication.

It should be noted that the compound with structure shown in formula (1) also plays a role as retardation controlling agent.Cause This, the compound with structure shown in formula (1) can be led to a compound performance phase-difference control function with to aqueous The variation of delay rth carry out suppression function both functions.

With respect to resin 100 mass % using as film base material, the addition of these retardation controlling agent is preferably 0.5 In the range of～20 mass %, in the range of more preferably 1～10 mass %.

[manufacture method of phase retardation film]

The phase retardation film of present embodiment can be manufactured using such as solution curtain coating masking method or melting casting film method. But, during the phase retardation film of manufacture thin film, the reduction in order to suppress the aqueous delay rth leading to increases it is necessary to increase as delay Plus the addition of the nitrogen-containing heterocycle compound of agent.In the case that the addition of nitrogen-containing heterocycle compound is many, in melting casting film In method, nitrogen-containing heterocycle compound produces burnt burnt grade in film-forming process and does not melt, it is therefore preferable that with solution curtain coating masking method Lai Masking.Hereinafter, the example of the phase retardation film making present embodiment with solution curtain coating masking legal system is illustrated.

(solution curtain coating masking method)

Fig. 2 schematically shows an example of the device making phase retardation film using solution curtain coating masking legal system.In solution In casting film method, carry out successively: (1) at least makes the additives such as cellulose esters resinoid, nitrogen-containing heterocycle compound and organic ester It is dissolved in solvent and prepare the operation of rubber cement；(2) rubber cement is cast the operation in the metal support of banding or drum type；(3) The evaporation of the solvent in the rubber cement of curtain coating in metal support is made to obtain the operation of wet film；(4) by wet film from metal support The operation of upper stripping；(5) operation so as to be dried is stretched to the wet film (film) peeled off；(6) it is wound after making film cooling Operation.

(1) rubber cement preparation section

In this operation, in the organic solvent based on the good solvent with respect to cellulose esters resinoid, in dissolution kettle In 31, to this cellulose esters resinoid and nitrogen-containing heterocycle compound according to circumstances, sugar ester, polycondensation ester, polyol ester or Other compounds, while being stirred, make it dissolve, thus forming rubber cement.Or, in this cellulose esters resin solution In make nitrogen-containing heterocycle compound, sugar ester, polycondensation ester, polyol ester or the mixing of other compound solution, formed as main lysate Rubber cement.

When making phase retardation film with solution curtain coating masking legal system, as long as dissolve to forming the useful organic solvent of rubber cement simultaneously Cellulose esters resinoid and the solvent of other compound, can use without limitation.

For example, as chlorine class organic solvent, dichloromethane can be enumerated, as non-chlorine class organic solvent, can enumerate: second Sour methyl ester, ethyl acetate, pentyl acetate, acetone, oxolane, 1,3- dioxa penta ring, 1,4- dioxane, Ketohexamethylene, formic acid Ethyl ester, 2,2,2 tfifluoroethyl alcohol, the fluoro- 1- propanol of 2,2,3,3- tetra-, the fluoro- 2- propanol of 1,3- bis-, 1,1,1,3,3,3- hexafluoro -2- first Base -2- propanol, HFIP, 2,2,3,3,3- five fluoro- 1- propanol, nitroethane etc. are it may be preferred to make With dichloromethane, methyl acetate, ethyl acetate, acetone.

In rubber cement, in addition to above-mentioned organic solvent, preferably comprise 1～40 mass % scope carbon number 1～4 straight Chain or the aliphatic alcohol of branched.When in rubber cement, the ratio of alcohol raises, wet net carries out gelation, becomes from the stripping of metal support Obtain easily, in addition, when the ratio of alcohol is few, it may have promote the cellulose esters resinoid in non-chlorine class organic solvent system and other The effect of the dissolving of compound.In the masking of phase retardation film, from the aspect of the flatness improving the phase retardation film obtaining, can Method to be filmed using the rubber cement in the range of 0.5～15.0 mass % using determining alcohol.

Cellulose acylate and other compound is particularly preferably made to be dissolved in the scope amounting to 15～45 mass % and contain There is the composition of colloidal slurry being formed in dichloromethane and the solvent of the aliphatic alcohol of straight or branched of carbon number 1～4.

As the aliphatic alcohol of the straight or branched of carbon number 1～4, methanol, ethanol, normal propyl alcohol, different can be enumerated Propanol, n-butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol.Wherein, from the stability of rubber cement, boiling point also than relatively low, drying property might as well etc. in terms of examine Consider, preferably methanol and ethanol.

In cellulose esters resinoid, nitrogen-containing heterocycle compound, sugar ester, polycondensation ester and polyol ester or other compound In dissolving, following various dissolving methods: the method carrying out at ambient pressure, the side carrying out below the boiling point of main solvent can be adopted Method, the method carrying out of pressurizeing more than the boiling point of main solvent, with Japanese Unexamined Patent Publication 9-95544 publication, Japanese Unexamined Patent Publication 9- The method that hot-cold lysis method described in No. 95557 publications or Japanese Unexamined Patent Publication 9-95538 publication is carried out, in Japanese Unexamined Patent Publication Method carrying out under high pressure described in flat 11-21379 publication etc., pressurizes particularly preferably more than the boiling point of main solvent and enters The method of row.

The concentration of the cellulose esters resinoid in rubber cement is preferably the scope of 10～40 mass %.In dissolving or after dissolving Rubber cement in add compound and dissolved and disperseed, then, filter and carry out deaeration with filter material, be pumped into next with liquor charging Operation.

Filter and preferably use the filter material that trapping particle diameter is 0.5～5 μm and drainage time 10～25sec/100ml.

