CN106104333B

CN106104333B - Retardation film, and polarizing plate and display device using same

Info

Publication number: CN106104333B
Application number: CN201580015601.2A
Authority: CN
Inventors: 森井里志; 世良贵史; 高木隆裕
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 2014-03-25
Filing date: 2015-03-12
Publication date: 2018-11-13
Anticipated expiration: 2035-03-12
Also published as: KR20160124867A; WO2015146599A1; JPWO2015146599A1; JP6627748B2; CN106104333A

Abstract

The invention provides a phase difference film capable of maintaining high phase difference display performance and inhibiting phase difference variation under a humid heat environment, and a polaroid and a display device using the same. A retardation film comprising a retardation enhancer comprising a nitrogen-containing compound (A) represented by the following general formula (1) and a nitrogen-containing compound (B) represented by the following general formula (2), Ar-X₂‑Ar‑Y₂-Ar … … Nitrogen-containing Compound (A) (in the general formula (1), Ar is independently a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted nitrogen-containing aromatic heterocycle, X₂And Y₂Each independently represents a substituted or unsubstituted nitrogen-containing aromatic heterocycle) Ar-X₃‑Ar‑Y₃‑Ar‑Z₃-Ar … … Nitrogen-containing Compound (B) (in the general formula (2), Ar is independently a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted nitrogen-containing aromatic heterocycle, X₃、Y₃And Z₃Each independently represents a substituted or unsubstituted nitrogen-containing aromatic heterocycle).

Description

Phase difference film and the polarizing film using the phase difference film, display device

Technical field

The present invention relates to a kind of phase difference film, polarizing film and display devices.Further specifically, it is related to one kind damp and hot Phase difference under environment changes the phase difference film for being able to inhibit, has the excellent polarizing film of the humidity resistance of the phase difference not and show Showing device.

Background technology

Liquid crystal display device is used on the way in liquid crystal display of liquid crystal TV set or laptop etc., expanded demand.It is logical Often, liquid crystal display device liquid crystal cells and setting made of clamping transparent electrode, liquid crystal layer, colored filter etc. with glass plate 2 polarizing films in its both sides are constituted, and each polarizing film has with 2 protective film for polarizing plate (hereinafter also referred to as protective film) Clamp the structure of polarizer (hereinafter, also becoming light polarizing film).As above-mentioned protective film for polarizing plate, it is widely used with high transparency Property can easily be ensured that film with the adaptation of the polyvinyl alcohol used in polarizer.

Additionally, it is known that the phase difference by configuring optically biaxial property between the polarizer and liquid crystal layer of liquid crystal display device Film may be implemented wider array of field angle, can improve display characteristic.This phase difference film can show excellent optical Can, therefore be concerned, it is used for liquid crystal display device.In addition, even if phase difference film is as having both polarizing film protection film work( The film of energy, is also used for liquid crystal display device.

But since the penetrability of phase difference film is high, by making moisture penetrate to inside, easily cause phase difference The variation of film length of delay (phase difference value), as a result, there are problems that generating the irregular colour of liquid crystal display device.

As the method for the variation (phase difference variation) for improving above-mentioned phase difference film length of delay, can enumerate makes phase difference film The thinning method of film thickness adds additivated method in large quantities in order to control penetrability.But make the film thickness of phase difference film It is thinning or in large quantities add additive when, length of delay becomes smaller, therefore, it is necessary to length of delay ascending ability (showing property of phase difference) height Compound.

As the equable phase difference elevator of above-mentioned phase difference film phase difference caused by humidity, such as propose miazines Compound (Japanese Unexamined Patent Publication 2012-214683 bulletins) or compound in triazine class (such as Japanese Unexamined Patent Publication 2003-344655 public affairs Report).In addition, it is proposed that further add the liquid crystal compounds of the molecular weight with bigger and improve showing property of phase difference etc. (Japanese Unexamined Patent Publication 2007-119737 bulletins).

Invention content

But change recorded in Japanese Unexamined Patent Publication 2012-214683 bulletins or Japanese Unexamined Patent Publication 2003-344655 bulletins Closing object, there are the following problems：The warm-up movement of molecule is big under hygrothermal environment, and phase difference changes big.In addition, Japanese Unexamined Patent Publication 2012- Recorded compound, showing property of phase difference are insufficient in No. 214683 bulletins or Japanese Unexamined Patent Publication 2003-344655 bulletins. In addition, in order to improve showing property of phase difference, even if addition Japanese Unexamined Patent Publication 2007-119737 bulletins are such to have two or more Aromatic ring compound, sufficient showing property of phase difference is also unable to get, in addition, the additive amount of this compound is made to increase When, it leads to the problem of phase difference film, polarizing film and is further deteriorated using the humidity resistance of its liquid crystal display device.In addition, When adding additive in large quantities to control phase difference film penetrability, the base materials tree such as some kinds of additive and cellulose esters The intermiscibility of fat can be deteriorated, and therefore, there is limitation on additive amount.It is aobvious therefore, it is necessary to have both the phase difference of phase difference elevator Existing property and high humidity resistance.

The present invention is in view of the above subject and the invention completed, a kind of maintains high phase difference aobvious it is intended that providing Show property and can inhibit the phase difference film of the variation of the phase difference under hygrothermal environment and use the polarizing film of the phase difference film, show Showing device.

The present inventor has made intensive studies to solve the problem above-mentioned.Itself as a result, it has been found that, by be used as Nitrogenous compound (A) shown in the following general formula (1) of phase difference elevator while by nitrogenous compound shown in the following general formula (2) (B) it is mixed, high showing property of phase difference can be maintained, and the phase difference under hygrothermal environment is inhibited to change, until complete At the present invention.

That is, the present invention is a kind of phase difference film, with phase difference elevator, the phase difference rising contains the following general formula (1)：

[chemical formula 1]

Ar-X₂-Ar-Y₂- Ar ... nitrogenous compounds (A)

(in general formula (1), Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted contains Nitrogen heteroaromatic, X₂And Y₂Separately indicate substituted or unsubstituted nitrogenous heteroaromatic) indicate nitrogenous compound (A) and

The following general formula (2)：

[chemical formula 2]

Ar-X₃-Ar-Y₃-Ar-Z₃- Ar ... nitrogenous compounds (B)

(in general formula (2), Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted contains Nitrogen heteroaromatic, X₃、Y₃And Z₃Separately indicate substituted or unsubstituted nitrogenous heteroaromatic) indicate nitrogen Close object (B).

Description of the drawings

Fig. 1 is phase difference film manufacturing device (the rubber cement system of solution casting film device of an embodiment of the invention Standby process, curtain coating process and drying process) skeleton diagram.Wherein, 1 indicate dissolution kettle, 2,5,11,14 indicate liquid-feeding pumps, 3,6, 12,15 filter is indicated, 4,13 indicate storage tank, and 8,16 indicate conduit, and 10 indicate additive feed chamber, and 20 indicate collecting fitting, 21 indicate mixing machine, and 30 indicate mold, and 31 indicate metal support, and 32 indicate wet film, and 33 indicate stripping position, and 34 indicate tentering Device, 35 indicate roller drying device, and 36 indicate roller, and 37 indicate up- coiler, and 41 indicate feed chamber, and 42 indicate storage tank, and 43 indicate pump, 44 indicate filter.

Fig. 2 is the summary section of an example for the LCD device structure for indicating an embodiment of the invention.Its In, 101A, 101B expression polarizing film, 102 expression protective films, 103A, 103B expression active energy ray-curable bonding agent, 104 Indicate polarizer, 105 indicate phase difference film, and 106 indicate functional layer, and 107 indicate liquid crystal cells, and 108 indicate liquid crystal display dress It sets.

Specific implementation mode

The present invention relates to a kind of phase difference films, and with phase difference elevator, the phase difference elevator contains following logical Formula (1)：

[chemical formula 3]

Ar-X₂-Ar-Y₂- Ar ... nitrogenous compounds (A)

The following general formula (2)：

[chemical formula 4]

Ar-X₃-Ar-Y₃-Ar-Z₃- Ar ... nitrogenous compounds (B)

(in general formula (2), Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted contains Nitrogen heteroaromatic, X₃、Y₃And Z₃Separately indicate substituted or unsubstituted nitrogenous heteroaromatic) indicate nitrogen Close object (B).(inhibit damp and hot according to the present invention it is possible to provide and can have both high showing property of phase difference and high wet heat durability Phase difference under environment changes) phase difference film and the polarizing film using the phase difference film, display device.

The phase difference film of the present invention is characterized in that, including containing the nitrogenous compound for using general formula (1) and (2) to indicate respectively (A) and the phase difference elevator of nitrogenous compound (B).Phase difference film with this structure can have both high phase difference and show Property and high wet heat durability.Here, the mechanism speculate of the performance of above-mentioned function and effect caused by the composition of the present invention is as follows.It needs It is noted that the present invention is not limited to following mechanism.That is, first, before being placed under hygrothermal environment, in ambient temperature and moisture In the state of, in phase difference film, the phase difference elevator containing above-mentioned nitrogenous compound (A) and nitrogenous compound (B) makes point The long axis of son is orientated along the direction parallel with the phase difference film draw direction.In addition, at this point, by above-mentioned orientation, Above-mentioned nitrogenous compound (A) and nitrogenous compound (B) show phase difference respectively.

But the phase difference amount of showing of above-mentioned nitrogenous compound (A) and nitrogenous compound (B) its each molecule and damp and hot The disorderly situation of orientation under environment is respectively different.Specifically, the nitrogenous compound (B) that molecular weight is big because with cellulose esters The variation inhibition of the strong and optical characteristic of interaction of equal substrate resins is excellent.On the other hand, small nitrogenous of molecular weight The intermiscibility of the substrate resins such as compound (A) and cellulose esters is excellent.Then, nitrogenous compound (A) passes through hydrogen bond etc. and and base The nitrogenous compound (B) that the interaction of material resin is strong interacts, therefore, the disorder for inhibiting it to be orientated.On the other hand, For nitrogenous compound (B), made by being combined with the good nitrogenous compound of intermiscibility (A) with the substrate resins such as cellulose With and be easy it is indissoluble with substrate resin, further suppress phase difference change.Think：Contained as a result, by being applied in combination 2 kinds Nitrogen compound, the influence under hygrothermal environment suffered by two nitrogenous compounds are cancelled out each other.As a result, being carried out as phase difference film When investigation, phase difference variation is improved, and provides and individually makees with by above-mentioned nitrogenous compound (A) and nitrogenous compound (B) It is compared for the case where phase difference elevator use, the phase difference film of excellent in te pins of durability.

Hereinafter, embodiments of the present invention will be described.It should be noted that the present invention be not limited to it is below Embodiment.In addition, the dimensional ratios of attached drawing are exaggerated for convenience of explanation and, it is sometimes different from actual ratio.

《Phase difference film》

The phase difference film of the present invention is characterized in that, including the nitrogenous compound indicated containing above-mentioned general formula (1) and (2) (A) and the phase difference elevator of nitrogenous compound (B).

The phase difference film of the present invention can have high phase difference to show by the phase difference elevator containing the present invention Property, and the phase difference under hygrothermal environment is inhibited to change smaller.In phase difference film, the preferred equable phase difference of length of delay Film, when using the polarizing film containing phase difference film in liquid crystal display device, from the viewpoint of preventing irregular colour etc., preferably Phase difference changes small.

In the phase difference film of the present invention, in order to further decrease color caused by the phase difference caused by humidity changes not , preferably R_OThe rate of change meets ± 4%, more preferably ± 3%, further preferably ± 2.5%.About the Rt rate of change, also base It in same reason, preferably satisfies within ± 5%, within more preferably ± 4%, within further preferably ± 3.5%.

The film thickness of the phase difference film of the present invention is preferably 15 μm or more 35 μm or less.It, can be with if it is 15 μm or more Irregular colour can be prevented in the case where being set as large area by carrying out homogeneous film formation.Furthermore it is possible to obtain sufficient phase difference. On the other hand, in the case of film thickness is 35 μm below, increased by the absolute value of the amount of moisture of moisture absorption, it is possible thereby to inhibit to be made aobvious Irregular colour is generated when showing device.From the aspect of homogeneous film formation, Ro, Rt humidity change, preferably 15~35 μ ms are more excellent It is selected as 20~35 μm.

The thickness of rubber cement or fusant, and/or stretching condition that above-mentioned film thickness is cast when can be by adjusting film forming and Control is in above-mentioned desired range.

In addition, the width direction of phase difference film and the film thickness deviation of length direction of the present invention are both preferably 0~4 μm.This When, the phase difference deviation in phase difference film surface is can inhibit if even if being the phase difference film of large area, irregular colour can be prevented. In order to further suppress phase difference deviation, film thickness deviation is preferably 0~2.5 μm, more preferably 0~1.5 μm.

It should be noted that phase difference film film thickness can use the film thickness gauges such as micrometer to be measured.Specifically, in phase Potential difference film width direction measures film thickness (μm) with the point more than at the intervals pair 10mm 100, their average value is set as phase difference Film film thickness (μm).In addition, the difference of the maximum value of film thickness and minimum value is set as film thickness deviation (μm).

In general, the method that phase difference film generates phase difference includes：(1) it is produced by substrate resins such as cellulose esters (vinegar cotton) Raw phase difference；(2) the methods of phase difference is generated by adding phase difference elevator.In the former case, due to base material tree Fat has penetrability, and therefore, Ro, Rt are changed because of humidity.On the other hand, in the latter case, Ro, Rt are not easy due to humidity It changes, therefore preferably.In addition, by adding elevator, therefore filming can be carried out by improving showing property of phase difference.But When the additive amount of elevator is excessive, it is possible to which mist degree is deteriorated.

By addition plasticizer, phase difference film is plasticized, is easy integrally to apply stress to phase difference film when stretching, Film thickness deviation becomes smaller and (becomes good).In addition, being hydrophobic in phase difference film and cannot adsorb water, therefore, Ro, Rt humidity change It reduces.But plasticizer it is excessive when, it is possible to mist degree be deteriorated, not preferably.

The film thickness of phase difference film is thinner, and whole amount of moisture is more reduced, and therefore, Rt humidity, which changes, to be reduced.But phase difference When the film thickness of film is excessively thin, it is difficult to which homogeneous film formation, film thickness deviation become larger (variation).

The phase difference film of the present invention includes that the phase difference containing above-mentioned nitrogenous compound (A) and nitrogenous compound (B) is promoted Agent further contains (a) plasticizer, the binding affinity chemical combination of (b) hydrogen as needed preferably using substrate resins such as celluloses as principal component Object, the binding affinity compound of (c) hydrogen and (d) other additives such as other any ingredients and constitute.It should be noted that in this hair In bright phase difference film, " principal component " refers to the ingredient of the 50 mass % or more to account for phase difference film entirety, preferably 60 matter Measure % or more, more preferably 70 mass % or more.

< phase difference elevators >

Phase difference elevator (also referred to as postponing visualization reagent) refers to the change for having the function of that phase difference film length of delay is made to increase Close object.Specifically, referring to compound with the following functions：Contain 3 mass of compound relative to 100 mass parts of substrate resin Part phase difference film measures the thickness direction in wavelength 590nm length of delay Rt (590) and the phase that is not added with phase difference elevator Potential difference film is compared, the value of 1.1 times of display or more.

Ro, Rt humidity change can by adjust phase difference elevator type and additive amount, plasticizer type and add Dosage etc. and control in desired range.

Phase difference elevator contains contained in the phase difference film of the present invention：

The following general formula (1)：

[chemical formula 5]

Ar-X₂-Ar-Y₂- Ar ... nitrogenous compounds (A)

The following general formula (2)：

[chemical formula 6]

Ar-X₃-Ar-Y₃-Ar-Z₃- Ar ... nitrogenous compounds (B)

(in general formula (2), Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted nitrogenous Heteroaromatic, X₃、Y₃And Z₃Separately indicate substituted or unsubstituted nitrogenous heteroaromatic) indicate nitrogenous chemical combination Object (B).

If it is such compound, the intermiscibility to substrate resin, orientation can be improved.It is additionally possible to suppress Orientation of the hydrone in substrate resin.Said effect is to form hydrogen with substrate resin by the nitrogen-atoms in above-mentioned nitrogenous compound Caused by with substrate resin interaction etc. occurs for the aromatic series pi-electron in key or above-mentioned nitrogenous compound.

Therefore, if the polarizing film with the phase difference film containing this phase difference elevator filled for liquid crystal display It sets, then high showing property of phase difference can be obtained, phase difference caused by humidity changes can be reduced and changed, liquid crystal display can be inhibited The reduction of contrast or the generation of irregular colour caused by the humidity of device changes.

In the general formula (1) and (2), Ar is separately that substituted or unsubstituted aromatic series hydrocarbon ring or substitution or nothing take The heteroaromatic in generation, preferably substituted or unsubstituted 5 yuan or 6 yuan of aromatic series hydrocarbon ring.

There is no limit from can for described 5 yuan or 6 yuan of aromatic series hydrocarbon ring or the structure of 5 yuan or 6 yuan of heteroaromatic To obtain the variation excellent effect of optical characteristics, the phase difference film viewpoint of excellent in te pins of durability is set out, and preferably indicates the fragrance such as phenyl ring Race's hydrocarbon ring；Pyridine ring, pyrimidine ring, pyridine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings, 1,2,4- tri- The nitrogenous heteroaromatic such as azoles ring, tetrazole ring；The oxygen-containing heteroaromatic such as furans；The sulfur-containing aromatics heterocycle such as thiophene；Oxazole ring, Oxadiazole rings, oxatriazole ring, isoxazole ring etc. are containing there are many heteroatomic heteroaromatics.Wherein, more preferably aromatic hydrocarbon Ring or nitrogenous heteroaromatic, further preferably aromatic series hydrocarbon ring, particularly preferably phenyl ring.What general formula (1) and (2) indicated contains Nitrogen compound can have aromatic ring or heteroaromatic mutually of the same race as multiple Ar, it is possible to have different types of Aromatic ring or heteroaromatic.From the viewpoint of manufacturing cost or optical characteristics, the preferably at least Ar of end is mutually same The aromatic series hydrocarbon ring or heteroaromatic of kind, more preferably whole Ar are aromatic series hydrocarbon ring or heteroaromatic of the same race.

