CN1908772A - LCD device - Google Patents

Abstract

The invention provide a liquid crystal display apparatus having improved viewing angle dependence of chromaticity. The liquid crystal display apparatus includes polarizing plates disposed on both sides of a liquid crystal cell, and an optical compensation film, wherein the polarizing plate comprises a polarizer and a protective film. The protective film mounted on the polarizer an at least near one surface of the liquid crystal cell, and mounted between the polarizer and the liquid crystal cell (therein, the protective film can also be the structure of the optical compensation film), and satisfies the following expressions (1) and (2) in a wavelength range of 400 to 700 nm, and the optical compensation film satisfies the following expressions (3) to (8), wherein, Re(lambada) and Rth(lambada) represent Re and Rth under wavelengh. They are (1):0 mm<=Re([lambda])<=5 nm, (2):-20 nm<=Rth([lambda])<=20 nm, (3):20 nm<Re(548)<150 nm, (4):50 nm<Rth(548)<400 nm, (5):0.5<Re(446)/Re(548)<1, (6):1.0<Re(628)/Re(548)<2.0, (7):1.0<Rth(446)/Rth(548)<2.0, and (8):0.5<Rth(628)/Rth(548)<1.0.

Description

Liquid crystal display device

Technical field

The present invention relates to liquid crystal display devices.

Background technique

The purposes of the liquid crystal display device section space-efficient image display device small as consumption electric power is all expanding every year.In the past, the visual angle interdependence of image is the larger disadvantage of liquid crystal display device greatly, but in recent years, the high field angle liquid crystal mode of VA mode is able to functionization, is thus rapidly expanding even if TV etc. requires the demand of liquid crystal display device in the market of high quality image.

VA mode usually has the advantages that contrast is high compared with other liquid crystal display devices, on the other hand changes problem greatly with the contrast and color degree generated by field angle.In contrast, it is known to use the positive direction optical compensating film different with the wavelength dispersion characteristics of thickness direction retardation can efficiently solve the problem, and the method using the different two panels thin polymer film of optical characteristics is disclosed in patent document 1 and 2.In addition, Patent Document 3 discloses the methods of the coating setting polymerizable liquid crystal layer on stretching polymer film.

But although all having some improvement effect in above-mentioned any one method, changed still very greatly by the color degree that field angle generates, it is desirable that further improved.

[patent document 1] International Publication WO2003/032060 pamphlet

[patent document 2] special open 2005-77853 bulletin

[patent document 3] special open 2004-326089 bulletin

Disclosure of the invention

The object of the present invention is to provide the liquid crystal display devices for improving color degree (color intensity) field angle interdependence.

Present inventor etc. has carried out wholwe-hearted research; as a result, it has been found that close to the possessed delay of the protective film of liquid crystal cell side due to being affected to the color variation generated by field angle among polarizing film; so not only adjusting the delay of optical compensating film, but also adjusts and be necessary total delay that the protective film among optical compensating film and polarizing film close to liquid crystal cell side is added together to the color variation that reduction is generated by field angle.Furthermore; it was found that by make among two polarizing films close to liquid crystal cell side protective film at least one of substantially do not have delay; the total delay that may be easy to be added together the protective film among optical compensating film and polarizing film close to liquid crystal cell side is adjusted, and so far completes the present invention.In particular, realizing by the following means.

(1) liquid crystal display device, it is with liquid crystal cells, two polarizing films of the liquid crystal cells two sides are set, and optical compensating film, the protective film that above-mentioned polarizing film has the polarizer and is arranged on a face at least adjacent to above-mentioned liquid crystal cell side for the polarizer, above-mentioned optical compensating film is arranged between above-mentioned liquid crystal cells and the above-mentioned polarizer (wherein, above-mentioned protective film is also possible to the structure as above-mentioned optical compensating film), above-mentioned protective film meets the relationship of following formula (1) and formula (2) in 400-700nm wave-length coverage, and, above-mentioned optical compensating film meets following formula (3)-formula (8) relationship,

0nm≤Re(λ)≤5nm                                  (1)

-20nm≤Rth(λ)≤20nm                              (2)

20nm < Re (548) < 150nm (3)

50nm < Rth (548) < 400nm (4)

0.5 < Re (446)/Re (548) < 1 (5)

1.0 < Re (628)/Re (548) < 2.0 (6)

1.0 < Rth (446)/Rth (548) < 2.0 (7)

0.5 < Rth (628)/Rth (548) < 1.0 (8)

(wherein Re (λ) and Rth (λ) indicates the Re and Rth under wavelength X.)

(2) according to the liquid crystal display device recorded in above-mentioned (1), wherein meet above-mentioned formula (3)-formula (8) relationship optical compensating film with more than two thin polymer films stretched, the thin polymer film of above-mentioned two above stretching is laminated according to the mode for keeping mutual draw direction perpendicular.

(3) according to the liquid crystal display device recorded in above-mentioned (1), wherein meeting above-mentioned formula (3)-formula (8) relationship optical compensating film is overlay on stretching polymer film with liquid crystal compounds and the laminated body formed.