In the method, the agglomerate remaining when particle disperses or the agglomerate producing when main rubber cement adds can be led to Cross the filter material using trapping particle diameter is 0.5～5 μm and drainage time 10～25sec/100ml and only remove agglomerate.Main rubber cement In, the concentration of particle is also fully little compared with annex solution, therefore, agglomerate will be occurred to cling each other when filtering and make filter Pressure sharp rises.

(2) it is cast operation

In this operation, the rubber cement in dissolution kettle 31 is passed through liquid-feeding pump (such as pressing type quantitative gear pump) liquor charging and extremely adds Pressing mold 32, on the casting position on the endless metal support body 33 ad infinitum moving, from pressurization die head 32 curtain coating rubber cement.To plus Pressing mold 32 can adjust the shape of slit of the nozzle segment of die head, thus easily making in uniform film thickness aspect preferably.Compression molding 32 There are clothes hanger die head or t die head etc. it is preferably to use.In order to improve film speed, can arrange in metal support 33 2 with Upper pressurization die head 32, overlapping layer is made in the segmentation of rubber cement amount.

Metal support 33 is made up of the stainless steel band being set up using 2 rollers 34, roller 34.As metal support 33, Preferred pair surface carries out the metal support of minute surface polish, in addition to above-mentioned stainless steel band, it is possible to use with foundry goods to table Face has carried out metal roller etc. obtained from plating polish.

The width of curtain coating (casting) can be set to the scope of 1～4m, the preferably scope of 1.5～3m, further preferred 2～ The scope of 2.8m.Curtain coating operation in metal support 33 surface temperature be set as -50 DEG C～solvent boiling and bubble-tight Temperature, further preferably -30～0 DEG C of scope.The high metal support of temperature can accelerate the rate of drying of wet film, therefore excellent Choosing, but when temperature is too high, wet film bubbles sometimes, or flatness deterioration.Support temperature as preferred, suitable at 0～100 DEG C Work as determination, further preferred 5～30 DEG C of scope.Or, it is wet film gelation to be made by cooling and is more containing residual Peeling off from supporter in the state of staying solvent is also method for optimizing.

The method controlling the temperature of metal support 33 is not particularly limited: blows the method for warm braw or cold wind or makes temperature The method of the backside contact of water and metal support 33.Using the method for warm water, effectively carry out the transmission of heat, therefore, until The temperature of metal support 33 becomes constant time short preferred.Using in the case of warm braw it is considered to the evaporation of solvent is hidden The temperature of thermally-induced wet film reduces, and sometimes using the warm braw more than boiling point of solvent, and makes under the purpose preventing from bubbling With the temperature wind higher than target temperature.Particularly preferably from being cast to the change temperature of supporter and the temperature of dry wind between stripping Degree, is dried effectively.

(3) solvent evaporization process

In this operation, the casting films (wet film) that the rubber cement passing through curtain coating in metal support 33 is formed carry out adding Heat, makes solvent evaporate.In order that solvent evaporation has: the side dried from the surface (with metal support 33 opposite side) of wet film Method, the method conducted heat using liquid from the back side (face with wet film opposition side) of metal support 33, using radiant heat from Positive and negative method conducted heat etc., but the drying efficiency of rear surface liquid heat-transferring method is good, preferably.Additionally, it is preferred that being applied in combination The method of these methods.The wet film in metal support 33 after preferred pair curtain coating props up under 40～100 DEG C of atmosphere, in metal It is dried on support body 33.In order to maintain under 40～100 DEG C of atmosphere, to above wet film, preferably blow the warm braw of this temperature, or Heated using methods such as infrared ray.

From the viewpoint of face quality, poisture-penetrability, fissility, preferably within 30～120 seconds, this wet film is propped up from metal Peel off on support body 33.

(4) stripping process

In this operation, using stripper roll 35, to the wet film after the evaporation of solvent in metal support 33 in specified stripping Off normal to put and peeled off.Hereinafter, the wet film after peeling off is set to wet film 36.Wet film 36 delivers to subsequent processing.

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

It should be noted that for the residual solvent amount in the wet film in the metal support 33 peeling off the moment, preferably According to the power of drying condition, and the length of metal support 33 etc., peeled off in the scope of 50～120 mass %.Residual In the case of staying quantity of solvent more moment to be peeled off, when wet film is excessively soft, damages flatness during stripping, easily produce stripping The adhesion (gauffer) causing from tension force or vertical stripe, therefore, determine residual when peeling off according to the balance of economic pace and quality Quantity of solvent.It should be noted that the residual solvent amount following formula of wet film defines.

Residual solvent amount (quality the %)={ (matter after the heat treated of quality-wet film before the heat treated of wet film Amount)/(quality after the heat treated of wet film) } × 100

Here, the heat treated measuring during residual solvent amount represents the heat treated carrying out at 115 DEG C 1 hour.

Stripping tension force when peeling off wet film metal support 33 is usually in the range of 196～245n/m, but in stripping From when easily gauffer occurs in the case of, preferably peeled off with the tension force of below 190n/m.

In the present embodiment, preferably the temperature on position of peeling off in metal support 33 is set to -50～40 DEG C In the range of, in the range of more preferably 10～40 DEG C, most preferably it is set in the range of 15～30 DEG C.

(5) stretching, drying process

In this operation, carry out predry drying process, stretching process, actual drying operation successively.Predrying enter as needed Row.

＜ predry drying process ＞

Wet film 36 obtained from stripping from metal support 33 is made to be dried.For the drying of wet film 36, can will be wet Film 36 while by the multiple rollers conveying configuring up and down, is dried it is also possible to as stenter drying machine, while with pressing from both sides The both ends conveying of the fixing wet film 36 of tool, is dried.