5 yuan or 6 yuan of aromatic series hydrocarbon ring or 5 yuan or 6 yuan of heteroaromatic or nitrogenous heteroaromatic are had Substituent group to the present invention effect do not generate big influence, therefore, arbitrary substituent group can be imported.Therefore, as substitution Base is not particularly limited, as concrete example, including：Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkyl (first Base, ethyl, n-propyl, isopropyl, tertiary butyl, n-octyl, 2- ethylhexyls etc.), naphthenic base (cyclohexyl, cyclopenta, 4- positive ten Dialkyl cyclic hexyl etc.), alkenyl (vinyl, allyl etc.), cycloalkenyl group (2- cyclopentene -1- bases, 2- cyclohexene -1- bases Deng), alkynyl (acetenyl, propinyl etc.), aryl (phenyl, p-methylphenyl, naphthalene etc.), heteroaryl (2- pyrrole radicals, 2- furans Base, 2- thienyls, pyrrole radicals, imidazole radicals, oxazolyls, thiazolyl, benzimidazolyl, benzoxazolyl, 2-[4-morpholinodithio base, pyrrole Oxazoline ketone group, pyridyl group, pyriconyl, 2- pyrimidine ketone groups etc.), cyano, hydroxyl, nitro, carboxyl, alkoxy (methoxyl group, ethoxy Base, isopropoxy, tert-butoxy, n-octyloxy, 2- methoxy ethoxies etc.), aryloxy group (phenoxy group, 2- methylphenoxies, 4- Tert-butyl benzene oxygroup, 3- nitro-phenoxies, 2- tetradecanoic acid acyl amino phenoxy groups etc.), acyl group (acetyl group, pivaloyl benzene first Acyl group etc.), acyloxy (formyloxy, acetoxyl group, pivaloyl oxygroup, stearoyl-oxy, benzoyloxy, to methoxybenzene Base carbonyl oxygroup etc.), amino (amino, methylamino, dimethylamino, anilino-, N- metlyl-phenylamines base, diphenyl amino Deng), acyl amino (formamido group, acetyl-amino, pivaloyl amino, lauroyl amino, benzamido etc.), alkyl and virtue Base sulfuryl amino (Methylsulfonylamino, butyl sulfuryl amino, phenyl sulfonyl amino, 2,3,5- trichlorophenyl sulphonyl Base amino, p-methylphenyl sulfuryl amino etc.), sulfydryl, alkyl sulfenyl (methylsulfany, ethylsulfanyl, n-hexadecyl sulfenyl Deng), artyl sulfo (phenylsulfartyl, rubigan sulfenyl, m-methoxyphenyl sulfenyl etc.), sulfamoyl (N- ethyl sulfonamides Base, N- (3- dodecyloxies propyl) sulfamoyl, N, N- DimethylsuIfamoyls, N- acetylsulfamoyls, N- benzoyls Sulfamoyl, N- (N ' phenylcarbamoyls) sulfamoyl etc.), sulfo group, carbamoyl (carbamoyl, N- methylaminos Formoxyl, N, N- formyl-dimethylaminos, N, N- di-n-octyls carbamoyl, N- (methyl sulphonyl) carbamoyl Deng) etc..These groups can further be replaced by same group.

In above-mentioned substituent group, the preferably alkyl of carbon atom number 1~5 or the acyl group of carbon atom number 1~5, particularly preferably It is unsubstituted.In addition, from the same viewpoint, the substituent group being preferably bonded with following carbon atoms or hetero atom is unsubstituted, institute It states carbon atom or hetero atom refers to and X₂、X₃、Y₂、Y₃Or Z₃The carbon atom that is bonded adjacent carbon atom or hetero atom, more preferably The hetero atoms such as nitrogen-atoms are unsubstituted.When the substituent group is unsubstituted, steric hindrance becomes smaller, therefore, Ar and X₂、X₃、Y₂、Y₃ Or Z₃Become to be not easy to reverse, Ar and X₂、X₃、Y₂、Y₃Or Z₃It is easy to interact with substrate resins such as cellulose fiber compounds, therefore special Not not preferably.

As described above, the nitrogen heterocyclic ring structure X in general formula (1)₂、Y₂, nitrogen heterocyclic ring structure X in general formula (2)₃、 Y₃、Z₃Separately indicate substituted or unsubstituted nitrogenous heteroaromatic, preferably substituted or unsubstituted 5 yuan or 6 yuan Nitrogenous heteroaromatic.As X₂、Y₂、X₃、Y₃And Z₃Concrete example, be not particularly limited, can separately enumerate：Pyrroles Ring, imidazole ring, pyrazole ring, pyridine ring, pyridine ring, pyridazine ring, triazole ring, triazine ring, indole ring, imidazole ring, purine ring, thiazole Quinoline ring, thiazole ring, Thiadiazole, oxazoline Huan, oxazole ring, oxadiazole rings, quinoline ring, isoquinolin ring, phthalazines ring, naphthyridines ring, Quinoxaline ring, quinazoline ring, cinnolines ring, pteridine ring, acridine ring, coffee are around quinoline ring, azophenlyene ring, tetrazole ring, benzimidazole ring, benzo Oxazole ring, benzothiazole ring, benzotriazole ring, purine ring, pyrrolo- triazole ring, Pyrazolotriazole ring etc..Wherein, imidazoles Ring, pyrazole ring or triazole ring, it is especially excellent to the inhibition for changing generation phase difference variation due to humidity, and can be obtained durable Property excellent resin combination, therefore preferably, particularly preferred pyrazole ring.X₂、X₃、Y₂、Y₃And Z₃The nitrogenous heteroaromatic ring indicated It can be tautomer.

Preferred other embodiment of the invention is the nitrogenous fragrance in nitrogenous compound shown in general formula (1) as a result, Race heterocycle structure X₂、Y₂, nitrogenous heteroaromatic structure X in nitrogenous compound shown in general formula (2)₃、Y₃、Z₃Separately For the phase difference film for selecting by the nitrogenous heteroaromatic in imidazole ring, pyrazole ring or triazole ring.

It is as follows shown in concrete structure when 2,4- triazole ring for example, pyrazole ring, imidazole ring, 1,2,3-triazoles ring or 1.

[chemical formula 7]

In formula, ※ indicates the bonding position with general formula (1) or the Ar in (2).From ensuring and the base materials such as cellulose acylate From the perspective of the interaction of resin, R⁵Expression substituent group same as the substituent group that Ar can have, preferably hydrogen atom.

In addition, from the same viewpoint, the X being bonded via Ar₂、Y₂、X₃、Y₃And Z₃It is preferred that mutually via 3 atoms with Above it is bonded.In addition, from the same viewpoint, the substituent group being incorporated on following carbon atoms or nitrogen-atoms is preferably hydrogen, institute It states carbon atom or nitrogen-atoms refers to：Form X₂、Y₂、X₃、Y₃Or Z₃Carbon atom in the carbon adjacent with the carbon atom that Ar is bonded it is former Son or nitrogen-atoms, more preferable nitrogen-atoms are unsubstituted.

Ar and X₂、Y₂、X₃、Y₃Or Z₃Between key be singly-bound.If it is singly-bound, resin chain is sent out at nitrogen heterocyclic ring position Raw interaction, and cause torsion appropriate in singly-bound portion and be easy to follow resin chain.

As X₂、Y₂、X₃、Y₃And Z₃, can have heteroaromatic mutually of the same race, it is possible to have different types of virtue Fragrant race's heterocycle, but from the viewpoint of manufacturing cost or optical characteristics, preferably X₂、Y₂、X₃、Y₃And Z₃It is miscellaneous for aromatic series of the same race Ring.

The nitrogenous compound (A) or nitrogenous compound (B) can form hydrate, solvate or salt.It needs to illustrate , in the present invention, hydrate can contain organic solvent, in addition, solvate can contain water.That is, at " hydrate " And " solvate " includes that any mixed solvent containing water and organic solvent closes object.As salt, including by inorganic acid Or organic acid is formed by acid-addition salts.As the example of inorganic acid, including halogen acids (hydrochloric acid, hydrobromic acid etc.), sulfuric acid, phosphoric acid Deng in addition, being not limited to these.In addition, the example of organic acid can be enumerated：Acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, Citric acid, benzoic acid, alkyl sulfonic acid (methanesulfonic acid etc.), allyl sulphonic acid (benzene sulfonic acid, 4- toluenesulfonic acids, 1,5- naphthalenedisulfonic acids etc.) Deng in addition, being not limited to these.Wherein, preferably hydrochloride, acetate, propionate, butyrate.

As the example of salt, can enumerate the acidic moiety that is present in close compound by metal ion (such as alkali metal salt, Such as sodium or sylvite, alkali salt, such as calcium or magnesium salts, ammonium salt alkali metal ion, alkaline-earth metal ions or aluminium ion) Substitution is formed by salt when organic base (ethanol amine, diethanol amine, triethanolamine, morpholine, piperidines etc.) is made, in addition, simultaneously It is not limited to these.Wherein, preferably sodium salt, sylvite.

It is any comprising general organic solvent in the example of solvent contained by solvate.Specifically, can arrange It lifts：Alcohol (such as：Methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, the tert-butyl alcohol), ester (such as：Ethyl acetate), Hydrocarbon (such as：Toluene, hexane, heptane), ether (such as：Tetrahydrofuran), nitrile (such as：Acetonitrile), ketone (acetone) etc..Preferred alcohols (example Such as：Methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, the tert-butyl alcohol) solvate.These solvents can be Used reaction dissolvent when the compound is synthesized, can also be used solvent when carrying out partial crystallization purifying in post synthesis, Or can be the mixing of these solvents.

In addition, can both contain solvent of more than two kinds simultaneously, can also be containing hydrous solvent form (such as water and Alcohol (such as methanol, ethyl alcohol, tert-butyl alcohol etc.) etc.).

It should be noted that the nitrogenous compound (A) or nitrogenous compound (B) can not contain the shape of water, solvent, salt State is added, and forms hydrate, solvate or salt in the present invention in resin combination or phase difference film that can also be.

The molecular weight of the nitrogenous compound (A) and nitrogenous compound (B) is not particularly limited, and molecular weight is smaller, with tree The intermiscibility of fat is more excellent, and molecular weight is bigger, and the variation inhibition that optical value changes ambient humidity is higher, therefore, excellent It is selected as 100~2000, more preferably 200~1500, more preferably 300~1000.

As the concrete example with the nitrogenous compound (A) of structure shown in the general formula (1) for the present invention, can enumerate down The compound stated.

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

[chemical formula 11]

[chemical formula 12]

As the concrete example with the nitrogenous compound (B) of structure shown in general formula (2) for the present invention, can enumerate down The compound stated.

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

The phase difference film of the present invention contains general formula (1) and the nitrogenous compound (A) and nitrogenous compound (B) of (2) expression, is Desired delay is obtained, nitrogenous compound (A) and nitrogenous compound (B) be added in phase difference film substrate resin.Quilt Make an addition in substrate resin refers to being dissolved or dispersed in substrate resin.Only pass through nitrogenous compound (A) and nitrogenous compound (B) Only it is coated on phase difference film surface, it is possible to be unable to get desired delay.It is added in substrate resin to be formed Following method may be used in form：Preparation is mixed with the glue of substrate resin and nitrogenous compound (A) and nitrogenous compound (B) Slurry makes it carry out the method for solution curtain coating or make to heat in advance to have melted substrate resin and nitrogenous compound (A) and nitrogen The method for closing the fusant curtain coating of the mixture of object (B).

For the phase difference film of the present invention, in the case where being installed on VA type liquid crystal display devices, from raising field angle Or from the perspective of the identifications such as contrast, preferably following formula (i) and (ii) indicate, in phase difference film surface direction phase difference In the range of value Ro is 45~60nm, the phase difference value Rt of film thickness direction is in the range of 110~140nm.Phase difference film passes through It at least stretches, can be adjusted in the range of above-mentioned phase difference value while adjusting stretching ratio in the directions TD.

[mathematical expression 1]

Formula (i):Ro=(n_x-n_y)×d(nm)

Formula (ii):Rt={ (n_x+n_y)/2-n_z}×d(nm)

[in formula (i) and formula (ii), n_xIndicate that direction refractive index is the refractive index on maximum direction x in film surface.n_yTable Show the refractive index on direction is vertical with the direction x in film surface direction y.Nz indicates the refractive index on film thickness direction z.d Indicate film thickness (nm).]

Total usage amount of nitrogenous compound (A) and nitrogenous compound (B) in the phase difference film of the present invention does not limit especially System.But desired delay in order to obtain, preferably relative to resins 100 such as cellulose esters as phase difference film base material Mass parts are the compound containing general formula (1) and (2) expression in the range of total 0.1~20 mass parts, more preferably 1~15 matter In the range of measuring part, in the range of further preferably 1.5~10 mass parts, the further preferably range of 2~8 mass parts It is interior, the particularly preferably range of 3~6 mass parts.If it is within the scope of this, the phase difference film imparting of the present invention is adequately prolonged Late, meanwhile, intermiscibility and exudation patience become good.

When the gross mass of nitrogenous compound (A) and nitrogenous compound (B) total is set as 100, in phase difference elevator Nitrogenous compound (A) and the containing ratio of nitrogenous compound (B) be preferably nitrogenous compound (A):Nitrogenous compound (B)=2: 98~98:2.If it is such range, the phase difference elevator containing above-mentioned 2 kinds of nitrogenous compounds with as film base material The balance that the intermiscibility of the resins such as cellulose esters and the phase difference under hygrothermal environment change between inhibiting is good.More preferably Nitrogenous compound (A):Nitrogenous compound (B)=30:70~70:30, further preferred nitrogenous compound (A):Nitrogenous compound (B)=50:50~70:30.

Preferred other forms of the invention are a kind of phase difference film as a result, wherein by nitrogenous compound (A) and nitrogen When quality total for closing object (B) is set as 100, nitrogenous compound (A) and nitrogenous compound (B) in phase difference elevator contain It is nitrogenous compound (A) to have ratio:Nitrogenous compound (B)=2:98~98:2.

(synthesis of nitrogenous compound)

The nitrogenous compound (A) and nitrogenous compound (B) can be synthesized with well known method.In nitrogenous compound (A) in, the compound with 1,2,4- triazole rings can use any raw material, but preferably derive carbonitrile derivatives or imido ether The method that object is reacted with hydrazide derivatives.It, can be with as long as the solvent not reacted with raw material as the solvent for reaction For any solvent, can enumerate：Esters (such as ethyl acetate, methyl acetate etc.), amides (dimethylformamide, dimethyl Acetamide etc.), ethers (ethylene glycol dimethyl ether etc.), alcohols (such as methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, 2- fourths Alcohol, ethylene glycol, ethylene glycol single methyl ether etc.), aromatic hydrocarbon (such as toluene, dimethylbenzene etc.), water.It is excellent as the solvent used It is selected as alcohols solvent.In addition, these solvents can be used in mixed way.

The usage amount of solvent is not particularly limited, relative to the quality of the hydrazide derivatives used, preferably 0.5~30 times In the range of amount, further preferably 1.0~25 times amounts, in the range of particularly preferably 3.0~20 times are measured.

When carbonitrile derivatives and hydrazide derivatives being made to react, catalyst can not also be used, but in order to make reaction accelerate, preferably Use catalyst.As the catalyst used, acid can be used, alkali can also be used.As acid, can enumerate：Hydrochloric acid, sulfuric acid, Nitric acid, acetic acid etc., preferably hydrochloric acid.For acid, it can be diluted and add in water, can also be blown into system The method of gas is added.As alkali, inorganic base (potassium carbonate, sodium carbonate, saleratus, sodium bicarbonate, hydroxide can be used Potassium, sodium hydroxide etc.) and organic base (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium butoxide, butanol potassium, diisopropyl ethyl Amine, N, N '-dimethyl aminopyridines, 1,4- diazabicyclos [2.2.2] octane, N-methylmorpholine, imidazoles, N- methylimidazoles, Pyridine etc.) it is any, as inorganic base, preferably potassium carbonate, as organic base, preferably sodium ethoxide, sodium ethoxide, butanol Sodium.Inorganic base can be added with the state of powder, can also be added in the state of being scattered in solvent.In addition, organic base can be with It is added under the state (such as 28% methanol solution etc. of sodium methoxide) for being dissolved in solvent.

As long as the amount that the usage amount reaction of catalyst carries out, is just not particularly limited, relative to being formed by triazole ring, In the range of preferably 1.0~5.0 times moles, in the range of further preferably 1.05~3.0 times moles.

In the case of so that iminoether derivatives and hydrazide derivatives is reacted, catalyst need not be used, can by It is heated in solvent and obtains purpose thing.

Adding method for the raw material of reaction, solvent and catalyst is not particularly limited, and can finally add catalyst, Solvent can also finally be added.It is also preferable to carbonitrile derivatives is made to be dispersed or dissolved in after solvent, addition catalyst, addition The method of hydrazide derivatives.

As long as in reaction solution temperature reaction carry out temperature, can be any temperature, preferably 0~150 In the range of DEG C, in the range of further preferably 20~140 DEG C.Furthermore it is possible to remove the water of generation on one side, carry out on one side anti- It answers.

The processing method of reaction solution may use any method, when alkali is used as catalyst, preferably in reaction solution The method that acid is added and neutralizes.As the acid for neutralization, it can be mentioned, for example：Hydrochloric acid, sulfuric acid, nitric acid or acetic acid etc., it is especially excellent It is selected as acetic acid.As long as the pH of the amount reaction solution of the acid for neutralization becomes 4~9 range, just it is not particularly limited, relatively In the range of the alkali used, preferably 0.1~3 times mole, particularly preferably 0.2~1.5 times mole.

It, preferably after the extraction will be organic molten when being extracted using organic solvent appropriate as the processing method of reaction solution Agent washes with water, the method followed by concentrated.Organic solvent appropriate said here is ethyl acetate, toluene, dichloromethane The water-insoluble solvent such as alkane, ether；Or the mixed solvent of the water-insoluble solvent and tetrahydrofuran or alcohols solvent, preferably For ethyl acetate.

In the case of making nitrogenous compound (A) or nitrogenous compound (B) partial crystallization, it is not particularly limited, the sum preferably in Additional water in reaction solution and make the method for its partial crystallization or the water-soluble of nitrogenous compound (A) or nitrogenous compound (B) will be dissolved with The method that liquid was neutralized and made its partial crystallization.

(synthesis of example compound 1)

Example compound 1 can be synthesized by path below.

[chemical formula 18]

In n-butanol 40ml be added 1,3- dicyanobenzenes 2.5g (19.5mmol), benzoyl hydrazine 7.9g (58.5mmol), Potassium carbonate 9.0g (68.3mmol) is stirred 24 hours under nitrogen atmosphere, at 120 DEG C.After reaction solution is cooled down, pure water is added The solid of precipitation after being stirred at room temperature 3 hours, is filtered separation, is cleaned with pure water by 40ml.Add in obtained solid Enter water and ethyl acetate and carry out liquid separation, organic layer is cleaned with pure water.Organic layer is dried with magnesium sulfate, decompression evaporates Solvent.Obtained coarse crystallization is purified with silica gel chromatography (ethyl acetate/heptane), obtains 5.5g example compounds 1.Yield with 1, 3- dicyanobenzenes benchmark are calculated as 77%.

Obtained example compound 1¹H-NMR spectrum are as described below.

¹H-NMR (400MHz, solvent：Weight DMSO, benchmark：Tetramethylsilane) δ (ppm)：8.83 (1H, s), 8.16~ 8.11(6H、m)、7.67-7.54(7H、m)

(synthesis of example compound 55)

Example compound 55 can be synthesized by diagram below.