(4) liquid crystal display device, it is with liquid crystal cells, at least two optical compensating films that two polarizing films of the liquid crystal cells two sides are set and are arranged between the polarizing film and liquid crystal cells, above-mentioned polarizing film is by the polarizer and two protective films of the polarizer two sides are arranged in (wherein, protective film among above-mentioned protective film close to liquid crystal cell side is also possible to the structure as above-mentioned optical compensating film) composition, at least one of the protective film of close liquid crystal cell side meets the relationship of following formula (1) and formula (2) in the wave-length coverage of 400-700nm among above-mentioned protective film, and, one of above-mentioned optical compensating film meets following formula (9)-formula (12) relationship, another of above-mentioned optical compensating film meets following formula (13)-formula (16) relationship,

0nm≤Re(λ)≤5nm                               (1)

-20nm≤Rth(λ)≤20nm                           (2)

50nm < Re (548) < 200nm (9)

30nm < Rth (548) < 150nm (10)

0.5 < Re (446)/Re (548) < 1 (11)

1.0 < Re (628)/Re (548) < 2.0 (12)

0nm≤Re (548) < 10nm (13)

100nm < Rth (548) < 300nm (14)

1.0 < Rth (446)/Rth (548) < 2.0 (15)

0.5 < Rth (628)/Rth (548) < 1.0 (16)

(5) it according to the liquid crystal display device recorded in above-mentioned (4), is applied on the acylated cellulose film for meeting above-mentioned formula (1) and formula (2) and/or formula (17) wherein meeting above-mentioned formula (13)-formula (16) optical compensating film.

-10nm≤Rth(446)-Rth(629)≤10nm                 (17)

(6) according to the liquid crystal display device recorded in above-mentioned (1)-(5) any one, wherein the protective film for meeting above-mentioned formula (1) and formula (2) relationship meets the relationship of following formula (17).

-10nm≤Rth(446)-Rth(629)≤10nm                 (17)

(7) according to the liquid crystal display device recorded in above-mentioned (1)-(6) any one, wherein the protective film for meeting above-mentioned formula (1) and formula (2) relationship is acylated cellulose film.

(8) according to the liquid crystal display device recorded in above-mentioned (1)-(4) any one, wherein the protective film for meeting above-mentioned formula (1) and formula (2) relationship is the acylated cellulose film for meeting following formula (17) relationship.

-10nm≤Rth(446)-Rth(629)≤10nm                (17)

(9) according to the liquid crystal display device recorded in above-mentioned (1)-(8) any one, wherein the protective film for meeting above-mentioned formula (1) and formula (2) relationship contains at least one compound indicated by following formula (A).

[chemical formula 1]

Formula (A)

(in formula (A), R⁴、R⁵And R⁶Respectively indicate substituted or unsubstituted alkyl.)

(10) according to the liquid crystal display device recorded in above-mentioned (1)-(9) any one, wherein the protective film for meeting above-mentioned formula (1) and formula (2) relationship contains at least one compound indicated by following formula (B).

[chemical formula 2]

Formula (B)

(in formula (B), R¹And R²Respectively indicate alkyl or aryl.)

(11) according to the liquid crystal display device recorded in above-mentioned (1)-(10) any one, wherein liquid crystal cells are VA modes.

According to the present invention it is possible to it is easy and inexpensively manufactured, and the liquid crystal display device for improving color degree field angle interdependence can be provided.

Detailed description of the invention

Fig. 1 is the schematic diagram for showing the example of preferred disposition of optical compensating film and polarizer protection film.

Fig. 2 is the schematic diagram for showing the example of liquid crystal display device of the invention.

Fig. 3 is the schematic diagram for showing the example of preferred disposition of optical compensating film and polarizer protection film.

The explanation of symbol:

1 upside polarizing film

The direction of 2 upside polarizing film absorption axiss

5 liquid crystal cells side electrode substrates

The tropism control direction of 6 upper boards

7 liquid crystal layers

Electrode base board on the downside of 8 liquid crystal cells

The tropism control direction of 9 lower boards

10 liquid crystal display devices

12 lower-side polarizing plates

The direction of 13 lower-side polarizing plate absorption axiss

Specific embodiment

In the following, the contents of the present invention are described in detail.In addition, the numerical value that "-" in the specification of the present application, "~" include front and back record is lower limit value and upper limit value.Number it is subsequent " more than ", " following " include this number.It can be suitable for decision according to the range of the present application effect is realized in addition, indicating " n " of the number of repeat unit in this specification unless specifically stated, being positive integer.

In this specification, the film that formula (1) and formula (2) relationship are met in the wave-length coverage of 400-700nm is known as " low latency film ".In addition, will be low latency film sometimes, and it be known as " low latency acylated cellulose film " by the substance of main material of acylated cellulose.

In liquid crystal display device of the invention with regard to two polarizing films at least one of for, the protective film close to the polarizing film of liquid crystal cell side meets formula (1) and formula (2) relationship in the wave-length coverage of 400-700nm.

Liquid crystal display device of the invention can take two kinds of structures.The first structure is that have to meet formula (3)-formula (8) relationship optical compensating film.The optical compensating film is arranged between the polarizer and liquid crystal cells, is also possible to the structure of the protective film (hereinafter referred merely to as " protective film ") as polarizing film, in addition the protective film can also be arranged.In liquid crystal display device of the invention, meet the protective film that formula (3)-formula (8) relationship optical compensating film is preferably used as close liquid crystal cell side.

Second of structure is that liquid crystal display device of the invention while having meets formula (9)-formula (12) relationship optical compensating film and meets formula (13)-formula (16) relationship optical compensating film.Meet formula (9)-formula (12) relationship optical compensating film to be preferably provided on the protective film of liquid crystal cell side, is used as the preferred acylated cellulose film of protective film at this time.It can also be as the protective film close to liquid crystal cell side in addition, meeting formula (13)-formula (16) relationship optical compensating film.

<close to the protective film of liquid crystal cell side among polarizing film>

The low latency film used in the present invention is roughly divided into two kinds.

The first is using norborneol alkenes film as representative, the thin polymer film for making intrinsic birefringent small monomer component carry out polymerizeing formation.