So that the method that wet film 36 is dried is not particularly limited, typically can pass through hot blast, infrared ray, heating roller, microwave etc. And carry out, in terms of easy degree, carry out preferably by hot blast.

For the baking temperature in the drying process of wet film 36, preferably below -5 DEG C of the glass transition temperature of film, It is effective for carrying out more than 10 minutes 60 minutes heat treatment below for more than 100 DEG C.Baking temperature is preferably 100～200 DEG C In the range of, in the range of more preferably 110～160 DEG C.

＜ stretching process ＞

In this operation, with respect to carrying out peeling off in metal support 33, carried out pre-dried wet film as needed 36, along the md direction (machine direction) as length direction (curtain coating direction, conveying direction) and/or as width The td direction (transverse direction) in direction is stretched.Now, preferably at least utilize stenter stretching device 37 Stretched along td direction.

Stretching in stretching process can be set to be stretched uniaxially or biaxially.In biaxial stretch-formed, including along a side To being stretched, make the tension recovery of other direction and the mode shunk.

The phase retardation film of present embodiment preferably along md direction and/or td direction, preferably along td direction, (tg+15)～ DEG C (tg+50) temperature range is stretched, and makes the thickness after stretching become desired scope.It should be noted that tg is The glass transition temperature (DEG C) of film.When said temperature scope is stretched, the adjustment easily being postponed, furthermore it is possible to Reduce tensile stress, therefore, mist degree step-down.In addition, can obtain suppressing the generation of fracture, flatness, film colored by themselves excellent Polaroid phase retardation film.Draft temperature is preferably (tg+20)～(tg+40) DEG C of scope.

It should be noted that glass transition temperature tg said here is to be measured using commercially available Differential Scanning Calorimetry Device, with programming rate, 20 DEG C/min are measured, and the intermediate point glass transition temperature obtained according to jis k7121 (1987) Degree (tmg).The assay method of the glass transition temperature tg of specific phase retardation film according to jis k7121 (1987), using essence The differential scanning calorimeter dsc220 that work Co., Ltd. manufactures is measured.

Wet film 36 is preferably at least stretched more than 1.1 times along td direction by the phase retardation film of present embodiment.The scope of stretching It is preferably 1.1～1.5 times with respect to former width, more preferably 1.05～1.3 times.If in above range, then in film point The movement of son is big, not only can get desired length of delay, and can be by the change in size Behavior- Based control of film in desired scope Interior.

And, after masking, when residual solvent amount is more than 40 mass %, preferably along md direction, this film is stretched, When residual solvent amount is less than 40 mass %, preferably stretched along td direction.

In order to be stretched in md direction, preferably peeled off with peeling off more than tension force 130n/m, particularly preferably 150～ 170n/m.Because the wet film after peeling off is high residue solvent state, therefore, by maintaining the tension force same with peeling off tension force, can To carry out the stretching along md direction.It is dried with wet film, residual solvent amount reduces, the extensibility along md direction reduces.

It should be noted that the stretching ratio in md direction can be by the rotary speed with supporter and stenter running speed Calculate.

In order to be stretched along td direction, for example have the full operation of drying shown in Japanese Unexamined Patent Application 62-46625 publication or The width two ends of wet film are kept width in width fixture or pin by the operation of a part, while making it be dried Method (is referred to as tentering mode), wherein, it is preferred to use the tentering mode using fixture and the pin tentering mode using pin.

The phase retardation film of present embodiment necessarily has delay by stretching, but delay ro and the prolonging of thickness direction in the face in Each value of rth can use automatic birefringence meter axo scan (axo scan mueller matrix late Polarimeter:axometrics company manufactures), in the environment of 23 DEG C, 55%rh, carry out three-dimensional under the wavelength of 590nm Detecting refractive index, is calculated by refractive index nx, ny obtaining, nz.

For the phase retardation film of present embodiment, in the case of possessing in va type liquid crystal indicator, can from improving From the viewpoint of property, the delay ro in direction and the thickness being defined with following formula (ii) in the face that preferably defined with following formula (i) The delay rth in direction is in following scope.Phase retardation film passes through at least to adjust stretching ratio along td direction, and is drawn Stretch, can be adjusted to postponing ro, rth in above range.

30nm ＜ ro ＜ 70nm

100nm ＜ 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 the refractive index on the maximum direction x of direction refractive index in the face of film.Ny table Show the refractive index on the direction direction y vertical with described direction x in the face of film.Nz represents the refraction on the thickness direction z of film Rate.D represents the thickness (nm) of film.]

＜ actual drying operation ＞

Wet film 36 after stretching is delivered to drying device 38 as film f, therefore, with above-mentioned predrying same method It is dried.It should be noted that the drying condition in actual drying operation can be different from predry drying process.Actual drying work In sequence, it is made to be difficult aqueous thus suppressing the aqueous dimensional variations causing and postponing what rth changed from the space reduced film f Viewpoint is set out, and preferably after the stretch, is dried, more more than 115 DEG C under less than 160 DEG C of baking temperature (heat treatment temperature) Preferably it is dried under less than 150 DEG C of baking temperature more than 120 DEG C.In addition, preferably more than 5 minutes drying time, more It is preferably more than 10 points below 20 minutes.

＜ annular knurl processes ＞

After the end of above-mentioned actual drying, before the winding of film f, setting cutter cut away the end of film f, obtain good Volume appearance, therefore preferably.Further preferably implement annular knurl processing at the horizontal both ends of film.

Annular knurl (jog) can be formed through the dandy roll of heating by pushing.Dandy roll is formed tiny recessed Convex, formed concavo-convex on film by pushing, the height of end can be made to increase.The height of the annular knurl at horizontal both ends of film f Degree is preferably 4～20 μm, and width is preferably 5～20mm.