[chemical formula 19]

Acetophenone 80g (0.67mol), dimethyl isophthalate 52g are added in being dehydrated tetrahydrofuran 520ml (0.27mol), under nitrogen atmosphere, ice water it is cold it is lower be stirred on one side, amide sodium 52.3g is added dropwise bit by bit on one side (1.34mol).After the cold lower stirring of ice water 3 hours, stirred 12 hours under water cooling.In reaction solution be added the concentrated sulfuric acid and in and Later, pure water and ethyl acetate is added and carries out liquid separation, organic layer is cleaned with pure water.Organic layer is done with magnesium sulfate Dry, decompression evaporates solvent.Methanol is added in obtained coarse crystallization and carries out suspension cleaning, thus obtains intermediate A 55.2g.

Intermediate A 55g (0.15mol) is added in tetrahydrofuran 300ml, ethyl alcohol 200ml, is stirred at room temperature on one side It mixes, 1 hydrate 18.6g (0.37mol) of hydrazine is added dropwise bit by bit on one side.After completion of dropwise addition, it is heated to reflux 12 hours.It is reacting Pure water and ethyl acetate are added in liquid and carries out liquid separation, organic layer is cleaned with pure water.Organic layer is dried with magnesium sulfate, Decompression evaporates solvent.The coarse crystallization being refining to obtain with silica gel chromatography (ethyl acetate/heptane), obtains 27g example compounds 55.

Obtained example compound 55¹H-NMR spectrum are as described below.It should be noted that since there are tautomerisms Body is added few drops of trifluoroacetic acids in measuring solvent and is measured in order to avoid Chemical Software is complicated.

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)

(synthesis of example compound 37)

[chemical formula 20]

1,3- diiodo-benzene 3.2g, 4- phenylimidazoles 3.08g, cupric iodide 0.18g, cesium carbonate are added in DMF15ml 9.48g, trans- 1,2- cyclohexane diamines 0.44g under a nitrogen, are heated 5 hours and are stirred at 130 DEG C.By reaction solution After cooling, ethyl acetate 100ml is added, is cleaned 3 times with pure water, organic phase is concentrated under reduced pressure.With silica gel column chromatography (first Benzene/ethyl acetate) purifying residue, thus obtain 2.1g example compounds 37.Obtained example compound 37 is carried out using mass spectrum Identification.

It, can also be by changing adding for reactant in same reaction about nitrogenous compound (B) shown in general formula (2) Add ratio to prepare.In addition, about other compounds, can also synthesize by the same method.

It should be noted that according to above-mentioned synthetic method, can generate the quantity of aromatic series hydrocarbon ring and heteroaromatic with Nitrogenous compound (A) or the different nitrogenous compound of nitrogenous compound (B).This compound is sometimes also in mesh after isolating and purifying Slightly contain in mark product, but be typically free of, is micro containing, as long as not damaging as the purpose of the present invention The range of wet heat durability can then contain.

< substrate resins >

The phase difference film of the present invention preferably comprises thermoplastic resin as substrate resin.About hot contained in phase difference film Plastic resin is not particularly limited, and preferred substrates layer is made of stretchable thermoplastic resin.As stretchable thermoplastic resin Fat, it can be mentioned, for example：Acrylic resin, styrene resin, cyclenes hydrocarbon resins, cellulosic resin, PP type tree Fat, polyester resin or combination thereof.At this point, as acrylic resin, it is preferable to use containing methyl methacrylate is come from The Component units of ester contain the acrylic compounds of the Component units from the monomer component that can be copolymerized with it as principal component, further Resin.Also include the acrylic acid derivative with ring structure as copolymerizable monomer component.In addition, as phenylethylene tree Fat, can enumerate contain the Component units from styrene as principal component, further contain from the monomer that can be copolymerized with it at The styrene resin of the Component units divided.In addition, as cyclenes hydrocarbon resins, the drop for being referred to as cyclic olefine copolymer can be enumerated Borneol vinyl resin etc..In addition, as polypropylene-based resin, in addition to polypropylene, can enumerate poly- containing some polyethylene Propylene etc. can enumerate polyethylene terephthalate (PET) etc. as polyester resin.

Wherein, in a preferred embodiment, phase difference film contains cellulosic resin.About the specific of cellulosic resin Form, it is not also specifically limited, can be used cellulose esters, cellulose ether, cationized cellulose, in various vinyl monomers The grafting such as the cellulosic resin being polymerize Deng in the presence of and various vinyl monomers form polymer etc..Wherein, especially excellent Choosing uses cellulose esters.

Preferred other embodiment of the invention is using cellulosic resin as the phase difference film of principal component as a result,.

Cellulose esters refer to constitute cellulose β -1,4 be bonded glucose unit in 2,3 and 6 hydroxyls (- OH the cellulose fiber compound resin that part or all of hydrogen atom) is replaced by acyl group.

Cellulose esters is not particularly limited contained in the phase difference film of the present invention, preferably carbon atom number 2~22 or so Linear chain or branched chain carboxylic acid ester.The carboxylic acid for constituting ester both can be aliphatic carboxylic acid, can also form ring, or virtue Fragrant race's carboxylic acid.It can be mentioned, for example the hydrogen atoms of the hydroxylic moiety of cellulose by acetyl group, propiono, bytyry, isobutyryl, penta The cellulose of the acyl group substitution of the carbon atom numbers such as acyl group, pivaloyl group, caproyl, caprylyl, lauroyl, stearoyl 2~22 Ester.The carboxylic acid (acyl group) for constituting ester can have substituent group.It is 6 below low that the carboxylic acid of composition ester, which is particularly preferably carbon atom number, Grade aliphatic acid, further preferably carbon atom number are 3 lower fatty acids below.It should be noted that the acyl in cellulose esters Base both can be single kind, or the combination of multiple acyl groups.

It in the concrete example of preferred cellulose esters, can enumerate, diacetyl cellulose (DAC), triacetyl fiber Cellulose ethanoates such as plain (TAC), can also enumerate cellulose acetate propionate (CAP), cellulose acetate-butyrate, acetate propionate fourth The mixed aliphatic ester of the such cellulose that propionic acid ester group or butyric acid ester group are also bonded in addition to acetyl group of acid cellulose.This A little cellulose esters can both use individually one kind, can also be applied in combination a variety of.

(type of acyl group, degree of substitution)

By adjusting the type and degree of substitution of the acyl group of cellulose esters, above-mentioned Ro, Rt humidity can be changed to control in institute Desired range can improve the uniformity of film thickness.

The degree of substitution of the acyl group of cellulose esters is smaller, and showing property of phase difference more improves, thus, it is possible to carry out filming.Separately On the one hand, when the degree of substitution of acyl group is too small, it is possible to which durability is deteriorated, not preferably.

On the other hand, the degree of substitution of the acyl group of cellulose esters is bigger, does not show phase difference, and therefore, it is necessary in film So that stretching ratio is increased, but be difficult to equably be stretched with high stretching ratio, therefore, film thickness deviation becomes larger (variation).In addition, Rt humidity change by the carbonyl in cellulose water of coordination molecule by generate, that accordingly, there exist the degree of substitution of acyl group is high, i.e. fibre In dimension element carbonyl is more, Rt humidity changes the tendency being more deteriorated.

Total degree of substitution of cellulose esters is preferably 2.1~2.5.By being set as the range, environmental turbulence can be inhibited (especially It is that Rt caused by humidity changes), while improving the uniformity of film thickness.From the curtain coating and draftability improved when being film-made, further From the perspective of the uniformity for improving film thickness, more preferably 2.2~2.45.

More specifically, cellulose esters is satisfied by following formula (a) and (b).In formula, X is the degree of substitution of acetyl group, Y third The degree of substitution of acyl group or bytyry, or mixtures thereof degree of substitution.

[mathematical expression 2]

Formula (a) 2.1≤X+Y≤2.5

[mathematical expression 3]

Formula (b) 0≤Y≤1.5

Cellulose esters is more preferably cellulose ethanoate (Y=0) and cellulose acetate propionate (CAP) (Y：Propiono, Y > 0), from the aspect of reducing film thickness deviation, the further preferably cellulose ethanoate of Y=0.From by showing property of phase difference, Rt humidity change, film thickness deviation be set as from the aspect of desired range, the cellulose ethanoate particularly preferably used be 2.1≤ Two cellulose diacetates (DAC) of X≤2.5 (further preferred 2.15≤X≤2.45).In addition, in the case of Y > 0, it is special Not it is preferable to use cellulose acetate propionate (CAP) be 0.95≤X≤2.25,0.1≤Y≤1.2,2.15≤X+Y≤2.45.

By using above-mentioned cellulose ethanoate or cellulose acetate propionate, can obtain postponing excellent, mechanical strength, The excellent phase difference film of environmental turbulence.

It should be noted that the degree of substitution of acyl group indicates the average of the acyl group of every 1 glucose unit, 1 Portugal is indicated The hydrogen atom of 2,3 and 6 hydroxyls of grape sugar unit has several to be replaced by acyl group.Therefore, maximum degree of substitution is 3.0, In this case, refer to that 2,3 and 6 hydrogen atoms of hydroxyl are all replaced by acyl group.These acyl groups both can be in grape Fifty-fifty replaced on 2,3,6 of sugar unit, it is possible to have be distributed and replaced.Degree of substitution utilizes ASTM- Method specified in D817-96 and find out.

The different cellulose ethanoate of degree of substitution can be mixed and be made by desired optical characteristics in order to obtain With.The mixing ratio of different cellulose ethanoates is not particularly limited.

The number-average molecular weight (Mn) of cellulose esters is 2 × 10⁴~3 × 10⁵Range, further be 2 × 10⁴~1.2 × 10⁵Range, further be 4 × 10⁴~8 × 10⁴Range when, obtained phase difference film mechanical strength increases, therefore excellent Choosing.The number-average molecular weight Mn of cellulose esters uses the gel permeation chromatography (GPC) under following determination conditions to be measured and calculate Go out.

The weight average molecular weight (Mw) of cellulose esters is 2 × 10⁴~1 × 10⁶Range, further be 2 × 10⁴~1.2 × 10⁵Range, further be 4 × 10⁴~8 × 10⁴Range when, obtained phase difference film mechanical strength increases, therefore excellent Choosing.The weight average molecular weight Mw of cellulose esters is measured by using the gel permeation chromatography (GPC) under following determination conditions And it calculates.

Solvent：Dichloromethane

Column：ShodexK806, K805, K803G (Showa Denko K. K's manufacture) three is connected and is used

Column temperature：25℃

Sample solution concentration：0.1 mass %

Detector：RI Model 504 (manufacture of GL science Co., Ltd.)

Pump：L6000 (Hitachi Co., Ltd's manufacture)

Flow：1.0ml/min

Calibration curve：Use standard polystyren STKstandard polystyrene (TOSOH Co., Ltd's manufacture) Mw= The calibration curve that 1000000~500 13 samples are formed.13 samples substantially to use at equal intervals.

The raw cellulose of cellulose esters is not particularly limited, and can enumerate velveteen, wood pulp, mestha etc..In addition, by these The cellulose esters that substance obtains can be used in mixed way with arbitrary ratio respectively.

The cellulose esters such as cellulose ethanoate, cellulose acetate propionate can be manufactured by well known method.Generally For, by raw cellulose, defined organic acid (acetic acid, propionic acid etc.) and acid anhydrides (acetic anhydride, propionic andydride etc.), catalyst (sulphur Acid etc.) it is mixed, cellulose is esterified, is reacted to three esters for forming cellulose.In three esters, glucose unit Three hydroxyls (hydroxyl) replaced by the acyl group acid of organic acid.When simultaneously using two kinds of organic acids, mixing ester type can be made Cellulose esters, such as cellulose acetate propionate or cellulose acetate butyrate.Then, by the way that three esters of cellulose are carried out water Solution synthesizes the cellulose ester resin with desired acyl substitution.Thereafter, by filtering, precipitation, washing, dehydration, drying Etc. processes, complete cellulose ester resin.Specifically, can be closed with reference to the method described in Japanese Unexamined Patent Publication 10-45804 At.

As sales item, L20, L30 of Co., Ltd.'s Daicel, L40, L50, Eastman Chemical can be enumerated Ca398-3, Ca398-6, Ca398-10, Ca398-30, Ca394-60S etc..

< others additives >

In the phase difference film of the present invention, apart from the above, substance below can be contained as other additives.

(a) plasticizer

The phase difference film of the present invention preferably at least contains a kind of plasticizer with the purpose for assigning processability to phase difference film.Increase Modeling agent is preferably used alone or two or more is used in mixed way.

In plasticizers, it mixes from the control that can highly have both penetrability effect and with the substrate resins such as cellulose esters From the perspective of property, preferably comprise at least one kind of in following saccharide ester compounds, petchem and acrylic compounds Plasticizer.

For the plasticizer, from the improvement for making humidity resistance and with the intermiscibilities of the substrate resins such as cellulose esters and deposit Viewpoint is set out, and preferred molecular weight is 15000 hereinafter, being further 10000 or less.The molecular weight is 10000 compounds below For polymer when, weight average molecular weight (Mw) is preferably 10000 or less.Ranging from the 100~10000 of preferred molecular weight (Mw) In range, in the range of further preferably 400~8000.

The weight average molecular weight (Mw) of plasticizer is measured using the gel permeation chromatography (GPC) under following determination conditions And it calculates.

Solvent：Dichloromethane

Column：Three connections of ShodexK806, K805, K803G (Showa Denko K. K's manufacture) use

Column temperature：25℃

Sample solution concentration：0.1 mass %

Detector：RI Model 504 (manufacture of GL science Co., Ltd.)

Pump：L6000 (Hitachi Co., Ltd's manufacture)

Flow：1.0ml/min

Calibration curve：Use standard polystyren STK standard polystyrene (TOSOH Co., Ltd's manufacture) Mw= The calibration curve that 1000000~500 13 samples are formed.13 samples substantially to use at equal intervals.

Preferably it is being 6~40 mass parts relative to 100 mass parts of substrate resin especially for the effect of the present invention is obtained In the range of containing the molecular weight be 1500 compounds below, more preferably in the range of 10~20 mass parts contain above-mentionedization Close object.By containing above compound within the above range, the control of penetrability effect and the phase with substrate resin can be had both Dissolubility, therefore it is preferred that.

< saccharide ester compounds >

In the phase difference film of the present invention, saccharide ester compound can be contained for the purpose of preventing water solution.Specifically, making For saccharide ester compound, can use it is at least one kind of with 1 or more and 12 pyranose structure or furanose structure below, And by all or part of saccharide ester compound being esterified of the OH bases of its structure.

The example of the sugar of the synthesis material of saccharide ester compound as the present invention, can enumerate sugar for example as described below, The present invention is not limited to these.It can enumerate：Glucose, galactolipin, mannose, fructose, xylose or arabinose, lactose, sugarcane Sugar, Nystose, 1F- fructosyls Nystose, stachyose, maltol, lactitol, lactulose, cellobiose, maltose, fibre Tie up trisaccharide, maltotriose, raffinose or ketose.In addition, can also enumerate：Gentiobiose, gentianose, rough gentian tetrose, wood Trisaccharide, galactosyl sucrose etc..

As single carboxylic for all or part of of the OH bases in pyranose structure or furanose structure to be esterified Acid is not particularly limited, and can use well known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc..It uses Carboxylic acid can be a kind, or mixing of more than two kinds.

As the example of preferred aliphatic monocarboxylic acid, can enumerate：Acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, oneself Acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, 2- ethyl-hexanecarboxylic acids, hendecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, 15 Alkanoic acid, palmitic acid, Heptadecanoic acide, stearic acid, nonadecylic acid, arachidic acid, behenic acids, carnaubic acid, cerinic acid, heptacosane The saturated fatty acids such as acid, montanic acid, melissic acid, lacceroic acid acid, undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, Unsaturated fatty acids such as arachidonic acid, octenoic acid etc..

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

As the example of optimization aromatic monocarboxylic acid, benzoic acid, phenylacetic acid, methyl benzoic acid etc. can be enumerated in benzene first The aromatic monocarboxylate of 1~5 alkyl or alkoxy, cinnamic acid, benzyl acid, biphenyl carboxylic acid, naphthalene are imported on the phenyl ring of acid Carboxylic acid, tetralincarboxylic acid etc. have aromatic monocarboxylate or their derivative of 2 or more phenyl ring, particularly preferred benzene first Acid.

It is preferable to use the overall average degree of substitution that the following general formula (FA) indicates for phase difference film especially of the invention for 3.0~ 6.0 saccharide ester compound.

[chemical formula 21]

General formula (FA)

(in formula, R₁~R₈Each independently represent hydrogen atom, substituted or unsubstituted alkyl-carbonyl or substituted or unsubstituted Aryl carbonyl, R₁~R₈Can be mutually identical, it can also be different.)

The average substitution degree for the compound that above-mentioned general formula (FA) indicates is 3.0~6.0, it is possible thereby to highly have both moisture-inhibiting The control of property and the intermiscibility with cellulose esters.

In the application, the degree of substitution for the compound that general formula (FA) indicates indicates in 8 hydroxyls contained in general formula (FA) The number replaced by the substituent group other than hydrogen, that is, indicate the R of general formula (FA)₁~R₈In, number containing the group other than hydrogen.Cause This, in R₁~R₈In the case of all being replaced by the substituent group other than hydrogen, the 8.0 of degree of substitution become the maximum, in R₁~R₈All In the case of hydrogen atom, degree of substitution 0.0.

With general formula (FA) indicate structure compound be difficult to the number of synthesis of hydroxy, OR bases the fixed list of number One species compound, it is known that the compound mixed by the different Multiple components of the number of the hydroxyl in formula, OR bases can be become, Therefore, the degree of substitution as the general formula (FA) in present specification, it is more suitable using average substitution degree, routine can be passed through Method, chart by showing degree of substitution distribution using high performance liquid chromatography area than measuring average substitution degree.

In general formula (FA), R₁~R₈Indicate substituted or unsubstituted alkyl-carbonyl or substituted or unsubstituted aryl carbonyl Base, R₁~R₈It may be the same or different (hereinafter, by R₁~R₈Also referred to as acyl group).As R₁~R₈, specifically, can arrange Lift from synthesize it is above-mentioned illustrated by saccharide ester compound when used monocarboxylic acid acyl group.Specifically, can enumerate：Methanoyl Base, benzoyl, methyl benzoyl, phenyl acetyl, trimethoxybenzoy, isopropynyl etc..

The phase difference film of an embodiment of the invention preferably comprise phase difference film whole (100 mass %) 0.5~ The saccharide ester compound of 30 mass %, the particularly preferably saccharide ester compound containing 2~15 mass %.

Saccharide ester compound can be by making acylation agent (also referred to as esterifying agent, the carboxylic acid halides such as chloroacetic chloride, acetic anhydride etc. Acid anhydride) it is reacted with the sugar to manufacture, the distribution of degree of substitution can be by adjusting the amount of acylation agent, adding time, esterification Time carries out, but by mixing the different saccharide ester compound of degree of substitution or by the different chemical combination of the degree of substitution after simple separation Object is mixed, so that it may to prepare target average substitution degree, 4 ingredient below of degree of substitution.