Second is to have positive intrinsic birefringent ingredient and negative intrinsic birefringent ingredient simultaneously, is offset each other by the showing property of the two, does not show the type of delay actually.Introducing method as positive intrinsic birefringent ingredient and negative intrinsic birefringent ingredient, known such as special open 2003-321535, the method that the polymer for being formed the two polymerization disclosed in No. 2004-176051 each bulletin of special open becomes film, it will be by positive birefringent at the polymer being grouped as and by the negative birefringent method being blended at the polymer being grouped as disclosed in special open 2003-292639 bulletin, main chain is set to play positive intrinsic birefringent ingredient in the polymer with main chain and side chain as acylated cellulose, side chain is set to play the method etc. of negative intrinsic birefringent ingredient.

It the use of the method for acylated cellulose film is wherein particularly preferred from the viewpoint of raw material are cheap and process suitable for polarizing film.

[acylated cellulose]

Firstly, in the low latency film that uses of the present invention it is preferable to use acylated cellulose be illustrated.

The degree of substitution of acylated cellulose refers to the ratio that the single hydroxyl present in the structural unit (glucose that 1 → 4 glucosides of β combines) of cellulose is acylated.Degree of substitution can be calculated by measuring the conjugated fatty acid amount of the structural unit per unit weight of cellulose.Measurement method is carried out according to ASTM-D817-91.In addition, 2,3 and 6 respective degree of substitution of the glucose that 1 → 4 glucosides of β combines can be by C¹³Peak intensity corresponding with the carbonyl carbon in acyl group calculates in-NMR measurement.

The preferably following two types of acylated cellulose in low latency film of the invention.

First seed type is the acetylcellulose that degree of acetylation is 2.7-3.0.Degree of acetylation is more preferably 2.85-2.98, further preferably 2.90-2.97.

Second of type is that have carbon atom number for the substance of the two or more acyl groups of 2-6.Acylation degree is preferably 2.6-2.98, more preferably 2.7-2.95.As acyl group, preferably acetyl group, propiono or bytyry.In addition, the degree of substitution of acetyl group is preferably shorter than 2.5, more preferably less than 2.0 when acylated cellulose film of the invention has acetyl group and acyl group in addition to this.

Acylated cellulose of the invention preferably has the weight average degree of polymerization of 350-800, more preferably with the weight average degree of polymerization of 370-600.Acylated cellulose of the invention preferably has the number-average molecular weight of 70000-230000, more preferably with the number-average molecular weight of 75000-230000, most preferably with the number-average molecular weight of 78000-120000.

Acid anhydrides can be used in acylated cellulose of the invention and acid chloride is synthesized as acylating agent.When acylating agent is acid anhydrides, use organic acid (such as acetic acid) and methylene chloride as reaction dissolvent.As catalyst, the protic catalyst of such as sulfuric acid etc is used.When acylating agent is acid chloride, use alkali compounds as catalyst.Industrially in most common synthetic method, acylated cellulose is synthesized by the way that cellulose to be esterified in the mixed organic acid ingredient containing organic acid (acetic acid, propionic acid, butyric acid) corresponding with acetyl group and other acyl groups or their acid anhydrides (acetic anhydride, propionic andydride, butyric anhydride).In the method, such as continuous cellulose for spending cotton linter and timber slurry etc often carries out activation in the organic acid of such as acetic acid etc, then in the presence of sulfuric acid catalyst, is esterified using the mixed liquor of Determination of Organic Acids as described above.Organic acid anhydride ingredient is excessively used usually relative to the amount of the hydroxyl present in cellulose.In the esterification treatment, in addition to esterification, the hydrolysis (depolymerization reaction) of 1 → 4 glycosidic bond of cellulosic backbone β is also carried out.If carrying out the hydrolysis of main chain, the degree of polymerization decline of acylated cellulose, the physical property of the acylated cellulose film of manufacture is reduced.Therefore, being determined if the reaction condition of reaction temperature etc is the preferred degree of polymerization for considering the acylated cellulose obtained and molecular weight.

To obtain high (molecular weight the is big) acylated cellulose of the degree of polymerization, it is important that the maximum temperature of esterification process is adjusted to 50 DEG C or less.Maximum temperature is preferably adjusted to 35-50 DEG C, is more preferably adjusted to 37-47 DEG C.By making 35 DEG C of reaction temperature or more, esterification can be more successfully carried out.By the way that reaction temperature is defined as 50 DEG C hereinafter, the degree of polymerization of acylated cellulose can more efficiently be inhibited to decline.After esterification, if stopping reaction while controlling temperature and rising, further the degree of polymerization can be inhibited to decline, so as to the high acylated cellulose of synthesized polymer degree.That is, the excessive acid anhydrides for being not involved in esterification generates corresponding organic acid by the way that hydrolysis is secondary if reaction stopping agent (for example, water, acetic acid) is added after reaction.With very exothermic, the temperature in reaction unit rises the hydrolysis.If reaction stopping agent addition speed it is excessive, be more than reaction unit cooling capacity and sharply heat release.Therefore, the hydrolysis of cellulosic backbone carries out obvious, the degree of polymerization decline of the acylated cellulose of acquisition.In addition, in conjunction with cellulose, major part dissociates during reaction stopping agent is added with cellulose a part of catalyst in esterification.But the addition speed of reacting stopping agent it is excessive when, the enough reaction time of dissociation catalyst is not used for, so that a part of catalyst is remained with the state in conjunction with cellulose.Part combines the acylated cellulose stability of strong acid catalyst excessively poor, when product drying due to heat etc. is easily decomposes and the degree of polymerization declines.According to the reason, after esterification, it is desirable to add reaction stopping agent preferably through 4 minutes or more, more preferably by 4-30 minute, stop reacting.In addition, from the viewpoint of industry productivity preferably the addition time rule of reaction stopping agent be 30 minutes or less.As reaction stopping agent, usually using the water and alcohol for decomposing acid anhydrides.But in the present invention, in order to which three esters for keeping the dissolubility in various organic solvents low are not precipitated, the mixture of water and organic acid is preferably used as reaction stopping agent.If carrying out esterification under conditions, as described above, the high molecular weight acylated cellulose that weight average degree of polymerization is 500 or more can be easily synthesized.