(6) rolling step

This operation becomes below 2 mass % for residual solvent amount, then, the operation of wound film f in coiler device 39.Logical Cross and residual solvent amount is set to below 0.4 mass %, the good film of dimensional stability can be obtained.

The method for winding of film f adopt commonly used method, have determine calibrated wrench method, determine tensammetry, gradual change tensammetry, Constant program tension control method of internal stress etc., these methods are used separately.

[physical property of phase retardation film]

(mist degree)

The phase retardation film of present embodiment is preferably mist degree and is less than 1%, again more preferably less than 0.5%.By mist degree is set Be have the advantages that less than 1% the transparency of film raise further, as optical applications film be easier use.

(equilibrium moisture content)

For the phase retardation film of present embodiment, 25 DEG C, the equilibrium moisture content in relative humidity 60% be preferably 4% with Under, more preferably less than 3%.By equilibrium moisture content is set to less than 4%, the easily change of reply humidity, optical characteristics or chi Very little be less susceptible to change, preferably.

(film length and width degree, thickness)

The phase retardation film of present embodiment is preferably banding, specifically, preferably 100～10000m about length, It is wound into web-like.In addition, the width of the phase retardation film of present embodiment be preferably more than 1m, more preferably 1.4m with On, particularly preferably 1.4～4m.

From the viewpoint of the slimming of display device and productivity, the thickness of phase retardation film is preferably 10～100 μm In the range of.If thickness is more than 10 μm, necessarily above film-strength or phase contrast can be manifested.If thickness is 100 μm Hereinafter, then the variation of the phase contrast that heat or humidity lead to can be suppressed.The scope of preferably thickness is 20～80 μm, enters One step is preferably 20～40 μm.

For the thickness inequality of phase retardation film, preferred thickness direction or width be in the range of 0～5 μm, In the range of more preferably 0～3 μm, in the range of more preferably 0～2 μm.

[embodiment]

Hereinafter, enumerate embodiment, specifically describe the present invention, but the present invention is not limited to these embodiments.Need Bright, in embodiment, use the expression of " part " or " % ", as long as no specified otherwise then it represents that " mass parts " or " matter Amount % ".

The preparation ＞ of ＜ phase retardation film 1

＜ particle dispersion liquid 1 ＞

Microgranule (aerosil Co., Ltd. of aerosil r812 Japan manufactures) 11 mass parts

Ethanol 89 mass parts

By above material with, after dissolving rod stirring mixing 50 minutes, being disperseed with manton-gaulin, preparing microgranule and divide Dispersion liquid 1.

＜ particulate annex solution 1 ＞

While being sufficiently stirred in the dissolving tank be placed with dichloromethane, lentamente add particle dispersion liquid 1.Enter one Step is disperseed with attritor, makes the particle diameter of offspring become specified size.It is manufactured with Japan Jingxian Co., Ltd Fine met nf filtered, prepare particulate annex solution 1.

Dichloromethane 99 mass parts

Particle dispersion liquid 15 mass parts

The preparation ＞ of ＜ rubber cement

Then, dissolved under pressure tank adds dichloromethane and ethanol.And, in the dissolved under pressure tank being placed with solvent Add the cellulose ethanoate that total acyl substitution is 2.56 while being stirred.It is heated, stirring, one While being completely dissolved, amassing filter paper no.244 using the peace that An Ji filter paper Co., Ltd. manufactures and it is filtered, preparing main rubber cement.And And, it is added to the dissolution kettle being closed with following material, stirring, while dissolving, prepare rubber cement.

" composition of rubber cement "

Masking ＞ of ＜ film

Then, stainless steel band supporter make solvent evaporate, in the wet film that the rubber cement by curtain coating (casting) is formed Residual solvent amount become 75 mass %, then, to peel off tension force 130n/m, wet film is peeled off from stainless steel band supporter.Its Afterwards, the wet film of stripping is carried out 30% stretching using stenter in width.Residual solvent amount when stretching starts is 15 matter Amount %.It should be noted that being 160 DEG C with the draft temperature of stenter.

Then, convey arid region with multiple rollers, while making drying terminate.Baking temperature after stretching is 125 DEG C, Drying time is 5 minutes.Operate as described above, obtain the phase retardation film 1 of 37 μm of dry film thickness.

The preparation ＞ of ＜ phase retardation film 2

In rubber cement used in the preparation of phase retardation film 1, as postponing dose, add 2 mass parts nitrogen-containing hetero cyclisation Compound r1 (exemplary compounds 1, pyrazole compound) and prepare rubber cement, using preparation rubber cement, with the preparation with phase retardation film 1 Same method prepares phase retardation film 2.

The preparation ＞ of ＜ phase retardation film 3

In rubber cement used in the preparation of phase retardation film 2, as additive s1, add 10 mass parts sugar esters and prepare glue Slurry, using the rubber cement of preparation, prepares phase retardation film 3 with the same method of preparing with phase retardation film 2.

It should be noted that as additive s1 (sugar ester), using bzsc (benzoyl sucrose: saccharide residue is b-2, takes The mixture of the a1～a4 described in Dai Jiwei chemical formula 13, average ester substitution value=5.5).

The preparation ＞ of ＜ phase retardation film 4～21

Composition as described in table 1 select cellulose esters resinoid (cellulose acylate), postpone dose, additive and Prepare rubber cement.And, using the rubber cement of preparation, carried out to stretching with the same method of preparing with phase retardation film 1, after stretching, So that film is dried under the baking temperature (heat treatment temperature) recorded in Table 1, prepare phase retardation film 4～21.

Here, as cellulose acylate c2～c4, using following cellulose acylate.