(synthesis example：The synthesis example of saccharide ester compound)

[chemical formula 22]

Sucrose 34.2g is packed into the four-hole boiling flask with agitating device, reflux cooler, thermometer and nitrogen ingress pipe (0.1 mole), benzoyl oxide 135.6g (0.6 mole), pyridine 284.8g (3.6 moles) are imported from nitrogen under stiring on one side Pipe makes nitrogen boil, and heats up on one side, and 5 hours esterifications are carried out at 70 DEG C.

Then, it is 4 × 10 to make decompression in flask²After Pa at 60 DEG C hereinafter, evaporate excessive pyridine, make to subtract in flask Pressure is 1.3 × 10Pa hereinafter, be warming up to 120 DEG C, and the major part of benzoyl oxide, the benzoic acid of generation is evaporated.Moreover, then adding The aqueous sodium carbonate 300g for adding toluene 1L, 0.5 mass % after being stirred 30 minutes at 50 DEG C, stands, divides and take toluene layer.Most Afterwards, water 100g is added in point toluene layer taken, after washing 30 minutes at normal temperatures, divides and take toluene layer, under reduced pressure (4 × 10²Pa or less), evaporate toluene at 60 DEG C, obtain as mixtures such as compound A-1, A-2, A-3 and A-4 and A-5 Saccharide ester compound 1.

Obtained mixture is analyzed with high performance liquid chromatography quality analysis (HPLC-MS), as a result, average substitution degree is 5.5。

Then, by using a part for the column chromatography eluting obtained mixture of silica gel, purity is thus obtained 100% saccharide ester compound.

It should be noted that described " A-5 etc. " refers to for the whole ingredient below of degree of substitution 4, i.e. degree of substitution 4,3,2,1 Compound mixture.In addition, for average substitution degree, A-5 etc. is calculated as degree of substitution 4.

In the present invention, by the method that makes here combination addition close to the sugar ester of desired average substitution degree and A-1~A-5 etc. after separation, thus adjusts average substitution degree.

The determination condition > of < HPLC-MS

1) portions LC

Device：Column baking oven (JASCO (registered trademark) CO-965), the wave detector (JASCO of Japan Spectroscopy Corporation's manufacture (registered trademark) UV-970-240nm), pump (JASCO (registered trademark) PU-980), degasser (JASCO (registered trademark) DG- 980-50)

Column：5 μm of 4.6 × 250mm of Inertsil (registered trademark) ODS-3 grain sizes (manufacture of GL science Co., Ltd.)

Column temperature：40℃

Flow velocity：1ml/min

Mobile phase：THF (1% acetic acid)：H₂O(50:50)

Injection rate：3μl

2) portions MS

Device：LCQ DECA (manufacture of ThermoQuest Co., Ltd.)

Ionization method：Electro-spray ionization (ESI) method

Spray Voltage：5kV

Capillary temperature：180℃

Vaporizer temperature：450℃.

(petchem)

The phase difference film of the present invention preferably comprises petchem.

Petchem is not particularly limited, and can be used for example can be by dicarboxylic acids or their ester-forming derivatives End obtained from condensation reaction with glycol is the polymer (polyester polyol) of hydroxyl (hydroxyl) or is gathered to this with monocarboxylic acid Polymer (end capped polyesters) obtained from the terminal hydroxyl of ester polyol is blocked.Ester-forming derivatives mentioned here are two The carboxylate of carboxylic acid, the acid anhydride of dicarboxyl acyl chlorides, dicarboxylic acids.

, it is preferable to use the following general formula from the viewpoint of highly having both the intermiscibility of control and cellulose esters of penetrability (FB) petchem indicated.

General formula (FB)

B-(G-A)_n-G-B

(in formula, B indicates that hydroxyl or carboxylic acid residues, G indicate the aklylene glycol residue or carbon atom of carbon atom number 2~18 The oxyalkylene diol residue that the aryl-diol residue or carbon atom number of number 6~12 are 4~12, A indicate carbon atom number 4~12 Aryl dicarboxylic acid's residue of alkylene dicarboxylic acids residue or carbon atom number 6~12, n indicate 1 or more integer.)

The petchem that general formula (FB) indicates, aklylene glycol shown in hydroxyl or carboxylic acid residues and G shown in B Alkylene dicarboxylic acids residue or aryl dicarboxylic acid's residue shown in residue or oxyalkylene diol residue or aryl-diol residue, A It constitutes, is obtained by similarly being reacted with common ester type compound.

As the carboxylic acid composition for the polyesters compound that general formula (FB) indicates, such as：Acetic acid, propionic acid, butyric acid, benzoic acid, P-tert-butyl benzoic acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethylamino benzonitrile Acid, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, aliphatic acid etc., these substances can use a kind respectively Or use mixture of more than two kinds.

The aklylene glycol ingredient of the carbon atom number 2~18 of polyesters compound as general formula (FB) expression, has：Second two Alcohol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- propylene glycol, 2- methyl-1,3-propanediols, 1,4- butanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propylene glycol (neopentyl glycol), 2,2- diethyl -1,3- propylene glycol (3,3- dihydroxymethyls pentane), 2- normal-butyl -2- ethyl -1,3- propylene glycol (3,3- dihydroxymethyls heptane), 3- methyl-1s, 5- penta Glycol, 1,6-HD, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols, 2- methyl-1s, 8- ethohexadiols, 1,9- nonanediol, 1,10- decanediols, 1,12- octacosanols etc., these glycol use a kind or use mixing of more than two kinds Object.

In particular, the aklylene glycol of carbon atom number 2~12 and the intermiscibility of cellulose ester resin are excellent, therefore, especially It is preferred that.The more preferably aklylene glycol of carbon atom number 2~6, the further preferably aklylene glycol of carbon atom number 2~4.

The aryl-diol of the carbon atom number 6~12 of petchem as general formula (FB) expression, such as：1,4- hexamethylenes two The cyclic diols classes such as alcohol, 1,4-CHDM, hexamethylene diethanol, Isosorbide-5-Nitrae-benzene dimethanol, these glycol can use one It plants or as two or more mixtures.

In addition, as above-mentioned general formula (FB) indicate polyesters compound carbon atom number 4~12 oxyalkylene glycol Ingredient, such as have：Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol etc., these glycol can use 1 Kind uses mixture of more than two kinds.

The alkylene dicarboxylic acids ingredient of the carbon atom number 4~12 of polyesters compound as general formula (FB) expression, such as： Succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid etc., these substances can be with 1 kind is used respectively or uses mixture of more than two kinds.

Aryl dicarboxylic acid's ingredient of the carbon atom number 6~12 of polyesters compound as general formula (FB) expression, including：It is adjacent Phthalic acid, terephthalic acid (TPA), M-phthalic acid, 1,5- naphthalene dicarboxylic acids, 1,4- naphthalene dicarboxylic acids etc..

The weight average molecular weight for the polyesters compound that general formula (FB) indicates is suitble to preferably 300~1500, it is more preferable 400~ 1000 range.In addition, its acid value is 0.5mgKOH/g hereinafter, hydroxyl (hydroxyl) value is 25mgKOH/g hereinafter, more preferable acid value For 0.3mgKOH/g hereinafter, hydroxyl (hydroxyl) value is 15mgKOH/g or less.

The phase difference film of the present invention is poly- containing 0.1~30 mass % preferably with respect to phase difference film whole (100 mass %) Ester compounds particularly preferably contain 0.5~10 mass %.

(acrylic compounds)

The phase difference film of the present invention preferably contains acrylic compounds for the purpose of water resistance.As acrylic compounds chemical combination Object is not particularly limited, and can enumerate with from selected from (methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide The polymer of the repetitive unit of arbitrary at least one kind of acrylic monomer in class and (methyl) acrylonitrile.

Wherein, as acrylic compounds, the methyl methacrylate units of 50~99 mass % and total are preferably comprised Amount is the other monomeric units that can be copolymerized with it of 1~50 mass %.

As copolymerizable other monomers, can enumerate：The alkyl methacrylate that the carbon atom number of alkyl is 2~18； The alkyl acrylate that the carbon atom number of alkyl is 1~18；Acryloyl morpholine or N, N- dimethacrylamide etc. have acyl The vinyl monomer of amido；There is the methacrylate or acrylic acid of the alicyclic type hydrocarbon of carbon atom number 5~22 in ester moiety Ester；The α such as acrylic acid, methacrylic acid, beta-unsaturated acid；The binary carboxylic containing unsaturated group such as maleic acid, fumaric acid, itaconic acid Acid；The aromatic ethenyl compounds such as styrene, α-methylstyrene；The α such as acrylonitrile, methacrylonitrile, alpha, beta-unsaturated nitriles；Horse Come acid anhydrides, maleic amide, N- substitutions maleic amide, glutaric anhydride etc., these substances can be used alone, or combine two or more Monomer.

In addition, as used acrylic compounds in an embodiment of the invention, there can be ring knot Structure, specifically, can enumerate：Lactone ring structure, glutaric anhydride structure, glutarimide structure, N- replace maleic amide structure And maleic anhydride structure, pyranose ring structure.

Wherein, so that it may excellent from the viewpoint of the resistance to pyrolytic or mobility of copolymer for other monomers of copolymerization Select alkyl acrylate, acryloyl morpholine or dimethacrylamide etc. that the carbon atom number of alkyl is 1~18 that there is amide The vinyl monomer of base, ester moiety have carbon atom number 5~22 alicyclic type hydrocarbon methacrylate or acrylate, N- replaces maleic amide structure, pyranose ring structure etc..

The concrete example for the alkyl acrylate that carbon atom number as alkyl is 1~18, can enumerate：Methyl acrylate, third Olefin(e) acid ethyl ester, n-propyl, n-butyl acrylate, sec-butyl acrylate, 2-EHA etc., are preferably listed third E pioic acid methyl ester.

As the concrete example of the vinyl monomer with amide groups, can enumerate：Acrylamide, N methacrylamide, N- Butylacrylamide, N, N- dimethacrylamide, N, N- acrylamides, acryloyl morpholine, N- hydroxyethyls third Acrylamide, acryloyl group pyrrolidines, acryloylpiperidine, Methacrylamide, N- methyl methacrylamides, N- butyl methyls Acrylamide, N, N- dimethylmethacryl amides, N, N- diethyhnethacrylamides, methylacryloyl morpholine, N- hydroxyls Base ethyl methacrylamide, methylacryloyl pyrrolidines, methacryloylpiperidine, N- vinyl formamides, N- ethylene Yl acetamide, vinyl pyrrolidone etc..Acryloyl morpholine, N, N- dimethacrylamide, N- butyl propyleneglycols is preferably listed Amide, vinyl pyrrolidone, 2-hydroxyethyl methacrylate.

As the methacrylate of the alicyclic type hydrocarbon in ester moiety with carbon atom number 5~22 or the tool of acrylate Body example, it can be mentioned, for example：Acrylic acid ring pentyl ester, cyclohexyl acrylate, acrylic methyl cyclohexyl, acrylic acid 3-methyl cyclohexanol Ester, acrylic acid norbornyl ester, acrylic acid norborny methyl esters, acrylic acid cyano norbornyl ester, isobornyl acrylate, acrylic acid Norbornene ester, acrylic acid menthyl ester, acrylic acid turnip ester, acrylic acid Buddha's warrior attendant alkyl ester, acrylic acid dimethyladamantane ester, acrylic acid tricyclic [5.2.1.0^2,6] decyl- 8- base esters, acrylic acid tricyclic [5.2.1.0^2,6] decyl- 4- methyl esters, acrylic acid ring last of the ten Heavenly stems ester, methacrylic acid Ring pentyl ester, cyclohexyl methacrylate, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, metering system Sour norbornyl ester, norbornyl base methyl esters, methacrylic acid cyano norbornyl ester, methacrylic acid phenyl norborneol Ester, isobornyl methacrylate, methacrylic acid norbornene ester, Menthyl methacrylate, methacrylic acid turnip ester, methyl-prop Olefin(e) acid Buddha's warrior attendant alkyl ester, dimethylaminoethyl acrylate methyl ester Buddha's warrior attendant alkyl ester, methacrylic acid tricyclic [5.2.1.0^2,6] decyl- 8- base esters, methyl Acrylic acid tricyclic [5.2.1.0^2,6] decyl- 4- methyl esters, methacrylic acid ring last of the ten Heavenly stems ester, methacrylic acid bicyclopentane base ester etc..

Isobornyl methacrylate, methacrylic acid bicyclopentane base ester, dimethylaminoethyl acrylate methyl ester gold is preferably listed Rigid alkyl ester etc..

Replace maleic amide as N-, it can be mentioned, for example：N- methylycaconitines, N- ethylmaleimides, N- propyl horses Come amide, N- isopropyls maleic amide, N- butyl maleic amide, N- isobutyl groups maleic amide, N- tertiary butyls maleic amide, the N- months Osmanthus base maleic amide, N- cyclohexyl maleic amide, N- benzyls maleic amide, N- phenyl maleimides, N- (2- chlorphenyls) Malaysia Amide, N- (4- chlorphenyls) maleic amide, N- (4- bromophenyls) phenyl maleimide, N- (2- aminomethyl phenyls) maleic amide, N- (2- ethylphenyls) maleic amide, N- (2- methoxyphenyls) maleic amide, N- (2,4,6- trimethylphenyls) maleic amide, N- (4- benzyl phenyls) maleic amide, N- (2,4,6- tribromos phenyl) maleic amide etc..

N- methylycaconitines, N- cyclohexyl maleic amide, N- phenyl maleimides etc. is preferably listed.

These monomers can directly use the product that market is sold.

For acrylic compounds, go out from the control for having both penetrability and with the viewpoint of the intermiscibility of cellulose esters Hair, preferable weight-average molecular weight (Mw) is 15000 ranges below, in more preferably 10000 or less range, further preferably In the range of 5000~10000.

As the manufacturing method of acrylic compounds, be not particularly limited, can use suspension polymerisation, emulsion polymerization, Method is any well known to bulk polymerization or polymerisation in solution etc..Here, as polymerization initiator, common peroxide can be used The polymerization initiator of compound class and azo, alternatively, it is also possible to use redox system.About polymerization temperature, suspend or newborn Liquid polymerization can be implemented in the range of 30~100 DEG C, and ontology or polymerisation in solution can be implemented in the range of 80~160 DEG C. For the reduced viscosity of the copolymer controlled, alkyl hydrosulfide etc. can also be implemented to polymerize as chain-transferring agent.

Acrylic copolymer can add in the range of being 1~30 mass parts relative to 100 mass parts of substrate resin.

< others plasticizer >

It can be for phase difference film water resistance be improved, in the phase difference film of the present invention, except above-mentioned saccharide ester compound, polyester Except compound, acrylic compounds, or substitution above compound, use styrene compound.

(styrene compound)

Styrene compound both can be styrene monomer homopolymer, or styrene monomer and other Comonomer copolymer.In order to make molecular structure that there is a certain amount of above large volume, come from styrene compound The content ratio of the Component units of styrene monomer is preferably 30~100 moles of %, can more preferably be rubbed for 50~100 You are %.

Styrene monomer is preferably the compound that following formula (A) indicates.

[chemical formula 23]

R in formula (A)¹⁰¹~R¹⁰³Separately indicate hydrogen atom or the alkyl or aryl of carbon atom number 1~30.R¹⁰⁴ Indicate hydrogen atom, the alkyl of carbon atom number 1~30, naphthenic base, aryl, the alkoxy of carbon atom number 1~30, aryloxy, carbon The alkoxy carbonyl of atomicity 2~30, aryloxycarbonyl, the alkyl carbonyl epoxide of carbon atom number 2~30, aryl carbonyl epoxide, Hydroxyl, carboxyl, cyano, amino, amide groups, nitro.These groups can further have substituent group (such as hydroxyl, halogen respectively Atom, alkyl etc.).R¹⁰⁴Can be identical respectively, it can also be different, can be mutually bonded and form ring.

The example of styrene monomer includes styrene；α-methylstyrene, Beta-methyl styrene, p-methylstyrene etc. Alkyl-substituted styrene class；The halogen substituted phenylethylene class such as 4- chlorostyrenes, 4- bromstyrols；4-Vinyl phenol, Alpha-Methyl-are right The hydroxy styrenes classes such as hydroxy styrenes, 2- methyl -4-Vinyl phenol, 3,4- dihydroxy benzenes ethylene；Vinyl benzyl alcohols； To methoxy styrene, to alkoxy substituted vinyls such as t-butoxystyrene, t-butoxystyrenes；3- vinyl The vinyl benzoic acids classes such as benzoic acid, 4- vinyl benzoic acids；4- vinyl benzyl yl acetates；4- acetoxy-styrenes；2- Butyl amide styrene, 4- methyl nitrosoureas styrene, to the amides phenylethylene such as sulfonamide phenyl ethylene；3- aminostyryls, 4- The aminostyryls classes such as aminostyryl, 2- isopropenyls aniline, vinylbenzyl dimethyl amine；3- nitrostyrolenes, 4- nitre The nitrostyrolenes class such as base styrene；The cyano styrenes classes such as 3- cyano styrenes, 4- cyano styrenes；Ethenylphenyl second Nitrile；The arylstyrenes such as styryl phenyl class, indene etc..Styrene monomer can be one kind, can also combine two or more.

The comonomer that can be combined with styrene monomer includes (methyl) acrylate chemical combination that following formula (B) indicates Object, maleic anhydride, citraconic anhydride, cis- -1- cyclohexene -1,2- dicarboxylic anhydrides, 3- methyl-cis- 1- cyclohexene -1,2- dicarboxyls The radical polymerizations containing nitrile such as acid anhydrides, acrylonitrile, the methacrylonitriles such as acid anhydrides, 4- methyl-cis- 1- cyclohexene -1,2- dicarboxylic anhydrides Conjunction property monomer；The amide bonds such as acrylamide, Methacrylamide, trifluoromethanesulphonylamino ethyl (methyl) acrylate Free radical polymerization monomer；The fatty acid ethylenes esters such as vinyl acetate；Vinyl chloride, vinylidene chloride etc. are polymerize containing chlorine by base Property monomer；1,3-butadiene, isoprene, Isosorbide-5-Nitrae-dimethyl butadiene equiconjugate alkadiene etc., preferably following formula (B) table (methyl) acrylate compounds or maleic anhydride shown.

[chemical formula 24]

R in formula (B)¹⁰⁵~R¹⁰⁷Separately indicate hydrogen atom or the alkyl or aryl of carbon atom number 1~30.R¹⁰⁸ Indicate hydrogen atom, the alkyl of carbon atom number 1~30, naphthenic base or aryl.These groups can further have substituent group respectively (such as hydroxyl, halogen atom, alkyl etc.).