In the following, being illustrated to the additive contained in the low latency film used in the present invention.

In the low latency film used in the present invention, as additive, in addition to postponing depressant, anti-deterioration agent, ultraviolet absorbing agent, plasticizer etc. can also be contained.

(delay depressant)

When the low latency film that the present invention uses is low latency acylated cellulose film, as delay depressant, the compound high with the compatibility of acylated cellulose film is preferably comprised.

As delay depressant of the invention, the compound indicated with following formula (A) or formula (B) is since delay reducing effect is big, so being preferred.

The compound indicated with formula (A) is described in detail below.

[chemical formula 3]

Formula (A)

(in formula (A), R⁴、R⁵And R⁶Respectively indicate substituted or unsubstituted alkyl.)

In above-mentioned formula (A), R⁴、R⁵And R⁶Respectively indicate substituted or unsubstituted alkyl.Wherein alkyl can be straight chain, be also possible to branch, be also possible to ring-type.The preferred carbon atom number of alkyl is 1-20, more preferably 1-15, further preferably 1-12.As cricoid alkyl, particularly preferably cyclohexyl.

Alkyl in above-mentioned formula (A) also can have substituent group.As substituent group be halogen atom (such as; chlorine, bromine, fluorine and iodine), alkyl, alkoxy, acyl group, alkoxy carbonyl, acyloxy, sulfoamido, hydroxyl, cyano, amino and amide groups; more preferably halogen atom, alkyl, alkoxy, sulfoamido and amide groups, particularly preferably alkyl, sulfoamido and amide groups.

Then, following preferred examples shown with formula (A) compound indicated, but the present invention is not limited to these specific examples.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

Above compound can manufacture by known method.I.e., the compound indicated with formula (A) can be obtained by using the displacement of the carboxylic acids of condensing agent (for example, dicyclohexyl carbodiimide (DCC) etc.) and the dehydration condensation or carboxylic acid chloride derivative of amine and amine derivative reaction etc..

In the following, being illustrated to the compound indicated with following formula (B).

[chemical formula 8]

Formula (B)

(in formula (B), R¹And R²Respectively indicate alkyl or aryl.)

In addition, particularly preferred R¹And R²Carbon atom number summation be 10 or more.As the preferred fluorine atom of substituent group, alkyl, aryl, alkoxy, sulfo group and sulfoamido, particularly preferred alkyl, aryl, alkoxy, sulfo group and sulfoamido.In addition, alkyl can be straight chain, it is also possible to branch, it is also possible to ring-type, it is preferred that carbon atom number is 1-25, more preferably 6-25, particularly preferably 6-20 (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl).

It is 6-30, particularly preferred 6-24 (for example, phenyl, xenyl, terphenyl, naphthalene, binaphthyl, triphenyl phenyl) as the preferred carbon atom number of aryl.

Following preferred examples shown with formula (B) compound indicated, but the present invention is not limited to these specific examples.

[chemical formula 9]

[chemical formula 10]

In addition, postponing the additional amount of depressant relative to acylated cellulose, preferably 1-30 mass %, more preferably 2-30 mass %, further preferably 3-25 mass %, most preferably 5%-20 mass % in the present invention.

The delay depressant that the present invention uses for example can be added in cellulose acylate solutions (dope) and use after the organic solvent for being dissolved in pure and mild methylene chloride, dioxolanes, or is directly added into dope composition and uses.

(ultraviolet absorbing agent)

In order to which the wavelength dispersion for the low latency film for using the present invention becomes flat, it is preferably added to have the compound (ultraviolet absorbing agent) of maximum absorption as wavelength dispersion regulator in ultraviolet portion.The maximum absorption of ultraviolet absorbing agent ranges preferably from 230-380nm, more preferable 250-260nm.By having the effect of that maximum absorption can increase the yellowing for making wavelength dispersion become flat, and can inhibiting film in above range.

Well known ultraviolet absorbing agent can be widely used in the ultraviolet absorbing agent being added in low latency acylated cellulose film of the invention.

Ultraviolet absorbing agent is preferably added to 0.1-20 mass parts relative to 100 mass parts of acylated cellulose, and 0.1-15 mass parts are more preferably added, 0.1-10 mass parts are further preferably added.When being added a variety of, preferably these total amount is in above range.

As in the present invention it is preferable to use ultraviolet absorbing agent specific example, preferably with formula (III)-(VI) indicate compound.

[chemical formula 11]

Formula (III)

(in formula (III), Q¹And Q²Respectively indicate aromatic ring.X and Y be respectively with Q²In conjunction with group, indicate hydrogen atom or substituent group.)

Q¹And Q²It is respectively preferably phenyl ring or phenyl ring is condensed the substance to be formed.As the substituent group that X and Y can choose, preferably OR³⁰⁰, R³⁰⁰It is hydrogen atom or alkyl.

X and Y can also be respectively and with Q²Any one position of the aromatic ring of expression combines.

As the compound indicated with formula (III), for example, benzophenone compound can be enumerated.Preferred example as the compound corresponding to formula (III), aftermentioned ultraviolet absorbing agent UV-1,2 can be enumerated, 4- dihydroxy benaophenonel, 2,2 '-dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -5- diphenylsulfone ketone etc..