Cellulose acylate c2: cellulose ethanoate, degree of substitution with acetyl group 2.41, number-average molecular weight (mn) 5.6 ten thousand.

Cellulose acylate c3: cellulose acetate butyrate, degree of substitution with acetyl group 2.6, bytyry substitution value 0.28, total acyl Base substitution value 2.88, number-average molecular weight (mn) 6.6 ten thousand.

Cellulose acylate c4: cellulose ethanoate, degree of substitution with acetyl group 2.7, number-average molecular weight (mn) 6.5 ten thousand.

In addition, as nitrogen-containing heterocycle compound r2 and r3 postponing dose, using following compound.

Nitrogen-containing heterocycle compound r2: exemplary compounds 2 (azoles).

Nitrogen-containing heterocycle compound r3: there is exemplary compounds 3 (the Japanese Unexamined Patent Publication 2012-82235 publication of following structural formula Compound e-104 (pyrimidines)).

[chemical formula 25]

Exemplary compounds 3 (pyrimidines)

And, as additive s2, using above-mentioned polycondensation ester p5.

Mensure ＞ of ＜ ro and rth

Using automatic birefringence meter axo scan (axo scan mueller matrix polarimeter: Axometrics company manufactures) measure the delay ro in direction and thickness direction in the face of phase retardation film 1～21 of above-mentioned preparation Postpone rth.In the environment of 23 DEG C of temperature, relative humidity 55%rh, under mensure wavelength 590nm, carry out three-dimensional refractive index mensure, By refractive index n obtaining_x、n_y、n_z, ro and rth is 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 the refractive index on the maximum direction x of direction refractive index in the face of film.n_yRepresent in the face of film Refractive index on the direction y vertical with described direction x of direction.n_zRepresent the refractive index on the thickness direction z of film.D represents film Thickness (nm).)

Mensure (condition 1) ＞ of ＜ size changing rate

Phase retardation film 1～21 to above-mentioned preparation, operates as described below, measures size changing rate s (%).

By the phase retardation film of preparation in 23 DEG C of 55%rh relative humidities 24 hours, measure the long side of phase retardation film now respectively Length am (mm) in direction (md direction) and size at (mm) of width (td direction).

Then, by identical phase retardation film in 23 DEG C of 20%rh relative humidities 24 hours, measure phase retardation film now respectively Size bm (mm) of long side direction and width size bt (mm).

And, by identical phase retardation film in 23 DEG C of 80%rh relative humidities 24 hours, measure phase retardation film now respectively Size cm (mm) of long side direction and width size ct (mm).

By each value of am, bm, cm, at, bt, the ct obtaining, obtain the length side of phase retardation film using following calculating formula To size changing rate smd and width size changing rate std.

Smd (%)=(| bm-cm |/am) × 100

Std (%)=(| bt-ct |/at) × 100

And, smd and std sum is set to size changing rate s.That is, it is

S (%)=smd+std.

It should be noted that the mensure of each value of above-mentioned am, bm, cm, at, bt, ct is carried out using microscope.More For body, each sample (phase retardation film) is cut into 120mm × 120mm size, on this film surface along film length direction with about The sharp keen sharp weapon such as 100mm interval razor apply the symbol of ten character types.And, by this film as described above in specified temperature Damping 24 hours in the environment of degree and humidity, with the intersymbol distance of measurement microscope length direction and width.

Mensure (condition 2) ＞ of ＜ rth amount of change

Phase retardation film 1～21 to above-mentioned preparation, obtain as described below with respect to during film on-fixed, fixing when thickness The amount of change of the delay rth in degree direction.

Do not use binding agent with the phase retardation film of two glass sheets clamping preparations, relative humidity is at 23 DEG C of temperature The delay rth1 (nm) of thickness direction in the environment of 55%, is measured using above-mentioned automatic birefringence meter axo scan.

Then, with the phase retardation film of two glass sheets clamping preparations, and make binding agent between described phase retardation film and one Between glass plate, at 23 DEG C of temperature in the environment of relative humidity 55%, surveyed using above-mentioned automatic birefringence meter axoscan Determine the delay rth2 (nm) of thickness direction.

And, the difference of rth2 and rth1 is set to the amount of change δ r of rth.That is, it is

δ r (nm)=rth2-rth1.

Mensure (condition 3) ＞ of ＜ moisture content amount of change

Phase retardation film 1～21 to above-mentioned preparation, measures amount of change w (%) of equilibrium moisture content as described below.

By the phase retardation film of preparation in 23 DEG C of 20%rh relative humidities 24 hours, measure quality wa (g) now.Then, will Identical phase retardation film is set to the state of parching, and measures quality wb (g) now.

Then, by the phase retardation film of preparation in 23 DEG C of 80%rh relative humidities 24 hours, measure quality wc (g) now.Connect , identical phase retardation film is set to the state of parching, measure quality wd (g) now.

Then, equilibrium moisture content w1 under 23 DEG C of 20%rh of phase retardation film and 23 DEG C are obtained using following calculating formula Equilibrium moisture content w2 under 80%rh.

W1 (%)={ (wa-wb)/wb } × 100

W2 (%)={ (wc-wd)/wd } × 100

And, the difference of w2 and w1 is set to amount of change w of equilibrium moisture content.That is, it is

W (%)=w2-w1.

＜ evaluates ＞

(1. tone variations during high humidity)

Then, prepare polaroid using the phase retardation film of preparation as described above, this polaroid is equipped on liquid crystal display Device, the tone variations of display image during research high humidity.More specifically, as described below.