The example of (methyl) acrylic ester compound includes：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid (different, just) propyl ester, (methyl) acrylic acid (just, different, secondary, uncle) butyl ester, (methyl) acrylic acid (just, different, secondary) Pentyl ester, the own ester of (methyl) acrylic acid (just, different), (methyl) acrylic acid (just, different) heptyl ester, (methyl) acrylic acid (just, different) monooctyl ester, (methyl) acrylic acid (just, different) nonyl ester, (methyl) acrylic acid (just, different) tetradecane base ester, (methyl) acrylic acid (2- ethyl hexyls Base) ester, (methyl) acrylic acid (6-caprolactone), (methyl) acrylic acid (2- hydroxyethyls) ester, acrylic acid (2- hydroxypropyls) ester, (methyl) acrylic acid (3- hydroxypropyls) ester, (methyl) acrylic acid (4- hydroxybutyls) ester, (methyl) acrylic acid (2- hydroxyl fourths Base) ester, acrylic acid (2- methoxy ethyls) ester, (methyl) acrylic acid (2- ethoxyethyl groups) phenyl acrylate, (methyl) methyl Phenyl acrylate, (methyl) acrylic acid (2 or 4- chlorphenyls) ester, (methyl) acrylic acid (2 or 3 or 4- carboethoxyphenyls) Ester, (methyl) acrylic acid (adjacent or or p-methylphenyl) ester, (methyl) benzyl acrylate, (methyl) phenylethyl, (first Base) acrylic acid (2- naphthalenes) ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid (4- methylcyclohexyls) ester, (methyl) third Olefin(e) acid (4- ethylcyclohexyls) ester etc..

The concrete example of styrene compound includes phenylethylene/maleic anhydride copolymer, phenylethylene ethylene/propenoic acid ester copolymerization Object, styrene/hydroxystyrene polymers, styrene/acetoxystyrene polymer etc..Wherein, optimization styrene/Malaysia Acid anhydride copolymer.

Styrene compound can add in the range of being 1~30 mass parts relative to 100 mass parts of substrate resin.

(other)

In the phase difference film of the present invention, above-mentioned saccharide ester compound, petchem, acrylic compounds and styrene are removed Except class compound or replace these above-mentioned compounds, it is 15000 or less, preferably 10000 public affairs below that can use molecular weight The plasticizer known.It as other plasticizer, is not particularly limited, preferably from polybasic carboxylic acid esters plasticizer, glycolic esters It is selected in plasticizer, phthalic ester plasticizer, fatty acid ester plasticiser and polyalcohol ester plasticizer etc..Wherein, Preferred plasticizer is polyalcohol ester plasticizer.

From the viewpoint of efficiently controlling penetrability, preferably as polyalcohol ester type compound, Japanese spy can be enumerated Open compound recorded in numbered paragraphs [0170]~[0218] of 2010-32655 bulletins.Wherein, it is preferable to use season penta Four benzoic ether of tetrol.

The content of these plasticizer preferably with respect to 100 mass parts of substrate resin be 6~40 mass parts range, preferably 10 The range of~20 mass parts.

(c) the binding affinity compound of hydrogen

Phase difference in order to reduce the variation relative to humidity changes, and it is binding affinity that phase difference film of the invention preferably comprises hydrogen Compound.

As the binding affinity compound of the hydrogen, preferably in a molecule at least have selected from multiple hydroxyls, amino, mercapto, Functional group in carboxylic acid group more preferably has multiple and different functional groups in an intramolecular, particularly preferably has in an intramolecular Hydroxyl and carboxylic acid group.

The binding affinity compound of the hydrogen preferably comprises 1~2 aromatic ring as parent nucleus, contained in a molecule described in Value obtained by the number of functional group divided by the molecular weight of compound is preferably 0.01 or more.

Said effect presumption is due to acting on generation as follows：The above-mentioned binding affinity compound bonding (passing through hydrogen bonding) of hydrogen exists The position of the substrate resins such as the cellulose esters and hydrone interaction (hydrogen bonding) inhibits electric caused by the desorption of hydrone The variation of lotus distribution.

As specific compound example, can enumerate described in Japanese Unexamined Patent Publication 2011-227508 bulletins paragraph [0029] Compound is, it is preferable to use 3- cresotinic acids.

The binding affinity compound of hydrogen can add in the range of being 1~30 mass parts relative to 100 mass parts of substrate resin.

(d) other any ingredients

The phase difference film of the present invention can contain antioxidant, colorant, ultra-violet absorber, delustering agent, acrylic acid grain Other any ingredients such as son, hydrogen bond solvent, ionic surfactant.These ingredients can be relative to substrate resin 100 Mass parts be 0.01~20 mass parts in the range of add.

< antioxidants >

The phase difference film of the present invention can use commonly known substance as antioxidant.It especially can be it is preferable to use Lactone, sulphur class, phenols, double bond class, hindered amines, Phosphorus each compound.

As above-mentioned lactone compound, can enumerate by BASF Amada Co., Ltd.s sold " IrgafosXP40, IrgafosXP60 (trade name) " etc..

Above-mentioned sulphur class compound can enumerate " SumilizerTPL-R " for example sold by Sumitomo Chemical Co And " SumilizerTP-D ".

As above-mentioned phenolic compound, preferably there is the structure of 2,6- dialkyl group phenol, can enumerate for example by BASF days " Irganox (registered trademark) 1076 " that this Co., Ltd. is sold, " Irganox (registered trademark) 1010 ", by Co., Ltd. " ADK STAB (registered trademark) AO-50 " etc. that ADEKA is sold.

Above-mentioned double bond class compound by Sumitomo Chemical Co with " Sumilizer (registered trademark) GM " and The trade name of " Sumilizer (registered trademark) GS " is sold.In general, relative to resin, in 0.05~20 mass %, preferably It is added in the range of 0.1~1 mass %.

Above-mentioned hindered amine compound can enumerate " Tinuvin (the registrations for example sold by BASF Amada Co., Ltd.s Trade mark) 144 " and " Tinuvin (registered trademark) 770 ", by Asahi Denka Co., Ltd. sell " ADKSTAB (registered trademark) LA- 52”。

Above-mentioned phosphorus species can enumerate " Sumilizer (the registrars for example sold by Sumitomo Chemical Co Mark) GP ", by Asahi Denka Co., Ltd. sell " ADKSTAB (registered trademark) PEP-24G ", " ADKSTAB (registered trademark) PEP- 36 " and " ADKSTAB (registered trademark) 3010 ", sold by BASF Amada Co., Ltd.s " IRGAFOSP-EPQ ", by Sakai chemistry " GSY-P101 " of Industrial Co., Ltd's sale.

In addition, as sour enriching substance, it can be containing U.S. Patent No. 4,137,201 is recorded in specification, has The compound of epoxy group.

These antioxidants etc. can coordinate regeneration using when process determine the amount being properly added, it is however generally that, phase For phase difference film main material, that is, resin (such as cellulose esters etc.), 0.05~20 mass %'s, preferably 0.1~1 mass % Addition in range.

For these antioxidants etc., compared with using only a kind, by the chemical combination that a variety of different classifications are applied in combination Object can obtain synergy.For example, it is preferable to which lactone, Phosphorus, phenols and double bond class compound is applied in combination.

< colorants >

For the phase difference film of the present invention, in order to adjust tone, preferably within the scope of the effect of the invention Contain colorant.So-called colorant refers to dyestuff or pigment, refers to having the hue adjustment of liquid crystal panel to be in of the invention The substance of the effect of blue cast has the effect of adjusting the substance of the effect of yellow colour index, reduction mist degree.

As colorant, various dyestuffs, pigment can be used, but anthraquinone dye, azo dyes, phthalocyanine color etc. are effective 's.

< ultra-violet absorbers >

The phase difference film of the present invention can be used for identification side or the backlight side of polarizing film, therefore, to assign ultraviolet light suction For the purpose of receiving function, ultra-violet absorber can be contained.

As ultra-violet absorber, it is not particularly limited, it can be mentioned, for example：Benzotriazole, 2- hydroxy benzophenone ketones Or the ultra-violet absorbers such as phenyl salicylate class.It may be exemplified for example：2- (5- methyl -2- hydroxy phenyls) benzotriazole, 2- [bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl of 2- hydroxyls -3,5-] -2H- benzotriazole, 2- (3,5- di-t-butyl -2- hydroxy phenyls) benzene And the triazole types such as triazole, ESCALOL 567,2- hydroxyl -4- octyloxybenzophenones, 2,2 '-dihydroxy -4- The benzophenones such as methoxy benzophenone.

It should be noted that in ultra-violet absorber, the ultra-violet absorber that molecular weight is 400 or more is not easy to distil, Or boiling point height is not easy to disperse without volatile in phase difference film high temperature drying, therefore, from can be with fewer additive amount It is preferred that can effectively improve from the perspective of weatherability.

The ultra-violet absorber for being 400 or more as molecular weight, it can be mentioned, for example：2- [2- hydroxyls -3,5- bis- (α, α-two Methylbenzyl) phenyl] -2 benzotriazole, 2,2- di-2-ethylhexylphosphine oxides [4- (the 1,1,3,3- tetrabutyls) -6- (2H- benzotriazole -2- Base) phenol] etc. enumerate BTA systems, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis- (1,2,2,6,6- pentamethyls- 4- piperidyls) sebacate etc. be obstructed amine system and 2- (3,5- di-tert-butyl-4-hydroxyl benzyls) -2- n-butylmalonic acids it is double (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 1- [2- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy] second Base] -4- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy] -2,2,6,6- tetramethyl piperidines etc. have in the molecule Have the substance of the mixed system of the structure of fortified phenol and hindered amine, these substances can be used alone, or be applied in combination 2 kinds with On.Wherein, particularly preferred 2- [bis- (alpha, alpha-dimethylbenzyl) phenyl of 2- hydroxyls -3,5-] -2 benzotriazole or 2,2- methylene Bis- [4- (the 1,1,3,3- tetrabutyls) -6- (2H- benzotriazole -2- bases) phenol].

As these ultra-violet absorbers, sales item can be used, such as can it is preferable to use BASF Amada Co., Ltd.s Tinuvin (registered trademark) 109, Tinuvin (registered trademark) 171, Tinuvin (registered trademark) 234, the Tinuvin (notes of system Volume trade mark) 326, Tinuvin (registered trademark) 327, Tinuvin (registered trademark) 328, Tinuvin (registered trademark) 928 etc. Tinuvin series or 2,2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyls) phenol] (as molecular weight 659；The example of sales item is the LA31 of Asahi Denka Co., Ltd.'s manufacture).

Above-mentioned ultra-violet absorber can be used alone, or two or more is applied in combination.

The usage amount of ultra-violet absorber is different due tos the type of ultra-violet absorber, use condition etc., it is however generally that, phase For substrate resin, added in the range of 0.05~10 mass %, preferably 0.1~5 mass %.

< delustering agents >

The phase difference film of the present invention preferably adds the particle (delustering agent) for assigning phase difference film slipping.

It, then can be with as long as the phase difference film transparency do not damaged and heat resistance when with melting as delustering agent It is any for inorganic compound or organic compound.These delustering agents may be used singly or in combination of two or more.

Can highly it be had both by the different particles of grain size or shape (such as needle-shaped and spherical etc.) are applied in combination The transparency and slipping.

Wherein, it is preferable to use refractive index and the acrylic copolymer or cellulose esters as the resin that mixes close to thus Transparent (mist degree) excellent silica.

As silica concrete example it is preferable to use with AEROSIL (registered trademark) 200V, AEROSIL (note Volume trade mark) R972V, AEROSIL (registered trademark) R972, R974, R812,200,300, R202, OX50, TT600, NAX50 (with AEROSIL Co., Ltd. of upper Japan manufacture), SEAHOSTAR (registered trademark) KEP-10, SEAHOSTAR (registered trademark) KEP- 30, SEAHOSTAR (registered trademark) KEP-50 (more than, Nippon Catalyst K. K. manufacture), SYLOPHOBIC (registrars Mark) 100 (manufactures of Fuji Silysia Co., Ltd.), Nipsil (registered trademark) E220A (Japanese silica industry strain formula meetings Society manufactures), the sales items etc. of the trade names such as Admafine (registered trademark) SO (Co., Ltd. ADMATECHS manufactures).

It as the shape of particle, can use amorphous, needle-shaped, flat, spherical etc., especially make without particular limitation When with spherical particle, the phase difference film transparency that can make is good, therefore preferably.

For the size of particle, close to visible light wavelength when, light scattering and the transparency be deteriorated, it is therefore preferable that than The wavelength of visible light is small, further preferably 1/2 or less the wavelength of visible light.When the size of particle is too small, it cannot change sometimes Kind slipping, it is therefore especially preferred that for the range of 80nm~180nm.It should be noted that for the size of particle, particle Refer to the size of agglutination body in the case of agglutination body for 1 particle, refers to suitable in addition, in the case that particle is not spherical In the diameter of a circle of its projected area.

Delustering agent adds preferably with respect to substrate resin, in the range of 0.05~10 mass %, preferably 0.1~5 mass % Add.

< acrylic particles >

In order to improve phase difference film brittleness, the amount that phase difference film of the invention can be to be able to maintain that in the range of the transparency Contain the acrylic particles described in No. 2010/001668 pamphlet of International Publication No..

The example of sales item as this granular complex of multilayered structure acrylic acid series, it can be mentioned, for example：The beautiful sun of Mitsubishi " METABLEN (registered trademark) W-341 " of Co., Ltd.'s manufacture, " KANEACE (registrars of Co., Ltd. KANEKA manufactures Mark) ", Co., Ltd. Kureha manufacture " PARALOID (registered trademark) ", Rohm and Haas Co. manufacture " Acryloid ", " STAFYROID (registered trademark) ", Chemisnow (registered trademark) MR-2G, MS-300X of GANTZ chemical conversion industries society manufacture " Parapet (registered trademark) SA " etc. of (more than, Soken Chemical & Engineering Co., Ltd. manufacture) and Kuraray Co., Ltd. manufacture, these Substance can be used alone or use two or more.

< hydrogen bond solvents >

It in the present invention, can be for dissolving phase difference film constituent material when making phase difference film with solution casting method Solvent in hydrogen bond solvent added with the purpose of adjustment (reduction) solution viscosity.Hydrogen bond solvent refers to：Such as J.N.Israelachivili written " molecular separating force and surface force " (nearly rattan protects, the wide row in big island is translated, published by McGraw Hill, 1991) in it is recorded as, can generate in electronegativity atom (oxygen, nitrogen, fluorine, chlorine) and be bonded with electronegativity atom covalence Hydrogen atom between generate, the organic solvent of hydrogen atom medium " key ", i.e., by big containing bonding torque and contain hydrogen Key, such as O-H (oxygen hydrogen bond), N-H (hydrogen bound to nitrogen), F-H (fluorine hydrogen bond) and make neighbouring molecule can be with the organic of mutual arrangement Solvent.

Mixing of these substances with acrylic copolymer or cellulose ester resin or for making its other resin mutually dissolved The intermolecular hydrogen bonding of body itself is compared, and by forming the strong hydrogen bond between the resin and hydrogen bond solvent, can expect that solution is viscous The variation of degree.

In the solution casting method carried out in the present invention, relative to the resin solution used, except adjustment solution viscosity it Outside, the purpose of peeling force when can also be film-made with reducing in the solvent for dissolving using a hydrogen binding affinity solvent part or Total amount.

< ionic surfactants >

The purpose of peeling force when the phase difference film of the present invention is preferably film-made with reducing adds ionic surfactant.

As the ionic surfactant that can be used in the present invention, it can be mentioned, for example：Cationic surface's activity Agent, anionic surfactant, amphoteric surfactant etc..

As cationic surfactant, it can be mentioned, for example：Aliphatic amine salt, aliphatic quaternary ammonium salt, zephiran salt, benzyl Rope oronain, pyridiniujm, imidazole salts etc..

As anionic surfactant, including：Higher alcohol (C₈~C₂₂) sulfuric ester salt (such as lauryl alcohol sulfuric acid The sodium salt of ester, the sodium salt of octyl alcohol sulfuric ester, the ammonium salt of lauryl alcohol sulfuric ester, " Teepol-81 " (trade name, Shell Chemical Company manufactures), the second sodium alkyl sulfate etc.), aliphatic alcohol phosphates (such as sodium salt etc. of Phosphoric acid monohexadecyl ester), alkane Base salt aryl sulfonate (such as the sodium salt of the sodium salt of dodecyl benzene sulfonic acid, the sodium salt of isopropyl naphthalene sulfonic acid, two naphthalenedisulfonic acids, The sodium salt etc. of m-nitrobenzene sulfonic acid), the Sulfonates of alkylamide (such as C₁₇H₃₃CON(CH₃)CH₂SO₃Na etc.), di-fatty The Sulfonates (such as sodium sulfosuccinic acid dioctyl ester, sodium sulfosuccinic acid dihexyl ester etc.) of acid esters.Wherein, particularly preferably Use Sulfates or Sulfonates.

As amphoteric surfactant, can enumerate：Carboxy betaine type, sulfobetaine type, aminocarboxylate, imidazoles Glycine betaine etc..

Wherein, in the present invention, it is preferred to anionic surfactant.In addition, the usage amount of above-mentioned surfactant Total amount relative to the substrate resin for constituting phase difference film is preferably 0.01 mass % or more, 5 mass % or less, preferably 0.05 matter Measure % or more 3 mass % or less, more preferable 0.2 mass % or more, 2 mass % or less.When additive amount is more than the range, surface is lived Property agent be precipitated from phase difference film or phase difference film hygroscopicity increase etc., show in terms of optical phase difference film quality not preferably Quality.In addition, when additive amount is less than the range, it is unable to get the effect of the present invention using surfactant.

As described above, the phase difference film of the present invention preferably satisfies：(1) film thickness is 15 μm or more 35 μm hereinafter, (2) width side To and the film thickness deviation in band-like direction be 0~4 μm, the Ro amplitudes of fluctuation that (3) above-mentioned formula (1) indicates are within ± 4%, and Rt becomes Dynamic amplitude is within ± 5%.Above-mentioned (1)~(3) can pass through the casting conditions of control (a) rubber cement or fusant, (b) tension bar Part, (c) use the type of acyl group of the cellulose esters as substrate resin when and the phase difference elevator of degree of substitution, (d) present invention Contained in the type and additive amount of nitrogenous compound (A) and nitrogenous compound (B), the type of (e) plasticizer and additive amount etc. To realize.

For example, total degree of substitution of the cellulose esters of the phase difference film of the present invention is preferably 2.1~2.5.

In addition, total degree of substitution of the cellulose esters of the phase difference film of another embodiment of the invention is 2.1~2.5 (at least one kind of increasing in saccharide ester compound, petchem and acrylic compounds is contained in more preferable 2.15~2.45) Mould agent.More preferable the plasticizer contains saccharide ester compound.

In addition, total degree of substitution of the cellulose esters of the phase difference film of another embodiment of the invention is 2.1~2.5 (hydrogen bond compound is contained in more preferable 2.15~2.45).

《Phase difference film manufacturing method》

Then, the phase difference film manufacturing method of the present invention is illustrated.The present invention is not limited to this.