[chemical formula 12]

Formula (IV)

(in formula (VI), R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵It is the organic group of hydrogen atom, halogen atom (preferably fluorine atom or chlorine atom) or monovalence, R respectively⁴⁰¹、R⁴⁰²And R⁴⁰³At least one be total carbon atom number be 10-20 unsubstituted branched-chain or straight-chain alkyl.)

As R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Possessed organic group, in addition to alkyl, further preferably hydroxyl, alkoxy.

Preferred example as the compound corresponding to formula (IV), can enumerate 2- (2 '--5 '-aminomethyl phenyl of hydroxyl) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) benzotriazole, 2- (2 '--3 '-tert-butyls -5 of hydroxyl '-aminomethyl phenyl) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 '-(3 "; 4 " 5 ", 6 "-tetrahydro phenol imide methyl) -5 '-aminomethyl phenyl) benzotriazole etc..

[chemical formula 13]

Formula (V)

(in formula, R⁵⁰¹、R⁵⁰²、R⁵⁰⁴And R⁵⁰⁵It is organic group, the R of monovalence respectively⁵⁰⁶It is the alkyl with branch.)

Preferred example as the compound corresponding to formula (V) can enumerate the compound with following structural formula (UV-105), (UV-106) expression.

(UV-105)

[chemical formula 14]

(UV-106)

[chemical formula 15]

It, can also it is preferable to use the compounds indicated with formula (VI) in addition, as disclosed in special open 2003-315549 bulletin.

[chemical formula 16]

Formula (VI)

(in formula, R⁶⁰⁰And R⁶⁰¹Respectively indicate hydrogen atom, the phenylalkyl that the alkyl that carbon atom number is 1~25, carbon atom number are 7~9, it is unsubstituted or by carbon atom number be 1~4 alkyl-substituted phenyl, substituted or unsubstituted oxo carbonyl, substituted or unsubstituted amino carbonyl.R⁶⁰²~R⁶⁰⁵And R⁶¹⁹~R⁶²³Respectively indicate hydrogen atom, the substituted or unsubstituted alkyl that carbon atom number is 2~20.)

The preferred example with formula (IV) compound indicated has been illustrated below.

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

Then the ultraviolet absorbing agent indicated with following formula (VII)s is described in detail.

Q⁷⁰¹-Q⁷⁰²- OH formula (VII)

(in formula (VII), Q⁷⁰¹Indicate 1,3,5-triazines ring, Q⁷⁰²Indicate aromatic ring.) it is used as formula (VII), the compound more preferably indicated with following formula (VII-A).

[chemical formula 20]

Formula (VII-A)

(in formula (VII-A), R⁷⁰¹Indicate that carbon atom number is 1~18 alkyl；The naphthenic base that carbon atom number is 5~12；The alkenyl that carbon atom number is 3~18；Phenyl；The alkenyloxy group or halogen atom or-COOH or-COOR that the cycloalkyloxy or carbon atom number that the alkoxy or carbon atom number that phenyl or OH or carbon atom number are 1~18 are 5~12 are 3~18⁷⁰⁴Or-O-CO-R⁷⁰⁵Or-O-CO-O-R⁷⁰⁶Or-CO-NH₂Or-CO-NHR⁷⁰⁷Or-CO-N (R⁷⁰⁷)(R⁷⁰⁸) or CN or NH₂Or NHR⁷Or-N (R⁷⁰⁷)(R⁰¹⁸) or-NH-CO-R⁷⁰⁵Phenoxy group or by carbon atom number be 1~18 alkyl-substituted phenoxy group；By phenyl-carbon atom number be 1~4 alkoxy or carbon atom number be 6~15 bicycloalkoxy carbon atom number be 6~15 bicyclic alkyl alkoxy or carbon atom number be 6~15 bicycloenyl alkoxy or carbon atom number be 6~15 the carbon atom number that replaces of three cycloalkyloxies be 1~18 alkyl；The alkenyl or-O-CO-R for being 2~6 by OH or the carbon atom number alkyl for being 1~4 or carbon atom number⁷⁰⁵The naphthenic base that substituted carbon atom number is 5~12；Glycidyl；-CO-R⁷⁰⁹；-SO₂-R⁷¹⁰；The alkyl that carbon atom number being interrupted by 1 or more oxygen atom and/or being replaced by OH or phenoxy group or the carbon atom number alkyl phenoxy for being 7~18 is 3~50；-A；-CH₂-CH(XA)-CH₂-O-R⁷¹²；-CR⁷¹³R’⁷¹³-(CH₂)_m-X-A；-CH₂-CH(OA)-R⁷¹⁴；-CH₂-CH(OH)-CH₂-XA；

[chemical formula 21]

-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵；-CR⁷¹³R’⁷¹³-(CH₂)_m-CO-X-A；-CR⁷¹³R’⁷¹³-(CH₂)_m-CO-O-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵；Or with-CO-O-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵(in formula, A expression-CO-CR⁷¹⁶=CH-R⁷¹⁷.) indicate definition it-；

R⁷⁰²Respectively indicate the alkyl that carbon atom number is 6~18；The alkenyl that carbon atom number is 2~6；Phenyl；The phenylalkyl that carbon atom number is 7~11；COOR⁷⁰⁴；CN；-NH-CO-R⁷⁰⁵；Halogen atom；Trifluoromethyl；-O-R⁷⁰³；

R⁷⁰³With R⁷⁰¹It is synonymous；

R⁷⁰⁴Indicate that carbon atom number is 1~18 alkyl；The alkenyl that carbon atom number is 3~18；Phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；By more than one-O- ,-NH- ,-NR⁷⁰⁷,-S- interrupt and be 3~50 by the carbon atom number that the alkyl phenoxy that OH, phenoxy group or carbon atom number are 7~18 replaces alkyl；