" preparation of polaroid "

Make the polyvinyl alcohol film of 70 μm of thickness swelling in 35 DEG C of water.By the film immersion obtaining in by iodine 0.075g, iodine Change 60 seconds in the aqueous solution that potassium 5g and water 100g is constituted, impregnated in further and be made up of potassium iodide 3g, boric acid 7.5g and water 100g 45 DEG C of aqueous solution.The film obtaining is carried out uniaxial tension under conditions of 55 DEG C of draft temperature, 5 times of stretching ratio.To this After monadic stretching membrane washing, it is dried, obtains the polarizer of 15 μm of thickness.

Then, as the cellulose acylate film on a surface fitting in polarizer, prepare as commercially available polaroid The kc6ua that Konica Minolta Opto Inc. of 60 μm of the thickness of protecting film manufactures, through the preparation of following operation 1～5 partially Shake piece.

Operation 1: the phase retardation film of preparation and kc6ua be impregnated in respectively the sodium hydroxide solution 90 of 60 DEG C of 2 moles/l Second, then washed and be dried, saponification process is implemented to the side fitted with polarizer.

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

Operation 3: dab off the bonding agent of the excess being attached to polarizer in operation 2, and be carried out as follows configuration: On said one surface, load the phase retardation film being processed in operation 1, kc6ua is loaded on the surface of opposite side.

Operation 4: be adjusted to pressure 20～30n/cm², transporting velocity be set to about 2m/ minute, in operation 3 stacking phase place Difference film, polarizer and kc6ua are fitted.

Operation 5: in 80 DEG C of drying machine, the laminated body of laminating in operation 4 is dried 2 minutes, prepares polaroid.

Respectively above operation is carried out to the phase retardation film 1～21 of preparation, prepare polaroid.

" panel evaluation "

Fitted in the liquid crystal cells of the liquid crystal indicator (model: un55hu-8500) of samsung company manufacture in advance Two sides polaroid peel off, using acrylic adhesives, the polaroid of above-mentioned preparation is fitted in respectively the glass of liquid crystal cells On the two sides in glass face, phase retardation film is made to become liquid crystal cell side.And, the liquid crystal indicator being prepared is pasted on its surface The cloth of attached moistening is placed 3 days.Thereafter, peel above-mentioned cloth, placing in the environment of 23 DEG C of 55%rh makes it be dried in 24 hours.So Afterwards, the backlight continuous illumination 1 hour of liquid crystal indicator, after making hot and humid environment using the heat of backlight, base are made In following metewand visual valuation: make picture be black to display whether to observe uneven (tone variations).And, to pasting respectively Liquid crystal indicator with the polaroid with phase retardation film 1～21 each carries out this evaluation.

＜ metewand ＞

◎: inequality is not observed completely.

Zero: inequality is almost not observed.

△: angle by visual observation observes faint inequality, but the level for having no problem.

×: strong inequality is clearly observed on picture, for becoming the level of problem.

(2. wet heat durability)

Then, the wet heat durability to phase retardation film (dimensional variations under hot and humid environment and rth change), as follows Studied.

" dimensional variations "

Each sample (phase retardation film) is cut into 120mm × 120mm size, on this film surface along curtain coating direction, with about The sharp keen sharp weapon such as 100mm interval razor apply the symbol of ten character types.And, by this film in the environment of 23 DEG C of 55%rh Damping more than 24 hours, is measured apart from l1 (mm) between the symbol in the curtain coating direction of before processing with microscope.

Then, using electric constant-temp groove, this sample is placed 120 hours in the environment of 60 DEG C of 90%rh, carry out hot and humid Process.Thereafter, by the hot and humid sample having processed damping 24 hours in the environment of 23 DEG C of 55%rh again, with microscope to place Curtain coating the intersymbol of direction after reason is measured apart from l2 (mm).And, obtained before hot and humid process using following formula The size changing rate t in curtain coating direction afterwards.

Size changing rate t (60 DEG C of 90%rh120h)={ (l2-l1)/l1 } × 100 (%)

Finally, based on following metewand, from the viewpoint of dimensional variations, evaluate wet heat durability.

" metewand "

◎: | t | for 0% less than 0.5%.

Zero: | t | for 0.5% less than 0.9%.

δ: | t | for 0.9% less than 1.3%.

×: | t | is more than 1.3%, for becoming the level of problem.

" rth variation "

Damping more than 24 hours, the delay of mensure thickness direction in the environment of 23 DEG C of 55%rh by sample (phase retardation film) r1(nm).Then, using electric constant-temp groove, this sample is placed 120 hours in the environment of 60 DEG C of 90%rh, carry out hot and humid Process.Thereafter, by the hot and humid sample having processed damping 24 hours in the environment of 23 DEG C of 55%rh again, measure thickness direction Delay r2 (nm).And, rate of change δ of the delay of the thickness direction after hot and humid before processing is obtained using following formula rth.

Rate of change δ rth (60 DEG C of 90%rh120h)={ (r2-r1)/r1 } × 100 (%)

Finally, based on following metewand, from the viewpoint of δ rth, evaluate wet heat durability.

" metewand "

◎: | δ rth | for 0% less than 5%.

Zero: | δ rth | for 5% less than 11%.

△: | δ rth | for 11% less than 19%.

×: | δ rth | is more than 19%, for becoming the level of problem.

(3. adhesion)

The phase retardation film of winding preparation, places 3 months at room temperature afterwards, takes out film, visually observe the film overlapping each other Adhesion (attaching) state each other, carries out the evaluation of adhesion based on following benchmark.

" metewand "

◎: do not have adhesion.

Zero: almost there is no adhesion.

△: somewhat there is adhesion, but the level for having no problem.

×: significantly there is adhesion, for becoming the level of problem.

The result of characteristic, composition and evaluation to each phase retardation film 1～21 for the table 1 is concluded and is represented.It should be noted that closing In the evaluation of wet heat durability, in order that two sides that the dimensional variations of each phase retardation film and rth change are commenting of same levels Valency, they is concluded and is represented with 1 evaluation.