As the phase difference film manufacturing method of the present invention, common blow moulding, T- modulus methods, rolling process, cutting can be used The autofrettages such as method, the tape casting, emulsion method, pressure sintering, from optical defects such as coloring inhibition, the inhibition of foreign matter disadvantage, pressing mold lines The viewpoints such as inhibition are set out, and film-forming method is preferably solution curtain coating film method and melts casting film method, in order to obtain uniform table Face, particularly preferred solution casting method.

< solution curtain coatings are film-made method >

When being film-made using solution casting method, phase difference film manufacturing method of the invention preferably includes：Make thermoplastic resin and Above-mentioned additive is dissolved in solvent and prepares the process (dissolution process of rubber cement；Rubber cement preparation section), by rubber cement be cast in cycle Process (curtain coating process) on mobile endless metal support body, the process (evaporation of the solvent that the rubber cement of curtain coating is dried to wet film Process), the process that keeps of the process (stripping process) removed from metal support, drying, stretching, width (protect by stretching/width Hold/drying process), the process (rolling step) of phase difference film after coiling process.As thermoplastic resin, particularly preferably use Cellulose esters.

Fig. 1 is to schematically show the rubber cement preparation section of preferred solution casting film device in the present invention, curtain coating work The figure of sequence and an example of drying process (solvent evaporization process).

Big agglutinator, liquor charging to storage kettle 42 are removed from feed chamber 41 with filter 44.Thereafter, from storage kettle 42 to master Rubber cement dissolution kettle 1 adds various annex solutions.

Thereafter, main rubber cement is filtered with main filter 3, wherein by 16 online addition additive annex solutions.

In most cases, material can be returned containing 10~50 mass % or so in main rubber cement.

Return material be by phase difference film it is fine crush made of substance, generated phase when maying be used at film phase difference film The material or the substandard phase difference film original film because of scratch etc. that potential difference film two side portions are cut off.

In addition, as the raw material of the resin prepared for rubber cement, it is preferable to use in advance by the fibre as substrate resin Dimension plain ester and other additives etc., which are granulated, obtains material.

Hereinafter, being illustrated to each process.

1) dissolution process (rubber cement preparation section)

Hereinafter, as an embodiment of the invention, the case where cellulose esters is as thermoplastic resin conduct will be used An example illustrates dissolution process, but the present invention is not limited to this.

This process is following process：In the solvent based on cellulose esters good solvent, by the cellulose in dissolution kettle Ester, according to circumstances and other compounds for adding dissolve while stirring and the process that forms rubber cement, or in the fiber The process for according to circumstances mixing other compound solutions in plain ester solution and forming the rubber cement as main lysate.

When the concentration of cellulose esters in rubber cement is big, drying load of the curtain coating after metal support can be reduced, therefore It is preferred that but cellulose esters concentration it is excessive when, load when filtering increases, and filtering accuracy is deteriorated.As having both above-mentioned characteristic Concentration, preferably 10~35 mass %, further preferably 15~30 mass %.

Solvent used in rubber cement may be used singly or in combination of two or more, and be examined in terms of production efficiency Consider, preferably mix the good solvent of cellulose esters and poor solvent and uses, from the aspect of the dissolubility of cellulose ethanoate, Preferred good solvent is more.

The preferred scope of the blending ratio of good solvent and poor solvent is that good solvent is 70~98 mass %, and poor solvent is 2~30 mass %.Good solvent, poor solvent are such as given a definition：The solvent that the cellulose esters used will individually be dissolved is defined as Good solvent, the solvent that will be individually swollen or can not dissolve cellulose esters are defined as poor solvent.Therefore, good solvent, bad Solvent changes according to the difference of the average substitution degree of cellulose esters.

Good solvent used in the present invention is not particularly limited, and can enumerate the organic halogen compounds such as dichloromethane or dioxy Penta ring class, acetone, methyl acetate, methyl acetoacetate etc..Particularly preferably enumerate dichloromethane or methyl acetate.

In addition, the poor solvent used in the present invention is not particularly limited, such as preferably using methanol, ethyl alcohol, just Butanol, hexamethylene, cyclohexanone etc..Additionally, it is preferred that the water containing 0.01~2 mass % in rubber cement.

In addition, for the solvent of the dissolving used in cellulose esters, recycles and pass through in phase difference film film making process The solvent dried and removed from phase difference film, is recycled and is used.

Sometimes it is inhaled containing the micro additive for making an addition to cellulose esters, such as plasticizer, ultraviolet light in recycling design Agent, polymer, monomer component etc. are received, even if containing these substances, can also preferably recycle, can also carry out as needed pure It is recycled after change.

The dissolving method of cellulose esters when as the rubber cement for preparing above-mentioned record can use general method.Specifically For, can use carry out under normal pressure method, carried out below the boiling point of main solvent method, main solvent boiling point with Upper pressurization and the method, special with Japanese Unexamined Patent Publication 9-95544 bulletins, Japanese Unexamined Patent Publication 9-95557 bulletins or Japan carried out Method that the hot-cold lysis method opened described in flat 9-95538 bulletins etc carries out, in Japanese Unexamined Patent Publication 11-21379 bulletins In the various dissolving methods such as the method that carries out under recorded high pressure.Wherein, preferably pressurize more than the boiling point of main solvent and into Capable method when by being heated and pressurizeed combination, can be heated to the boiling point under normal pressure or more.

In addition, being carried out on one side at a temperature of solvent will not boil more than the atmospheric boiling point of solvent and under elevated pressure range The method for being stirred dissolving on one side is heated, is also prevented from the generation for the blocky insoluble matter for being referred to as gel or powder ball, therefore preferably.

In addition, it is also preferred that using cellulose esters is mixed with poor solvent and after being moistened or being swollen, further The method that addition good solvent is dissolved.

Pressurization can be by being pressed into the method for the inert gases such as nitrogen or by heating the side for making the vapour pressure of solvent increase Method carries out.Heating is preferably carried out from outside, such as the device of bushing type is easy to control temperature, therefore it is preferred that.

From the viewpoint of the dissolubility of cellulose esters, the heating temperature for preferably adding solvent is high, but heating temperature is excessively high When, the pressure needed increases, and productivity is deteriorated.

Preferred heating temperature is 45~120 DEG C, more preferably 60~110 DEG C, further preferably 70 DEG C~105 DEG C. In addition, pressure can be adjusted in such a way that solvent under set temperature will not boil.

Alternatively, hot-cold lysis method is further preferably used, it is possible thereby to dissolve cellulose esters in methyl acetate equal solvent.

Then, the cellulose ester solution (in dissolving or dissolved rubber cement) is preferably used into the filter materials appropriate such as filter paper Material is filtered.

As filtering material, in order to remove insoluble matter etc., the preferably small filtering material of filtering precision, but absolute filtration When precision is too small, there are problems that the blocking for easy ting produce filtering material.It is therefore preferable that filtering precision 0.008mm or less Filter material, the filter material of more preferable 0.001~0.008mm, the filter material of further preferred 0.003~0.006mm.

The material of filter material is not particularly limited, and can use common filter material, but polypropylene, teflon (registered trademark) etc. Filter material made of filter material or stainless steel metal made of plastics due to not no fiber fall off etc. and it is preferred that.

It is preferred that being removed by filtering and reducing impurity, particularly bright spot foreign matter contained in the cellulose esters of raw material.

Bright spot foreign matter refers to：2 polarizing films are configured with orthogonal Nikkor state, place phase difference film therebetween Deng, when from a piece of polarizing film side irradiation light and from another polarizing film side, the light leakage from opposite side and be seen Point (foreign matter), the bright spot number of preferably a diameter of 0.01mm or more is 200/cm²Below.More preferably 100/cm²Hereinafter, Further preferably 50/m²Hereinafter, further preferably 0~10/cm²Below.Additionally, it is preferred that 0.01mm bright spots below Also seldom.

The filtering of rubber cement can be carried out with usual way, and it is more than the boiling point under the normal pressure of solvent, and it is molten under elevated pressure The method being filtered while being heated at a temperature of the range that agent will not boil, before filtration after filtering pressure difference The rising of (being known as differential pressure) is small, therefore it is preferred that.

Preferred temperature is 45~120 DEG C, more preferably 45~70 DEG C, further preferably 45~55 DEG C.

It is preferred that filtering pressure is smaller.Filtering pressure is preferably 1.6MPa hereinafter, more preferably 1.2MPa is hereinafter, further preferably 1.0MPa following.

2) it is cast process

Then, by rubber cement curtain coating (cast) in metal support.That is, this process is following process：By rubber cement by sending Rubber cement is cast in loopy moving to compression molding 30 from compression molding slit by liquid pump (such as compression type quantitative gear pump) liquor charging Endless metal belt 31, on the casting position such as stainless steel band or the metal drum of rotation in metal support.

It is preferred that the shape of slit of the mouth mold part of mold can be adjusted, be easy to make the compression molding of uniform film thickness.Compression molding packet Include coat hanger die or T moulds etc., it is preferably to use.It is preferred that the surface of metal support becomes minute surface.It, can be in order to improve film speed 2 or more compression moldings are set in metal support, rubber cement amount is split and lamination.Or it is also preferred that by by a variety of glue Slurry simultaneously be cast common curtain coating method and obtain the phase difference film of laminated construction.

From the viewpoint of productivity, the preferred 1.4m or more of width of curtain coating.More preferably 1.4~4m.More than 4m's In the case of, it is possible to occur striped in manufacturing process, or the stability in conveying operation thereafter is lower.From transporting, life Yield aspects consideration, further preferably 2~3.5m.

It is cast metal support of the metal support in (cast) process preferably to surface mirror finishing, as metal Supporter, it is preferable to use stainless steel band or with casting to surface carried out plating finishing drum.

Be cast process metal support surface temperature be -50 DEG C~be less than solvent boiling point temperature, it is wet when temperature is high The rate of drying of film can be accelerated, thus preferably, but it is excessively high when, sometimes wet film can foam or flatness be deteriorated.

Preferred support temperature is 0~55 DEG C, further preferably 22~50 DEG C.Alternatively, keeping wet film solidifying by cooling Gelatinization, it is also preferred method to be removed from drum with the state containing more residual solvent.

The method for controlling the temperature of metal support is not particularly limited, and has the method for blowing warm wind or cold wind or makes temperature The method of water and metal support backside contact.The transmission of heat can be effectively performed using the method for warm water, therefore, metal support The time that temperature reaches constant is short, therefore it is preferred that.In the case of using warm wind, the temperature higher than target temperature is used sometimes Wind.

3) solvent evaporization process

This process is to flow wet film (in curtain coating with rubber cement is cast on supporter, will be formed by rubber cement film and be known as wet film) Adopt the process that evaporation of the solvent is heated, made on supporter.

In order to make evaporation of the solvent, following methods may be used：From the method for wet film cross air blasting and/or from supporter back side profit With the method that liquid conducts heat, the method etc. conducted heat from positive and negative by radiant heat, but rear surface liquid heat-transferring method, do Dry efficiency is good, therefore it is preferred that.In addition, it is also preferred that these methods are applied in combination.It is preferred that the wet film on the supporter after curtain coating is made to exist It is dried on supporter under 35~100 DEG C of atmosphere.In order to maintain 35~100 DEG C of atmosphere, preferably to blowing above wet film The warm wind of the temperature, or heated by modes such as infrared rays.

From the viewpoint of the quality in face, penetrability, fissility, by the wet film from support preferably within 30~120 seconds It is removed on body.

4) stripping process

Then, wet film is removed from metal support.That is, this process is following process：It will be steamed in metal support The process that the wet film of solvent is removed in stripping position is sent out.The wet film being stripped is admitted to subsequent processing.

The temperature on stripping position in metal support is preferably set in the range of -50~40 DEG C, more preferably 10~ In the range of 40 DEG C, most preferably it is set as in the range of 15~30 DEG C.

It should be noted that residual solvent amount can basis in the stripping of the wet film on supporter for the metal at stripping moment The power of drying condition, length of metal support etc. and suitably adjust.In order to which phase difference film shows good flatness, from gold The residual solvent amount belonged to when removing wet film on supporter is preferably 10~150 mass %.At the time of residual solvent amount is more into When row stripping, when wet film is excessively soft, when stripping, damages flatness, easy tos produce adhesion or vertical stripe caused by stripping tension, Therefore, residual solvent amount when stripping is determined according to the balance of economic pace and quality.Further preferably 20~40 mass % Or 60~130 mass %, particularly preferably 20~30 mass % or 70~120 mass %.

In the present invention, residual solvent amount is defined with following formula.

[mathematical expression 4]

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

In addition, M be during manufacturing or any time after manufacture take wet film or phase difference film sample quality, N is Quality after M is heated 1 hour at 115 DEG C.

Stripping tension when stripping metal supporter and phase difference film is preferably set to 300N/m or less.More preferably 196~ In the range of 245N/m, in the case of being susceptible to gauffer in stripping, preferably removed with 190N/m tension below.It is excellent Choosing is removed with 300N/m stripping tension below.

5) drying/stretching/width keeps process

(drying)

In phase difference film drying process, wet film is removed from metal support preferably, is further dried, Make residual solvent amount be 1 mass % hereinafter, further preferably 0.1 mass % hereinafter, particularly preferably 0~0.01 mass % with Under.

In phase difference film drying process, generally use (is alternately led to roller drying mode in the multiple rollers configured up and down The mode crossed wet film and made it dry) or stenter mode on one side convey wet film, while the mode that is dried.For example, stripping Afterwards, using by wet film in multiple rollers being configured in drying device alternately through and the drying device 35 that conveys, and/or The stenter stretching device 34 that the both ends of wet film are held with clip and are conveyed, wet film is dried.

Make wet film dry method be not particularly limited, usually can by hot wind, infrared ray, heating roller, microwave etc. into Row, from the aspect of simplicity, is preferably carried out by hot wind.It is flat that drying excessively drastically is easy the phase difference film that damage is completed Face property.It is that the left and right 8 mass % or less carries out to be dried caused by high temperature from residual solvent.By entirety, general 30~250 It is dried in the range of DEG C.Particularly preferably made it dry in the range of 35~200 DEG C.Drying temperature rises preferably in stages It is high.

, it is preferable to use the left and right grasping device of stenter can be utilized phase in the case of using stenter stretching device Since poor film hold length and carry out the device that left and right independently controls (to the distance for holding end holding).In addition, in tentering In machine process, in order to improve flatness, it is also preferred that intentionally making the region with different temperatures.

It is also preferable to which intermediate region is arranged between different temperature regions so that respective region is not done It relates to.

(stretching, width is kept)

Then, the wet film removed from metal support is at least preferably subjected to stretch processing in one direction.By into Row stretch processing can control the orientation of the molecule in phase difference film.In the present invention, in order to obtain the length of delay Ro of target, Rt, preferably phase difference film composition using the present invention further carry out the control of conveyance tension, are reflected by stretched operation Rate controls.For example, length of delay can be made to change by so that the tension of length direction is lower or is got higher.

It, can be along length direction (the film direction of wet film as specific drawing process；It is cast direction；The directions MD) and Vertical direction, i.e. width direction (directions TD) in wet film face, gradually or is carried out at the same time biaxial stretch-formed or is uniaxially stretched.It is preferred that edge It is cast direction (directions MD), width direction (directions TD) implements biaxial stretch-formed biaxial stretch-formed phase difference film, phase of the invention Poor film both can be to be uniaxially stretched phase difference film, or non-stretched phase difference film.It should be noted that stretched operation can be with Multistage it is split implementation.In addition, in the case where carrying out biaxial stretch-formed, simultaneously biaxial drawing can be both carried out, also may be used Periodically to implement.In this case, for interim, such as the different stretching of draw direction can be both carried out successively, The stretching multistage of the same direction can be split, and apply the stretching in different directions in its any one stage.That is, Such as can be following stretching step：

Edge curtain coating direction stretches → stretching → edge curtain coating direction stretching → edge curtain coating direction stretching in the width direction

→ stretching → edge curtain coating direction stretching → edge curtain coating direction stretching in the width direction is stretched in the width direction

Stretched in addition, simultaneously biaxial drawing is also included on a direction, in another direction relax tension and make The case where it shrinks.

Preferably final edge curtain coating direction is 0.8~1.5 times to the stretching ratio of orthogonal biaxially oriented respectively, along width Direction is set as 1.1~2.5 times of range, preferably carries out in the range of 0.8~1.2 times along curtain coating direction, exists in the width direction It is carried out in the range of 1.2~2.0 times.

For draft temperature, it is usually preferred within the temperature range of constituting Tg~Tg+60 DEG C of resin of phase difference film It carries out.Usual draft temperature is preferably 120 DEG C~200 DEG C, further preferably 120 DEG C~180 DEG C.

It is preferred that stretch when wet film in residual solvent be 20~0%, it is further preferred 15~0% under conditions of drawn It stretches.It is stretched under conditions of for example, it is preferable to which residual solvent is 8% at 135 DEG C, or is in residual solvent at 155 DEG C It is stretched under conditions of 11%.Or stretched under conditions of residual solvent is 2% preferably at 155 DEG C, or preferably exist It is stretched under conditions of residual solvent is less than 1% at 160 DEG C.

The method that wet film stretches is not particularly limited.It can be mentioned, for example：Circumference speed difference is imposed to multiple rollers, at it Between the method that is stretched along longitudinal direction using the circumference speed difference of roller；The both ends that wet film is fixed with clip or needle, by clip or needle It is spaced the method for extending along direction of travel and being stretched along longitudinal direction；The side for similarly transversely extending and transversely being stretched Method；Or along extension simultaneously in length and breadth and along the method etc. that two directions are stretched in length and breadth.Certainly, these methods can combine and make With.Wherein, particularly preferably (transverse direction) is stretched in the width direction in a manner of the stenter at the both ends for holding wet film with clip etc..

In addition, in the case of so-called tenter frame process, when driving clip portion with linear drive mode, can carry out smooth Stretching, it is possible to reduce fracture etc. danger, therefore preferably.

These width of film making process are kept or the stretching of transverse direction is carried out preferably by stenter, can be pin tentering Machine or clip stenter.

The phase difference film slow axis or fast axle of the present invention is present in phase difference film surface, by the angle of the composition with film direction When being set as θ 1, θ 1 is preferably -1 ° or more+1 ° hereinafter, more preferably -0.5 ° or more+0.5 ° or less.

The θ 1 can be defined as the angle of orientation, and the measurement of θ 1 can use automatic birefringence meter KOBRA-21ADH (prince's measurements Machine Co., Ltd. manufactures) it carries out.θ 1 respectively meets above-mentioned relation, can contribute to obtain in showing image high bright Degree, inhibits or prevents light from leaking, and can contribute to obtain loyal color reproduction in color liquid crystal display arrangement.

6) rolling step

Finally, by the way that obtained wet film (phase difference film after processing) to be wound, phase difference film can be obtained.More specifically For, which is to be used as phase difference film to utilize up- coiler 37 after the residual solvent amount in wet film reaches 2 mass % or less The process of winding, by the way that residual solvent amount is set as 0.4 mass % hereinafter, the good phase difference of dimensional stability can be obtained Film.Particularly preferably wound in the range of 0.00~0.10 mass %.