R⁷⁰⁵Indicate H；The alkyl that carbon atom number is 1~18；The alkenyl that carbon atom number is 2~18；The naphthenic base that carbon atom number is 5~12；Phenyl；The phenylalkyl that carbon atom number is 7~11；The bicyclic alkyl that carbon atom number is 6~15；The bicycloenyl that carbon atom number is 6~15；The tricyclic alkyl that carbon atom number is 6~15；

R⁷⁰⁶Indicate H；The alkyl that carbon atom number is 1~18；The alkenyl that carbon atom number is 3~18；Phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；

R⁷⁰⁷And R⁷⁰⁸Respectively indicate the alkyl that carbon atom number is 1~12；The alkoxyalkyl that carbon atom number is 3~12；The dialkyl aminoalkyl that carbon atom number is 4~16；The naphthenic base that carbon atom number is 5~12；

R⁷⁰⁷And R⁷⁰⁸The oxaalkylene that alkylidene, carbon atom number that carbon atom number is 3~9 are 3~9 or the aza-alkylene that carbon atom number is 3~9 can also be indicated by combining；

R⁷⁰⁹Indicate that carbon atom number is 1~18 alkyl；The alkenyl that carbon atom number is 2~18；Phenyl；The naphthenic base that carbon atom number is 5~12；The phenylalkyl that carbon atom number is 7~11；The bicyclic alkyl that carbon atom number is 6~15；The bicycloenyl that bicyclic alkyl alkyl that carbon atom number is 6~15, carbon atom number are 6~15；Or the tricyclic alkyl that carbon atom number is 6~15；R⁷¹⁰Indicate that carbon atom number is 1~12 alkyl；Phenyl；Naphthalene；Or the alkyl phenyl that carbon atom number is 7~14；

R⁷¹¹Respectively indicate H；The alkyl that carbon atom number is 1~18；The alkenyl that carbon atom number is 3~6；Phenyl；The phenylalkyl that carbon atom number is 7~11；Halogen atom；The alkoxy that carbon atom number is 1~18；

R⁷¹²Indicate that carbon atom number is 1~18 alkyl；The alkenyl that carbon atom number is 3~18；Phenyl；By carbon atom number be 1~8 alkyl, carbon atom number be 1~8 alkoxy, carbon atom number be 3~8 alkenyloxy, halogen atom or trifluoromethyl replace 1~3 phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；The tricyclic alkyl that carbon atom number is 6~15；The bicyclic alkyl that carbon atom number is 6~15；The bicyclic alkyl alkyl that carbon atom number is 6~15；The bicycloenyl alkyl that carbon atom number is 6~15；-CO-R⁷⁰⁵；It can also indicate by more than one-O- ,-NH- ,-NR⁷,-S- interrupt and be 3~50 by the carbon atom number that the alkyl phenoxy that OH, phenoxy group or carbon atom number are 7~18 replaces alkyl；

R⁷¹³And R '⁷¹³Respectively indicate H；The alkyl that carbon atom number is 1~18；Phenyl；

R⁷¹⁴Indicate that carbon atom number is 1~18 alkyl；The alkoxyalkyl that carbon atom number is 3~12；Phenyl；The alkyl that phenyl-carbon atom number is 1~4；

R⁷¹⁵、R’⁷¹⁵And R "⁷¹⁵Respectively indicate H or CH₃；

R⁷¹⁶Indicate H；-CH₂-COO-R⁷⁰⁴；The alkyl that carbon atom number is 1~4；Or CN；

R⁷¹⁷Indicate H；-COOR⁷⁰⁴；The alkyl that carbon atom number is 1~17；Or phenyl；

X expression-NH-；-NR⁷⁰⁷-；-O-；-NH-(CH₂)_p-NH-；Or

-O-(CH₂)_q-NH-；

M indicates 0~19 integer；

N indicates 1~8 integer；

P indicates 0~4 integer；

Q indicates 2~4 integer；

But in formula (VII-A), R⁷⁰¹、R⁷⁰²And R⁷¹¹At least one include more than two carbon atoms.

In addition the compound of formula (VII-A) is illustrated.

R as alkyl⁷⁰¹~R⁷¹⁰、R⁷¹²~R⁷¹⁴、R⁷¹⁶And R⁷¹⁷It is the alkyl of linear chain or branched chain, such as, methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, isobutyl group, tert-butyl, 2- ethyl-butyl, n- amyl, isopentyl, 1- methyl amyl, 1, 3- dimethylbutyl, n- hexyl, 1- methylhexyl, n- heptyl, different heptyl, 1, 1, 3, 3- tetramethyl butyl, 1- methylheptyl, 3- methylheptyl, n- octyl, 2- ethylhexyl, 1, 1, 3- trimethyl, 1, 1, 3, 3- tetramethyl amyl, nonyl, decyl, undecyl, 1- methylundecyl, dodecyl, 1, 1, 3, 3, 5, 5- hexamethyl hexyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl or octadecyl.

R as the naphthenic base that carbon atom number is 5~12⁷⁰¹、R⁷⁰³~R⁷⁰⁹And R⁷¹²E.g. cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl.It is preferred that cyclopenta, cyclohexyl, cyclooctyl and cyclo-dodecyl.

R as alkenyl⁷¹⁶、R⁷¹⁹、R⁷¹¹And R⁷¹²It especially include allyl, isopropenyl, 2- cyclobutenyl, 3- cyclobutenyl, isobutenyl, amyl- 2, the 4- diethyl of n-, 3- methyl-but-2-ene base, n- oct-2-ene base, 12-2- alkenyl of n-, 18-4- alkenyl of iso- laurylene base, 12-2- alkenyl of n- and n-.