According to the result of table 1, the color change in having the liquid crystal indicator of phase retardation film of embodiment, during high humidity Be evaluated as more than △ (◎, zero, △ any one), can get good result.It is considered because of the phase contrast of embodiment Film meets condition 1 and 2 simultaneously, and the variation of delay rth when the aqueous dimensional variations causing and film are fixing is all inhibited, its knot Really, in the occupation mode of the reality of the liquid crystal indicator that film is fixed, the change of the aqueous delay rth leading to of film during high humidity Move and be inhibited.

In addition, the phase retardation film of embodiment can get the good result of more than △ in wet heat durability.It is considered Because by meeting condition (1) and (2), suppressing the dimensional variations of film or the change postponing rth in the environment of 23 DEG C of 55%rh Dynamic, play its effect under the hot and humid environment of 60 DEG C of 90%rh to a certain extent.

In addition, as shown in Table 1: the heat treatment temperature after stretching is less than more than 115 DEG C 160 DEG C, can be met Condition (1) at least in condition (1)～(3) and the film of (2).It can thus be stated that by under the heat treatment temperature of above range Film is filmed, delay when reliably can simultaneously realize fixing to the aqueous dimensional variations causing during high humidity and film The phase retardation film that rth variation is suppressed.

In addition, as shown in Table 1: in addition to condition (1) and (2), when meeting condition (3) further, the effect of suppression adhesion Raise.It is considered due to following the reasons why.By meeting condition (3), can get humidity and change the moisture content variation causing relatively It is difficult aqueous film less.Being difficult can at the higher temperature of aqueous film heat treatment temperature after the stretch (such as 125 DEG C) Obtain.When heat treatment temperature is high, be chapped from the cold in film surface, therefore, is not likely to produce adhesion.

Even if in addition, by the evaluation result of phase retardation film 1 it can be said that being unsatisfactory for condition 3, as long as meeting condition 1 and condition 2 I.e. moisture content amount of change is big, even if being easily aqueous film according to humidity change, as long as the size producing with humidity change Change and rth change few film, can be inhibited high humidity when tone variations, thus improving the effect of wet heat durability Really.

In addition, by the evaluation result of phase retardation film 1～3 it can be said that in order to suppress tone variations during high humidity further, excellent It is selected in add in film and postpones dose, in order to improve wet heat durability further, add additive preferably in film.

The va phase retardation film of present embodiment described above, the manufacture method of va phase retardation film, polaroid and hang down Straight aligned liquid crystal display can show as follows.

1. a kind of va phase retardation film, it contains cellulose esters resinoid, and described va phase retardation film meets following simultaneously Condition (1) and (2):

Condition (1)

Smd+std≤0.65%

Smd=(| bm-cm |/am) × 100

Std=(| bt-ct |/at) × 100.

In above formula,

Am, bm and cm refer respectively in same film, at 23 DEG C of temperature, when relative humidity is 55%, 20% and 80%, The size (mm) of the length direction of described film.

rth2-rth1≤9nm

Wherein,

2. the va phase retardation film described in above-mentioned 1, it meets following condition (3) further:

Condition (3)

W2-w1≤2.4%

Wherein,

W1={ (wa-wb)/wb } × 100

W2={ (wc-wd)/wd } × 100,

In above formula,

Wa refers to, in 23 DEG C of temperature and under relative humidity 20%, carry out the quality (g) of film during damping in 24 hours, wb refers to Identical film is adjusted to the quality (g) when parching state,

Wc refers under 23 DEG C of temperature, relative humidity 80%, the quality (g) of the film after damping 24 hours, and wd refers to phase Same film is adjusted to the quality (g) when parching state.

3. the va phase retardation film as described in above-mentioned 1 or 2, it contains nitrogen-containing heterocycle compound as delay dose,

Described nitrogen-containing heterocycle compound is following compound with structure shown in formula (1),

[chemical formula 1]

Formula (1)

(in formula, a₁、a₂And b represents alkyl, cycloalkyl, aromatic series hydrocarbon ring or heteroaromatic, in described heteroaromatic, Remove pyrimidine ring and pyridine ring, t₁And t₂Represent the link group shown in following arbitrary structures formulas, l₁～l₄Respectively represent singly-bound or The link group of divalent, n represents 0～5 integer.)

[chemical formula 2]

(in formula, ※ represents the l in formula (1)₁、l₂、l₃Or l₄Bonding position, r⁵Represent that hydrogen atom or non-aromatic take Dai Ji.)

4. the va phase retardation film as described in above-mentioned 3, wherein, described nitrogen-containing heterocycle compound be selected from have pyrazole ring, At least any of in triazole ring, the compound of imidazole ring.

5. the va phase retardation film as described in above-mentioned 3 or 4, wherein, described nitrogen-containing heterocycle compound is that have following formulas The compound of shown structure,

[chemical formula 3]

Formula (3)

(in formula, a represents pyrazole ring, ar₁And ar₂Represent aromatic series hydrocarbon ring or heteroaromatic respectively, and optionally have and take Dai Ji；r₁Represent hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl, q represents 1～2 integer, n And m represents 1～3 integer.)

6. the va phase retardation film as any one of above-mentioned 1～5, wherein, total acyl of described cellulose esters resinoid Base substitution value is 2.2～2.9.

7. the va phase retardation film as any one of above-mentioned 1～6, wherein, described cellulose esters resinoid is fiber Plain acetate propionate.

8. the va phase retardation film as any one of above-mentioned 1～7, it contains at least in sugar ester and polycondensation ester Kind.