As long as winding method using commonly used, have and determines calibrated wrench method, determines tensammetry, taper tension method, inside The certain program tension control method etc. of stress, is used separately these methods.

Before being reeled up, end is cut according to the width of product and is cut, attaching or scratch in winding in order to prevent, It can implement annular knurl to both ends and process (Embossing processing).Side can be had the metal of the pattern of convex-concave by the method for annular knurl processing Ring is processed by heating or pressurizeing.It should be noted that the usual phase of the grip portion of the clip at phase difference film both ends Potential difference film deforms, and cannot function as product use, therefore be removed.In the case of the variation for not causing material caused by heat, It is reused after recycling.

The phase difference film of the present invention is preferably band-like phase difference film, specifically, indicating the phase of 100m~10000m or so Potential difference film, usually by roll provide in the form of phase difference film.In addition, phase difference film width should be according to liquid crystal display device Enlargement or production efficient activity requirement, preferably 1.3~4m, more preferably 1.4~4m, further preferably 2~3m.

< melts casting film method >

In addition, the phase difference film of the present invention can also utilize melting tape-casting.

Melted masking method refers to that will melt to display stream containing the heating of the composition of thermoplastic resin and above-mentioned additive The temperature of dynamic property, thereafter, the method that the fusant of the thermoplastic resin containing mobility is cast.As thermoplastic resin Fat particularly preferably uses cellulose esters.

As heating melting manufacturing process, specifically, can be classified as melting extrusion forming process, compression moulding method, Blow moulding, injection molding, blow-moulding process, stretcher forming etc..In these forming processes, from mechanical strength and surface accuracy Etc. consider, preferred molten extrusion molding.Multiple raw material for extrusion by melting are generally preferably kneaded and granulate in advance.

Granulating can be well known method, such as can be by by dry fiber element ester or plasticizer, other additives It is supplied to extruder with charger, is kneaded using the extruder of single screw rod or twin-screw, is squeezed out with strand shape from mold, It carries out water cooling or air cooling and cuts to carry out.

Additive can both be mixed before supplying to extruder, can also use an other charger supply respectively.

A small amount of additive such as particle or antioxidant is mixed in advance in order to equably mix.

Extruder preferably can be to inhibit shearing force, resin not to deteriorate the side of (molecular weight reduction, coloring, gel generation etc.) Formula granulates, and is processed at low temperature as far as possible.For example, it is preferable to use the spiral shell of deep channel type in the case of double screw extruder Bar makes its rotation equidirectional.From the aspect of the uniformity of kneading, preferred engagement type.

Phase difference film film is carried out using the particle obtained as described above.It is of course also possible to be incited somebody to action without granulating The powder of raw material is directly supplied with charger to extruder, is directly film-made phase difference film.

Melting temperature when above-mentioned particle is squeezed out using the extruder of single screw rod or double-screw type is set as 200~300 DEG C Temperature range flowed from T moulds with phase difference is membranaceous after being filtered with the filter etc. of leaf dish formula and removed foreign matter Prolong, phase difference film is clamped with chill roll and Elastic Contact roller, its solidification is made on chill roll.

When being imported from supply loading hopper to extruder, it is also preferred that be set as under vacuum or depressurize under lower or atmosphere of inert gases, The method for preventing oxygenolysis etc..

For squeezing out flow, preferably imports gear pump etc. and steadily carry out.In addition, the filtering of the removing for foreign matter It is preferable to use stainless steel fibre sintered filters for device.Stainless steel fibre sintered filter can make answering for stainless steel fibre body It is compressed on the basis of miscellaneous ground mutually winding state, by contact position sintering and integration, according to the rugosity of its fiber and compression It measures and changes density, adjust filtering accuracy.

The additives such as plasticizer or particle can both be mixed with resin in advance, can also be mixed in the midway of extruder.For Equably addition is, it is preferable to use the mixing arrangements such as static mixer.

When phase difference film is clamped using chill roll and Elastic Contact roller, the phase difference film temperature of contact roller side is preferably set to phase The temperature range of Tg~Tg+110 DEG C of potential difference film.The roller on the surface with the elastomer used with this purpose can use known Roller.

Elastic Contact roller also referred to as clamps rotary body.As Elastic Contact roller, the Elastic Contact sold can also be used Roller.

When removing phase difference film from chill roll, preferably controls tension and prevent phase difference film from deforming.

In addition, the phase difference film obtained as described above is by after the process that is contacted with chill roll, preferably passing through described Stretched operation is stretched.

The method of stretching can it is preferable to use well known roller stretching machine or stenters etc..Specific condition and solution casting method The case where it is same.

Finally, in the same manner as with the solution casting method the case where, by the way that the phase difference film obtained as described above is wound, Phase difference film can be obtained.

The composition of polarizing film and liquid crystal display device

The composition for the polarizing film and liquid crystal display device that phase difference film about the present invention has, is said with reference to attached drawing It is bright.

Fig. 2 is to indicate the polarizing film that the phase difference film of the present invention has and the liquid crystal display device that the polarizing film has The summary section of an example of composition.

< polarizing films >

The polarizing film of one embodiment of the present invention must contain the phase difference film of at least one one embodiment of the present invention And polarizer.

The polarizing film 101A of one embodiment of the present invention is to be preferably at least protective film 102, active energy line curing Property bonding agent 103A and polarizer 104 are with the sequence lamination, in addition in the polarizer with the face opposite side configured with the protective film The aspect of the composition of the active energy ray-curable bonding agent 103B of face superimposed layer and the phase difference film 105 of the present invention.That is, polarization Piece 101A has the phase difference film 105 by the present invention be bonded with polarizer 104 with active energy ray-curable bonding agent 103B It constitutes.

The phase difference film 105 of above-mentioned polarizing film 101A is bonded via liquid crystal cells 107 and adhesive or bonding agent etc., excellent It is selected in the liquid crystal cells face (backlight side of the opposite side in the face of polarizing film 101A and liquid crystal cells 107 being bonded：It is described in figure BL.) on identical with the polarizing film 101A composition of fitting polarizing film 101B the present invention phase difference film 105, composition liquid crystal Showing device 108.

Further, it is possible to use other well known bonding agent replaces active energy ray-curable bonding agent.

< polarizers >

The polarizer of main composition element as polarizing film is the element only by the light in the partial wave face of certain orientation, mesh The preceding known polarizer represented is polyethenol series light polarizing film.Polyethenol series light polarizing film has and makes iodine on polyvinyl alcohol mesentery The film of dyeing and the film for making dichroic dye dye.

As polarizer, can use polyvinyl alcohol water solution is filmed, so that it is uniaxially stretched and is dyed or It carries out being uniaxially stretched polarizer that is rear, preferably having carried out durability processing with boron compound after dyeing.The film thickness of polarizer In the range of preferably 5~30 μm, in the range of particularly preferably 5~15 μm.

In addition, it is also preferred that using Japanese Unexamined Patent Publication 2003-248123 bulletins and Japanese Unexamined Patent Publication 2003-342322 bulletins 99.0~99.99 moles of 1~4 mole of % of content of ethylene unit Deng described in, the degree of polymerization 2000~4000, saponification degree % Ethylene modified polyvinyl alcohol.Wherein, it is preferable to use the ethylene in the range of hot water cutting temperature is 66~73 DEG C is denaturalized polyethylene Alcohol film.Using the polarizer for having the ethylene modified polyvinyl alcohol film not only polarizing properties and excellent durability, but also color is not It is few, particularly preferred for large-scale liquid crystal display device.

< protective films >

In the polarizing film of one embodiment of the present invention, as needed, as shown in Fig. 2, it is preferred that of the invention with configuration The face opposite side of phase difference film be polarized on minute surface the further lamination protective film 102 via bonding agent.

The protective film can be used as sales item obtain, it can be mentioned, for example Konicaminoltatac KC4UE, KC8UE, KC8UX, KC5UX, KC8UY, KC4UY, KC4CZ, KC6UA, KC4UA and KC2UA (more than, Konica Minolta Opto Inc. System) etc..

Setting hard conating, antistatic layer, antireflection layer, easy slip particularly preferably on the protective film for being configured at identification side The functional layers such as layer, adhesive linkage, antiglare layer, barrier layer.

< bonding agents >

As described above, in form shown in Fig. 2, phase difference film 105 and polarizer 104 are via bonding agent 103A or 103B And it is glued.Using active energy ray-curable bonding agent, penetrability can be efficiently controlled, therefore preferably.But in this hair In bright, bonding agent is not particularly limited, and can not only use active energy ray-curable bonding agent, but also can use urethane system The curing types such as adhesive, epoxy adhesive, aqueous macromolecule-isocyanate system adhesive, thermohardening type acryloid cement Adhesive, moisture-curable urethane adhesive, methacrylates type, ester system methacrylate type, oxidized form polyethers first The anaerobies such as base acrylate adhesive, the instant adhesive of cyanoacrylate system, acrylate and 2 liquid of peroxide system Bonding agent well known to type instant adhesive etc..Both can be 1 liquid type as above-mentioned adhesive, or preceding by 2 liquid using The 2 liquid types for being mixed and being used above.Bonding agent both can be using organic solvent as the solvent system of medium, or as Can also be no-solvent type using water as water systems such as the emulsion-type of the medium of principal component, colloidal dispersions type, aqueous solution types.Bonding The concentration of agent liquid is suitably determined according to film thickness, coating method, the application conditions etc. after bonding, usually 0.1~50 matter Measure %.

In addition, protective film and phase difference film can carry out easily on the bonding plane of polarizer, the i.e. face of setting bonding agent Bonding processing.As the processing of easy bonding, it is not particularly limited, can be used for example known in sided corona treatment, corona treatment etc. Method.

(active energy ray-curable bonding agent)

Active energy ray-curable bonding agent has cationic polymerization type and radical polymerization mould assembly.It can be preferred for this hair Include the activity of each ingredient containing (α) below~(δ) in the preferred example of bright active energy ray-curable bonding agent Energy ray-curable adhesive composite.

(α) cationically polymerizable compound

(β) light cationic polymerization initiator

(γ) shows the photosensitizing agent of maximum absorption in light of the wavelength more than 380nm

(δ) naphthalene system light enhanced sensitivity auxiliary agent

In the present invention, the irradiation that cationically polymerizable compound passes through active energy ray is preferably made to carry out cationic polymerization simultaneously Make its solidification, forms adhesive layer, draw with closing light cationic polymerization preferably in active energy ray-curable adhesive composite Send out agent (β).

Light cationic polymerization initiator passes through active energy ray as luminous ray, ultraviolet light, X-ray, electron beam It irradiates and generates cation kind or Louis, start the polymerisation of cationically polymerizable compound (α).As active-energy Line, from use be easy and curing rate also fully from the aspect of, it is however generally that it is preferable to use ultraviolet lights.Hereinafter, about ultraviolet light The preferred form of curing type bonding agent, simply illustrates.

[ultraviolet hardening bonding agent]

In one embodiment of the present invention, pass through fitting in phase difference film 105 and polarizer 104 or protective film 102 With applicable ultraviolet hardening bonding agent in the fitting of polarizer, the excellent in te pins of durability of polarizer can be obtained with high production rate Characteristic.

[composition of ultraviolet hardening bonding agent]

Ultraviolet hardening adhesive composite as polarizing film, it is known to the light of optical free radical polymerization be utilized certainly By base polymerizable composition, the light cationic polymerization type composition of light cationic polymerization is utilized and optical free radical has been used in combination The mixed composition of polymerization and light cationic polymerization.

As optical free radical polymerizable composition, it is known to contain Japanese Unexamined Patent Publication 2008-009329 public affairs with special ratios The free-radical polymerised compound containing hydroxyl or carboxyl isopolarity group described in report and without containing the freedom of polar group The composition etc. of base polymerizable compound.Particularly preferred free-radical polymerised compound is with the second that can carry out free radical polymerization The compound of alkene unsaturated bond.In the preferred reality of the compound with the ethylene unsaturated bond that can carry out free radical polymerization In example, including the compound with (methyl) acryloyl group.In the example of the compound with (methyl) acryloyl group, including N replaces (methyl) acrylamides, (methyl) acrylic ester compound etc..(methyl) acrylamide refers to acryloyl Amine or Methacrylamide.

In addition, as light cationic polymerization type composition, can enumerate：Institute is public in Japanese Unexamined Patent Publication 2011-028234 bulletins Open, (α) cationically polymerizable compound, (β) light cationic polymerization initiator, (γ) are shown in light of the wavelength more than 380nm Show the ultraviolet hardening bonding agent combination of each ingredient of photosensitizing agent and (δ) containing naphthalene system light enhanced sensitivity auxiliary agent of maximum absorption Object.But it is also possible to use the ultraviolet hardening bonding agent other than it.

Other preferred embodiments of the invention are the phase at least having 1 one embodiment of the present invention as a result, The polarizing film of poor film.

< liquid crystal display devices >

The polarizing film of the present invention can be preferred for liquid crystal display device.Use the liquid crystal display for the polarizing film for having the present invention Therefore the phase difference film that device can be used moisture permeability low is not likely to produce the irregular colour of aqueous caused liquid crystal display device.

Glass plate used in the panel of liquid crystal display device is preferably the range of the thickness of 0.3~0.7mm, further The preferably range of 0.3~0.5mm.Since the polarizing film of the present invention is unlikely to deform, it is especially small in the thickness of glass plate When, it is preferably used.

The fitting on the surface of the phase difference film side of the present invention of polarizing film and at least one surface of liquid crystal cells can profit It is carried out with well known method.According to circumstances, it can be bonded via adhesive linkage.

About the pattern (type of drive) of liquid crystal display device, it is not also specifically limited, can use STN, TN, OCB, The liquid crystal display device of the various drive modes such as HAN, VA (MVA, PVA), IPS, OCB.

Especially because the phase difference film of the present invention has high length of delay, therefore, mended as the optics for expanding field angle Phase difference film (phase difference film) is repaid, is preferably provided in the liquid crystal display device of VA (MVA, PVA) type (vertical orientating type).That is, A mode according to the present invention provides a kind of vertical alignment-type liquid crystal for having above-mentioned polarizing film on one side at least liquid crystal cells Display device.

By having the polarizing film of the phase difference film containing the present invention in these liquid crystal display devices, can obtain durable Property (humidity resistance) excellent liquid crystal display device.

Preferred other embodiment of the invention is the liquid crystal for the polarizing film for having one embodiment of the present invention as a result, Display device.

《The manufacturing method of polarizing film》

Polarizing film can be bonded the present invention by using active energy ray-curable bonding agent on a face of polarizer Phase difference film manufacture.On phase difference film two sides in the case of cementability difference, preferably carried out in such a way that cementability is good Fitting.

Hereinafter, to using an example of the manufacturing method of the polarizing film of active energy-line solidifying type bonding agent to illustrate.

Polarizing film can be coated with following work by at least one side included in the bonding plane of polarizer and phase difference film Property energy-line solidifying type bonding agent and form the bonding agent painting process of adhesive layer, via the adhesive layer by polarizer and phase Potential difference film be bonded and be bonded bonding process, make in the state of being bonded with polarizer and phase difference film via the adhesive layer The manufacturing method of the cured curing process of adhesive layer manufactures.Furthermore it is possible to for will be bonded the face of phase difference film polarizer into The pretreatment procedure of row easily bonding processing.

(pretreatment procedure)

Pretreatment procedure be with the process easy to stick for connecing processing is carried out on the bonding plane of cellulose ester membrane, polarizer.It is rising In the case that the two sides of polariscope 104 is respectively bonded phase difference film 105 and protective film 102, to respective viscous with polarizer 104 Junction carries out easy bonding processing.As the processing of easy bonding, sided corona treatment, corona treatment etc. can be enumerated.

(painting process of active energy ray-curable bonding agent)

As the painting process of active energy ray-curable bonding agent, in the bonding plane of polarizer 104 and phase difference film 105 In at least one side on be coated with above-mentioned active energy ray-curable bonding agent.On the surface of polarizer 104 or phase difference film 105 In the case of being directly coated with active energy ray-curable bonding agent, its coating method is not particularly limited.For example, can utilize Scraper plate, bar, dispensing coating machine, unfilled corner wheel coating machine, gravure coating machine etc., various wet coating modes.Alternatively, it is also possible to profit Make between polarizer and phase difference film active energy ray-curable bonding agent be cast after, with roller etc. pressurizeed and equably The method spread out.

(bonding process)

After being coated with active energy ray-curable bonding agent by above-mentioned method, handled in bonding process.It should In bonding process, for example, being coated with active energy ray-curable bonding agent on the surface of polarizer 104 in painting process in front When, phase difference film 105 is overlapped herein.In painting process in front, initially it is coated with and lives on the surface of phase difference film 105 In the case of the mode of property energy ray-curable bonding agent, polarizer 104 is overlapped herein.In addition, in 104 He of polarizer In the case of being cast active energy ray-curable bonding agent between phase difference film 105, in this state by polarizer 104 and phase Potential difference film 105 is overlapped.In the case where the two sides of polarizer is bonded phase difference film 105 or protective film 102, two sides uses activity In the case of energy ray-curable bonding agent, on the two sides of polarizer 104 respectively via active energy ray-curable bonding agent and Overlapping phases difference film 105 or protective film 102.Moreover, usually (overlapping with phase on one side in polarizer from two sides in this state In the case of poor film 105 and protective film 102, in polarizer side and phase difference film side, in addition the two sides of polarizer overlaps with phase In the case of poor film 105 or protective film 102, the phase difference film for its two sides or protective film side) it is clamped and is carried out with pressure roller etc. Pressurization.The material of pressure roller can use metal or rubber etc..The pressure roller for being configured at two sides both can be identical material, It can be different materials.

(curing process)

In curing process, active energy ray is irradiated to uncured active energy ray-curable bonding agent, is made containing sun Photopolymerizable compound (such as epoxide or oxetane compound) or free-radical polymerised compound (such as third Olefin(e) acid ester type compound, acrylamides etc.) active energy ray-curable adhesive layer solidification, make via active energy Polarizer and phase difference film 105 bonding measured line curability bonding agent and be overlapped.It is bonded phase difference film 105 in the one side of polarizer In the case of, active energy ray can be irradiated from the either side of 105 side of polarizer side or phase difference film.In addition, in polarizer In the case that two sides is bonded phase difference film 105 or protective film 102, on the two sides of polarizer respectively via active energy ray-curable Bonding agent and overlap with and irradiate active energy ray in the state of phase difference film 105 or protective film, keep the active energy ray on two sides solid The property changed bonding agent cures simultaneously to be advantageous.

It should be noted that as active energy ray, can enumerate：X-ray, ultraviolet light, electron beam, luminous ray etc..