The substitution radix of substituted alkyl, naphthenic base or phenyl is 1,2 or more, can have substituent group (in alpha-position) or in other carbon atoms in the carbon atom of combination；When substituent group is combined by hetero atom (such as alkoxy), the binding site of substituent group is preferably other than α mono-, in addition, the carbon atom number of the alkyl replaced is preferably 2 or more, more preferably 3 or more.2 or more substituent groups are preferably combined from different carbon atoms.

By-O- ,-NH- ,-NR⁷⁰⁷, the alkyl that interrupts of-S- can also be usually that a group is inserted into a key by more than one interruption of these groups, respective situation, and do not generate miscellaneous-heterodesmic, such as O-O, S-S, NH-NH etc.；When the alkyl of interruption is replaced again, substituent group is not located at α generally relative to hetero atom.When generating more than two-O- ,-NH- ,-NR in a group⁷⁰⁷,-S- type interrupt group when, these are usually identical.

Aryl is usually aromatic hydrocarbyl, such as phenyl, xenyl or naphthalene, preferably phenyl and xenyl.Aralkyl is usually by aryl, especially the alkyl substituted by phenyl；Therefore the aralkyl that carbon atom number is 7~20 includes such as benzyl, α-methylbenzyl, phenylethyl, phenyl propyl, phenyl butyl, phenylpentyl and Phenylhexyl；The preferred benzyl of phenylalkyl, α-methylbenzyl and the alpha, alpha-dimethylbenzyl that carbon atom number is 7~11.

Alkyl phenyl and alkyl phenoxy are by alkyl-substituted phenyl or phenoxy group respectively.

Halogen atom as halogenic substituent is fluorine atom, chlorine atom, bromine atom or iodine atom, more preferable fluorine atom or chlorine atom, particularly preferred chlorine atom.

The alkylidene that carbon atom number is 1~20 is such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene.Wherein alkyl chain can be with branching, e.g. isopropylidene.

The cycloalkenyl that carbon atom number is 4~12 is such as 2- cyclobutane -2- base, 2- cyclopentene -1- base, 2,4- cyclopentadiene -1- base, 2- cyclohexene -1- base, 2- cycloheptene -1- base or 2- cyclo-octene -1- base.

The bicyclic alkyl that carbon atom number is 6~15 is such as bornyl, norborneol alkyl, [2.2.2] bicyclooctyl.It is preferred that bornyl and norborneol alkyl, particularly preferred bornyl and norbornane -2- base.

The bicycloalkoxy that carbon atom number is 6~15 is such as borneol oxygroup or norbornane -2- base oxygroup.

Bicyclic alkyl-the alkyl or-alkoxy that carbon atom number is 6~15 are the alkyl or alkoxy replaced by bicyclic alkyl, and the sum of carbon atom is 6~15；Specific example is norbornane -2- methyl and norbornane -2- methoxyl group.

The bicycloenyl that carbon atom number is 6~15 is such as norbornene, norbornadiene base.It is preferred that norbornene, particularly preferred norborneol -5- alkenyl.

The bicycloenyl alkoxy that carbon atom number is 6~15 is the alkoxy replaced by bicycloenyl, and the sum of carbon atom is 6~15；E.g. norborneol -5- alkene -2- methoxyl group.

The tricyclic alkyl that carbon atom number is 6~15 is such as 1- adamantyl, 2- adamantyl, preferably 1- adamantyl.

Three cycloalkyloxies that carbon atom number is 6~15 are such as Buddha's warrior attendant alkoxies.The preferred pyridyl group of heteroaryl, pyrimidine radicals, triazine radical, pyrrole radicals, furyl, thienyl or the quinolyl that carbon atom number is 3~12.

R is more preferably with the compound that formula (VII-A) indicates⁷⁰¹It is the alkyl that carbon atom number is 1~18；The naphthenic base that carbon atom number is 5~12；(chain) alkenyl that carbon atom number is 3~12；Phenyl；The alkenyloxy group or halogen atom or-COOH or-COOR that the cycloalkyloxy or carbon atom number that the alkoxy or carbon atom number that phenyl or OH or carbon atom number are 1~18 are 5~12 are 3~18⁷⁰⁴Or-O-CO-R⁷⁰⁵Or-O-CO-O-R⁷⁰⁶Or-CO-NH₂Or-CO-NHR⁷⁰⁷Or-CO-N (R⁷⁰⁷)(R⁷⁰⁸) or CN or NH₂Or NHR⁷⁰⁷Or-N (R⁷⁰⁷)(R⁷⁰⁸) or-NH-CO-R⁷⁰⁵Phenoxy group or by carbon atom number be 1~18 alkyl-substituted phenoxy group；By phenyl-carbon atom number be 1~4 alkoxy or the carbon atom number that replaces of borneol oxygroup or norbornane -2- base oxygroup or norbornane -2- methoxyl group or norborneol -5- alkene -2- methoxyl group or Buddha's warrior attendant alkoxy be 1~18 alkyl；The alkenyl and/or-O-CO-R for being 2~6 by OH or the carbon atom number alkyl for being 1~4 or carbon atom number⁷⁰⁵The naphthenic base that substituted carbon atom number is 5~12；Glycidyl；-CO-R⁷⁰⁹Or-SO₂-R⁷¹⁰；R⁷¹¹Indicate the alkyl that carbon atom number being interrupted by 1 or more oxygen atom and/or being replaced by OH or phenoxy group or the carbon atom number alkyl phenoxy for being 7~18 is 3~50；-A；-CH₂-CH(XA)-CH₂-O-R⁷¹²；-CR⁷¹³R’⁷¹³-(CH₂)_m-X-A；-CH₂-CH(OA)-R⁷¹⁴；-CH₂-CH(OH)-CH₂-XA；