9. a kind of manufacture method of va phase retardation film, it utilizes solution curtain coating masking method to manufacture any one of described 1～8 Described va phase retardation film, the manufacture method of described va phase retardation film includes:

Rubber cement containing described cellulose esters resinoid is cast on supporter and is dried, from described supporter Peel off the operation of casting films；

The operation that described casting films after peeling off are stretched；

Make the operation being dried at a temperature of less than 160 DEG C more than 115 DEG C of stretched described casting films.

10. a kind of polaroid is it is characterised in that have: the va any one of described 1～8 phase retardation film and patch Close the polarizer of described va phase retardation film.

A kind of 11. vertical orientating type liquid crystal display devices, it has: polaroid described in described 10 and

Fit the liquid crystal cells of described polaroid.

12. vertical orientating type liquid crystal display devices as described in above-mentioned 11, wherein,

Described polaroid is to fit positioned at viewing side and with described liquid crystal cells with respect to described liquid crystal cells, and makes institute State va phase retardation film and be located at described liquid crystal cell side with respect to described polarizer.

[industrial applicibility]

The va phase retardation film of the present invention can be used in polaroid and the liquid crystal indicator of va type.

Claims

1. a kind of va phase retardation film, it contains cellulose esters resinoid,

Described va phase retardation film meets following condition (1) and (2) simultaneously:

Condition (1)

Smd+std≤0.65%

Smd=(| bm-cm |/am) × 100

Std=(| bt-ct |/at) × 100,

In above formula,

Am, bm and cm refer respectively in same film, at 23 DEG C of temperature, when relative humidity is 55%, 20% and 80%, described The size (mm) of the length direction of film,

At, bt and ct refer respectively in same film, at 23 DEG C of temperature, when relative humidity is 55%, 20% and 80%, described The size (mm) of the width of film,

Condition (2)

rth2-rth1≤9nm

Wherein,

Rth1 refers to clamp this film with two panels transparency carrier and does not use binding agent, is 55% in 23 DEG C of temperature, relative humidity The delay (nm) of the thickness direction obtaining is measured under environment,

Rth2 refers to clamp this film with two panels transparency carrier, and so that binding agent is present between this film and a piece of transparency carrier, 23 DEG C of temperature, relative humidity are the delay (nm) measuring the thickness direction obtaining in the environment of 55%.

2. va phase retardation film as claimed in claim 1, it meets following condition (3) further:

Condition (3)

W2-w1≤2.4%

Wherein,

W1={ (wa-wb)/wb } × 100

W2={ (wc-wd)/wd } × 100,

In above formula,

The quality (g) of film when wa refers to carry out damping in 24 hours under 23 DEG C of temperature, relative humidity 20%, wb refers to will be identical Film be adjusted to quality (g) when parching state,

Wc refers to, under 23 DEG C of temperature, relative humidity 80%, carry out the quality (g) of film during damping in 24 hours, wd refers to phase Same film is adjusted to the quality (g) when parching state.

3. va phase retardation film as claimed in claim 1 or 2, it contains nitrogen-containing heterocycle compound as delay dose,

Described nitrogen-containing heterocycle compound is the compound with structure shown in following formulas (1),

[chemical formula 1]

Formula (1)

a₁-l₁-t₁-l₂-b-(l₃-t₂-l₄-a₂)_n

In formula, a₁、a₂And b represents alkyl, cycloalkyl, aromatic series hydrocarbon ring or heteroaromatic (but except pyrimidine ring and pyridine ring), t₁And t₂Represent the link group shown in following arbitrary structures formulas, l₁～l₄Represent the link group of singly-bound or divalent respectively, n represents 0～5 integer,

[chemical formula 2]

In formula, ※ represents and the l in formula (1)₁、l₂、l₃Or l₄Bonding position, r⁵Represent that hydrogen atom or non-aromatic replace Base.

4. va phase retardation film as claimed in claim 3, wherein, described nitrogen-containing heterocycle compound be selected from have pyrazole ring, At least any of in triazole ring, the compound of imidazole ring.

5. the va phase retardation film as described in claim 3 or 4, wherein, described nitrogen-containing heterocycle compound is that have following formulas The compound of shown structure,

[chemical formula 3]

Formula (3)

In formula, a represents pyrazole ring, ar₁And ar₂Represent aromatic series hydrocarbon ring or heteroaromatic respectively, and optionally there is substituent group； r₁Represent hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl, q represents 1～2 integer, n and m table Show 1～3 integer.

6. the va phase retardation film as any one of Claims 1 to 5, wherein, total acyl of described cellulose esters resinoid Base substitution value is 2.2～2.9.

7. the va phase retardation film as any one of claim 1～6, wherein, described cellulose esters resinoid is fiber Plain acetate propionate.

8. the va phase retardation film as any one of claim 1～7, it contains at least in sugar ester and polycondensation ester Kind.

9. a kind of manufacture method of va phase retardation film, it utilizes any one of solution curtain coating masking method manufacturing claims 1～8 Described va phase retardation film,

The manufacture method of described va phase retardation film includes:

Rubber cement containing described cellulose esters resinoid is cast on supporter and is dried, and shells from described supporter Operation from casting films；

The operation that described casting films after peeling off are stretched；

10. a kind of polaroid, it has:

Va any one of claim 1～8 with phase retardation film and

The polarizer fitted with described va phase retardation film.

A kind of 11. vertical orientating type liquid crystal display devices, it has:

Polaroid described in claim 10 and

The liquid crystal cells fitted with described polaroid.

12. vertical orientating type liquid crystal display devices as claimed in claim 11, wherein,

Described polaroid is located at viewing side with respect to described liquid crystal cells, and fits with described liquid crystal cells, and so that described va is used Phase retardation film is located at described liquid crystal cell side with respect to described polarizer.