When using ultraviolet light as active energy ray, as long as ultraviolet irradiation condition can will be suitable for the invention The cured condition of ultraviolet hardening bonding agent, so that it may with using arbitrary condition appropriate.Ultraviolet irradiation amount is to accumulate Quantometer is preferably 50~1500mJ/cm², further preferably 100~500mJ/cm²。

When using electron beam as active energy ray, the irradiation condition of electron beam with Absorption Line gauge be preferably 5~ 100kGy, further preferably 10~75kGy.Accelerating potential is preferably 5~300kV, further preferably 10~250kV.

In the case of the manufacturing process for carrying out polarizing film with continuous lines, linear velocity depends on the hardening time of bonding agent, but Preferably 1~500m/min, more preferably 5~300m/min, further preferably 10~100m/min.If linear velocity is 1m/min or more then may insure productivity, or can inhibit the loss to phase difference film, can make the inclined of excellent in te pins of durability Shake piece.In addition, if linear velocity be 500m/min hereinafter, if the solidification of active energy ray-curable bonding agent become abundant, can Have the hardness of purpose, active energy ray-curable adhesive layer excellent in adhesion to be formed.

In the polarizing film obtained as described above, the thickness of adhesive layer is not particularly limited, and usually 0.01~10 In the range of, in the range of preferably 0.5~5 μm.

Embodiment

Hereinafter, enumerating embodiment, the present invention is concretely demonstrated, but the present invention is not limited to these.It needs It is bright, in embodiment, the expression of " part " or " % " is used, unless otherwise specified, indicates " mass parts " or " matter Measure % ".

《Phase difference film makes》

[making of phase difference film 101]

< phase difference elevators >

Using by compound 38 (nitrogenous compound (A)) and compound 150 (nitrogenous compound (B)) with mass ratio 99.9: The 0.1 phase difference elevator being mixed into.

The composition > of the main rubber cement liquid of <

Following compositions are heated on one side, are sufficiently carried out stirring and dissolving on one side, prepare main rubber cement liquid.

The cellulosic resin C1 diacetyl cellulose of weight average molecular weight (Mw) 5.6 ten thousand (degree of substitution with acetyl group 2.41)： 100 mass parts

Phase difference elevator (nitrogenous compound (A)+nitrogenous compound (B))：3 mass parts

Sugar ester 1 (following)：10 mass parts

[chemical formula 25]

(in formula, R₁~R₈For hydrogen or benzoyl, benzoyl average substitution degree=5.5, hydrogen atom=2.5.)

By (two ends of the condensation product of the molar ratio of phthalic acid/adipic acid/1,2- propylene glycol=50/50/100 of plasticizer 1 Substance, molecular weight 440 made of end benzoic acid is ester terminated)：2 mass parts

AEROSIL R812 (delustering agent, the manufacture of AEROSIL Co., Ltd. of Japan)：0.20 mass parts

Dichloromethane：300 mass parts

Ethyl alcohol：40 mass parts

Using band casting device, with 2m width, by obtained rubber cement, uniformly curtain coating is supported in stainless steel band at 22 DEG C of temperature On body.Make evaporation of the solvent on stainless steel band supporter, until residual solvent amount become 30 mass %, to remove tension 162N/m It is removed from stainless steel band supporter.Then, so that the wet film of the rubber cement after stripping is evaporated solvent at 35 DEG C, cut, Afterwards, 1.1 are carried out along salivation direction (directions MD) in region stretches (method stretched along longitudinal direction using roller circumference speed difference) It stretches again, (directions TD) carries out 1.5 times of stretchings in the width direction in stenter stretching, while under 135 DEG C of drying temperature It makes it dry.Residual solvent amount when starting to stretch using stenter is 8%.After being stretched with stenter, implement at 130 DEG C 5 minutes relaxation processes are conveyed with multiple rollers in the arid region of 120 DEG C, 140 DEG C thereafter, terminate to do on one side on one side It is dry, it is cut with 1.5m width, after width 10mm is implemented at phase difference film both ends, the annular knurl of 5 μm of height is processed, wound on core On.The phase difference film 101 of 35 μm of dry film thickness is obtained as a result,.

(weight average molecular weight measurement)

The measurement of the weight average molecular weight of cellulose esters is measured using gel permeation chromatography.The following institute of determination condition It states.

Solvent：Dichloromethane

Column temperature：25℃

Sample solution concentration：0.1 mass %

Detector：RI Model 504 (manufacture of GL science Co., Ltd.)

Pump：L6000 (Hitachi Co., Ltd's manufacture)

Flow：1.0ml/min

Calibration curve：Standard polystyren STK standard

Correction using the 13 samples formation to polystyrene (TOSOH Co., Ltd's manufacture) Mw=1000000~500 is bent Line.13 samples substantially to use at equal intervals.

[making of phase difference film 102~110]

In the making of above-mentioned phase difference film 101, by nitrogenous compound (A) and nitrogen contained in phase difference elevator The ratio that the mass ratio of conjunction object (B) is set as described in table 1 (table 1-1 and table 1-2) in addition to this similarly operates, and makes phase Poor film 102~110.

[making of phase difference film 111~117]

In the making of above-mentioned phase difference film 101~110, using compound 6 as nitrogenous compound (A), (B) is used to change It closes object 93 in addition to this similarly to operate as nitrogenous compound, makes phase difference film 111~117.

[making of phase difference film 118~124]

In the making of above-mentioned phase difference film 101~110, using compound 41 as nitrogenous compound (A), chemical combination is used Object 151 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 118~124.

[making of phase difference film 125~131]

In the making of above-mentioned phase difference film 101~110, using compound 40 as nitrogenous compound (A), chemical combination is used Object 152 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 125~131.

[making of phase difference film 132~138]

In the making of above-mentioned phase difference film 104~110, using compound 42 as nitrogenous compound (A), chemical combination is used Object 154 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 132~138.

[making of phase difference film 139~145]

In the making of above-mentioned phase difference film 104~110, using compound 44 as nitrogenous compound (A), chemical combination is used Object 156 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 139~145.

[making of phase difference film 146~152]

In the making of above-mentioned phase difference film 104~110, using compound 18 as compound (A), compound is used 158 in addition to this similarly operate as nitrogenous compound (B), make phase difference film 146~152.

[making of phase difference film 153~159]

In the making of above-mentioned phase difference film 104~110, using compound 43 as nitrogenous compound (A), chemical combination is used Object 153 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 153~159.

[making of phase difference film 160~166]

In the making of above-mentioned phase difference film 104~110, using compound 45 as nitrogenous compound (A), chemical combination is used Object 155 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 160~166.

[making of phase difference film 167~173]

In the making of above-mentioned phase difference film 104~110, using compound 29 as nitrogenous compound (A), chemical combination is used Object 157 is in addition to this similarly operated as nitrogenous compound (B), makes phase difference film 167~173.

《Phase difference film is evaluated》

To each phase difference film of above-mentioned making, measurement and the evaluation of following each characteristic values are carried out.

(measurement of length of delay)

In the environment of 23 DEG C of temperature, relative humidity 55%, Axo Scan in terms of automatic birefringence are used by wavelength 590nm (Axo Scan Mueller Matrix Polarimeter：Axometrix companies manufacture) under the phase difference film measurement of making State length of delay Ro, Rt of formula expression.

Specifically, phase difference film to be carried out in the environment of 23 DEG C, 55%RH, under the wavelength of 590nm at 10 to 3 dimensions Detecting refractive index, find out refractive index n_x、n_y、n_zAverage value after, according to the length of delay Ro in direction in following formula calculating face, The length of delay Rt of thickness direction.

[mathematical expression 5]

Formula (i)：Ro (590)=(n_x-n_y)×d(nm)

[formula (i), n_xIndicate that direction refractive index is as the refractive index on maximum direction x in phase difference film surface.n_yIt indicates Refractive index in phase difference film surface on direction y vertical with the direction x on direction.n_zIndicate phase difference film thickness direction z On refractive index.D indicates phase difference film thickness (nm).]

[mathematical expression 6]

Formula (ii)：Rt={ (n_x+n_y)/2-n_z}×d(nm)

[in formula (ii), n_x、n_y、n_z, d it is identical as formula (i) meaning.]

《The evaluation of phase difference film phase difference and wet heat durability》

To each phase difference film of above-mentioned making, the front and back phase difference for being maintained at hygrothermal environment is measured as described below, is calculated Go out the phase difference rate of change, evaluates wet heat durability.

By phase difference film after 23 DEG C, relative humidity 55% time are kept for 24 hours, in 23 DEG C, the ring of relative humidity 55% Phase difference film phase difference (Ro is measured under border₁、Rt₁)。

Then, it after phase difference film being kept for 1000 hours in temperature 60 C, relative humidity 90% (hygrothermal environment), moves To 23 DEG C, the environment of relative humidity 55%, kept for 24 hours.Thereafter, phase is measured in the environment of 23 DEG C, relative humidity 55% Poor film phase difference (Ro_2,Rt₂)。

It keeps front and back measuring difference of phases value to be compared hygrothermal environment, calculates the rate of change.

About the phase difference film of the present invention, R_OThe rate of change (%) and the Rt rate of change (%) can use following formula (1) and (2) table Show.

Formula (1)：

[mathematical expression 7]

The Ro rate of change={ (Ro₁-Ro₂)/Ro₁}×100

Formula (2)：

[mathematical expression 8]

The Rt rate of change={ (Rt₁-Rt₂)/Rt₁}×100

Based on index below, phase difference film wet heat durability is evaluated.

The rate of change that the rate of change of Ro is ± 2.5%, Rt is ◎ within ± 3.5%

The rate of change that the rate of change of Ro is ± 3%, Rt is zero within ± 4%

The rate of change that the rate of change of Ro is ± 4%, Rt is △ within ± 5%

The rate of change of Ro more than 4%, Rt the rate of change be more than 5% ×

《The making of polarizing film》

[making of polarizing film 101]

(making of polarizer)

The polyvinyl alcohol film of 30 μm of thickness is set to be swollen in 35 DEG C of water.By obtained film by iodine 0.075g, potassium iodide It is impregnated 60 seconds in the aqueous solution that 5g and water 100g are constituted, is further impregnated in and is made of potassium iodide 3g, boric acid 7.5g and water 100g 45 DEG C of aqueous solution.Obtained film is uniaxially stretched under conditions of 55 DEG C of draft temperature, 5 times of stretching ratio.It should After monadic stretching membrane washing, makes it dry, obtain the polarizer of 10 μm of thickness.

(the preparation of active energy ray-curable bonding agent liquid：Cationic polymerization type bonding agent)

After following each ingredients are mixed, deaeration is carried out, active energy ray-curable bonding agent liquid is prepared.It needs Bright, triaryl matte hexafluorophosphate is coordinated in the form of 50% polypropylene carbonate ester solution, following middle expression triaryl mattes six The solid content of fluorophosphate.

45 mass parts of 3,4- epoxycyclohexylmethyl -3,4- epoxy-cyclohexanes formic acid esters

Epolead (registered trademark) GT-301 (alicyclic epoxy resin of Daisel chemical industry Co., Ltd's manufacture) 40 mass parts

15 mass parts of 1,4- butanediol diglycidyl ethers

2.3 mass parts of triaryl matte hexafluorophosphate

0.1 mass parts of 9,10- dibutoxies anthracene

2.0 mass parts of 1,4- diethoxies naphthalene

(making of polarizing film 101)

According to following methods, the polarizing film 101 of the structure of the polarizing film 101A with Fig. 2 is made.Numerical value in bracket Indicate the number of each integral part described in Fig. 2.

First, as protective film (102), prepare KC6UA films (Konica Minolta Opto Inc.'s manufacture), use dimple version Coating machine (gravure roll：#300,140%/linear speed of rotating speed) active energy ray of above-mentioned preparation is coated in a manner of as 5 μm of thickness Curability bonding agent liquid forms active energy ray-curable bonding agent (103A).

Then, it is coated in such a way that thickness is 5 μm on the phase difference film 101 (105) of above-mentioned making as described above The active energy ray-curable bonding agent liquid of above-mentioned preparation forms active energy ray-curable bonding agent (103B).

Polyvinyl alcohol-iodine of above-mentioned making is configured between the active energy ray-curable bonding agent (103A) and (103B) The polarizer (104) of system is bonded with roller machine, and obtaining lamination has protective film (102)/active energy ray-curable bonding agent The laminate of (103A)/polarizer (104)/active energy ray-curable bonding agent (103B)/phase difference film 101 (105).This When, it is bonded with roller machine, and the slow axis of phase difference film (105) and the absorption axiss of polarizer (104) are mutually perpendicular to.

From two surface side irradiating electron beams of the laminate, polarizing film 101 (101A) is made.

Linear velocity is set as 20m/min, and accelerating potential is set as 250kV, and illuminated line amount is set as 20kGy.

[making of polarizing film 102~110]

In the making of polarizing film 101, except the phase difference film that phase difference film 101 is changed to table 1 (table 1-1 and table 1-2) It except 102~110, similarly operates, makes polarizing film 102~110.

《The making of liquid crystal display device》

It will be fitted with 40 inch display BRAVIA (registered trademark) X1's of SONY (Sony Corp) manufactures in advance The polarizing film on two sides is removed, and the polarizing film 101 of above-mentioned making is fitted in the two sides of the glass-board surface of liquid crystal cells.At this point, just For the direction of the fitting of its polarizing film, in such a way that the face of phase difference film 101 is located at liquid crystal cell side, and in absorption axiss direction The mode in direction identical with the polarizing film being bonded in advance is bonded.The liquid crystal display dress for having polarizing film 101 is made as a result, It sets.

In addition, in addition to polarizing film 101 is substituted by polarizing film 102~110, similarly operate, making has polarizing film 102~110 liquid crystal display device.

《The evaluation of polarizing film and liquid crystal display device》

To each polarizing film of each liquid crystal display device and its making for above-mentioned making, following each evaluations is carried out.

(the evaluation of moisture-proof：The evaluation of irregular colour caused by aqueous variation)

The liquid crystal display device of above-mentioned making is set to tile and to be positioned over platform first-class, by BEMCOT (registered trademark) (Asahi Chemical Industry Fiber Co., Ltd. manufactures) part that is placed in evaluation polarizing film is allowed to containing water.It is covered with 100 μm of PET, so that BEMCOT (registered trademark) does not dry up, and the signal that black display is inputted in television set is thought from PC, in the state of the power source ON of television set It is lower to place 24 hours (room temperature is set as 23 DEG C, and panel temperature is 38 DEG C).After 24 hours, remove BEMCOT (registered trademark).It will L* there are the L* of the part of BEMCOT as water retting portion is measured with EZ contrasts (ELDIM companies manufacture).To not have There is L*s of the L* of the part of BEMCOT (registered trademark) as non-impregnated portion, is measured with EZ contrasts.It needs to illustrate It is in the measurement carried out using EZ contrasts, so that TV is become black display, be measured with color mode.With regard to the condition of water retting For, using following condition：It is ON to make the power supply of panel, and is attaching the BEMCOT (registered trademark) for fully immersing and having water In the state of stand 24 hours.Then, the L* for calculating the L*/non-impregnated portion in water retting portion carries out face according to following benchmark The evaluation of color unevenness.

◎：1.05 or more and 1.30 or less：The generation of irregular colour is not seen completely

○：More than 1.30 and it is 1.55 or less：It can be seen that the generation of faint irregular colour, but for practicality, above there is no problem Quality

△：More than 1.55 and it is 1.80 or less：It can be seen that the generation of irregular colour, problematic in practicality

×：More than 1.80 and it is less than 1.05：Strong irregular colour is generated, is problematic quality in moisture-proof

(the uneven evaluation of display)

By each liquid crystal display device of above-mentioned making in the environment of 40 DEG C, 90%RH after continuous illumination 400 hours, mesh Depending on the presence or absence of display uneven (brightness disproportionation), the striped unevenness for observing picture, commenting for display unevenness is carried out according to following benchmark Valence.

◎：The generation of display unevenness, brightness disproportionation is not seen completely

○：Uneven, brightness disproportionation generation is shown almost without seeing

△：It can be seen that the generation of extremely weak display unevenness, brightness disproportionation, but will not be noted in image is shown, Admissible range in practicality

×：It can be seen that the generation of strong display unevenness, brightness disproportionation, for practical problematic quality

Phase difference film constitution content and the conclusion of the result of above-mentioned evaluation are shown in following table 2.

Table 1-1

Table 1-2

It has confirmed that：Phase difference film (the phase difference film of the present invention containing nitrogenous compound (A) and nitrogenous compound (B) No.101~108,111~115,118~122,125~129,132~136,139~143,146~150,153~157, 160~164,167~171) with only by the phase of nitrogenous compound (A) or any comparative example constituted of nitrogenous compound (B) Potential difference film (phase difference film No.109,110,116,117,123,124,130,131,137,138,144,145,151,152, 158,159 it, 165,166,172,173) compares, wet heat durability is excellent.

It has confirmed that：Using the phase difference elevator for using the nitrogenous compound (A) containing the present invention and nitrogenous compound (B) The polarizing film (101~108) that the phase difference film of manufacture makes only contains nitrogenous compound (A) or nitrogenous compound (B) with use The polarizing film (109,110) that makes of any phase difference film compare, durability is high, shows uneven few.

The application be based on March 25th, 2014 apllied Japanese patent application number 2014-062654, openly in Hold and is introduced into as a whole according to reference.

Claims

1. a kind of phase difference film, with phase difference elevator, the phase difference elevator contains nitrogenous shown in the following general formula 1 Nitrogenous compound B shown in compound A and the following general formula 2,

[chemical formula 1]

General formula 1

Ar-X₂-Ar-Y₂- Ar ... nitrogenous compounds A

In general formula 1, Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted nitrogenous aromatic series Heterocycle, X₂And Y₂Separately indicate substituted or unsubstituted nitrogenous heteroaromatic,

[chemical formula 2]

General formula 2

Ar-X₃-Ar-Y₃-Ar-Z₃- Ar ... nitrogenous compounds B

In general formula 2, Ar is separately substituted or unsubstituted aromatic series hydrocarbon ring or substituted or unsubstituted nitrogenous aromatic series Heterocycle, X₃、Y₃And Z₃Separately indicate substituted or unsubstituted nitrogenous heteroaromatic.

2. phase difference film as described in claim 1, wherein the gross mass of nitrogenous compound A and nitrogenous compound B to be set as When 100, the containing ratio of nitrogenous compound A and nitrogenous compound B in phase difference elevator are nitrogenous compound A:Nitrogen Close object B=2:98~98:2.

3. phase difference film as claimed in claim 1 or 2, wherein the nitrogenous fragrance in nitrogenous compound shown in above-mentioned general formula 1 Race heterocycle structure X₂、Y₂, nitrogenous heteroaromatic structure X in nitrogenous compound shown in above-mentioned general formula 2₃、Y₃、Z₃Independently Ground is the nitrogenous heteroaromatic in imidazole ring, pyrazole ring or triazole ring.

4. phase difference film as claimed in claim 1 or 2, using cellulosic resin as principal component.

5. a kind of polarizing film at least has 1 phase difference film according to any one of claims 1 to 4.

6. a kind of liquid crystal display device, with the polarizing film described in claim 5.