[chemical formula 22]

-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵；-CR⁷¹³R’⁷¹³-(CH₂)_m-CO-X-A；With-CR⁷¹³R’⁷¹³-(CH₂)_m-CO-O-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵Or-CO-O-CR⁷¹⁵R’⁷¹⁵- C (=CH₂)-R”⁷¹⁵(in formula, A expression-CO-CR⁷¹⁶=CH-R⁷¹⁷.) one of the definition that indicates；

R⁷⁰²Indicate that carbon atom number is 6~18 alkyl；(chain) alkenyl that carbon atom number is 2~6；Phenyl；-O-R⁷⁰³Or-NH-CO-R⁷⁰⁵；

R⁷⁰³Respectively with R⁷⁰¹It is synonymous；

R⁷⁰⁴Indicate that carbon atom number is 1~18 alkyl；(chain) alkenyl that carbon atom number is 3~18；Phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；It can also be by 1 or more-O- ,-NH- ,-NR⁷⁰⁷,-S- is interrupted and the carbon atom number that is replaced by OH or phenoxy group or the carbon atom number alkyl phenoxy for being 7~18 is 3~50 alkyl；

R⁷⁰⁵Indicate H；The alkyl that carbon atom number is 1~18；The alkenyl that carbon atom number is 2~18；The naphthenic base that carbon atom number is 5~12；Phenyl；The phenylalkyl that carbon atom number is 7~11；Norbornane -2- base；Norborneol -5- alkene -2- base；Adamantyl；

R⁷⁰⁶Indicate H；The alkyl that carbon atom number is 1~18；The alkenyl that carbon atom number is 3~18；Phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；

R⁷⁰⁷And R⁷⁰⁸Indicate that carbon atom number is 1~12 alkyl independently of one another；The alkoxyalkyl that carbon atom number is 3~12；The dialkyl aminoalkyl that carbon atom number is 4~16；The naphthenic base that carbon atom number is 5~12；R⁷⁰⁷And R⁷⁰⁸It can also be bonded to each other to form the alkylidene that carbon atom number is 3~9；The aza-alkylene that the oxaalkylene or carbon atom number that carbon atom number is 3~9 are 3~9；

R⁷⁰⁹Indicate that carbon atom number is 1~18 alkyl；The alkenyl that carbon atom number is 2~18；Phenyl；The naphthenic base that carbon atom number is 5~12；The phenylalkyl that carbon atom number is 7~11；Norbornane -2- base；Norborneol -5- alkene -2- base；Adamantyl；

R⁷¹⁰Indicate that carbon atom number is 1~12 alkyl；Phenyl；Naphthalene；Or the alkyl phenyl that carbon atom number is 7~14；

R⁷¹¹Respectively indicate H；The alkyl that carbon atom number is 1~18；The phenylalkyl that carbon atom number is 7~11；

R⁷¹²It is the alkyl that carbon atom number is 1~18；(chain) alkenyl that carbon atom number is 3~18；Phenyl；By carbon atom number be 1~8 alkyl or carbon atom number be 1~8 alkoxy carbon atom number be 3~8 alkenyloxy group or halogen atom or trifluoromethyl replace 1~3 phenyl；The phenylalkyl that carbon atom number is 7~11；The naphthenic base that carbon atom number is 5~12；1- adamantyl；2- adamantyl；Norborneol alkyl；Norbornane -2- methyl -；-CO-R⁷⁰⁵；

R⁷¹²It can also indicate by 1 or more-O- ,-NH- ,-NR⁷⁰⁷,-S- is interrupted and the carbon atom number that is replaced by OH or phenoxy group or the carbon atom number alkyl phenoxy for being 7~18 is 3~50 alkyl；

R⁷¹³And R '⁷¹³Respectively indicate H；The alkyl that carbon atom number is 1~18；Phenyl, R⁷¹⁴Indicate that carbon atom number is 1~18 alkyl；The alkoxyalkyl that carbon atom number is 3~12；Phenyl；The alkyl that phenyl-carbon atom number is 1~4；

R⁷¹⁵With R '⁷¹⁵And R "⁷¹⁵H or CH is indicated independently of one another₃；

R¹⁶Indicate H；-CH₂-COO-R⁷⁰⁴；The alkyl that carbon atom number is 1~4；Or CN；R¹⁷Indicate H；-COOR⁷⁰⁴；The alkyl that carbon atom number is 1~17；Phenyl；

X expression-NH-；-NR⁷⁰⁷-；-O-；-NH-(CH₂)_p-NH-；-O-(CH₂)_q-NH-；

M indicates 0~19 integer；

N indicates 1~8 integer；

P indicates 0~4 integer；

Q indicates the case where 2~4 integer.

The compound indicated with formula (VII) and (VII-A) can use customary way, such as according to No. 434608 bulletins of European Patent No. or H.Brunetti and C.E.Luthi, Helv.Chim.Acta 55, method shown in the publication of 1566 (1972) is identical with this ground, by Knut Fridell-Kerafyrm thatch (mono- デ Le of Off リ-Network ラ Off Star) addition of halogenated triazine and suitable phenol, obtain identically as well known compound.

Then, following to show the preferred example of the compound indicated with formula (VII) and (VII-A), but the compound that can be used in the present invention is not limited to these specific examples.

[chemical formula 23]

Compound N o.	R3	R1
			UV-1	-CH2CH(OH)CH2OC4H8-n	-CH3
UV-2	-CH2CH(OH)CH2OC4H8-n	-C2H5
			UV-3	R3=R1=-CH2CH(OH)CH2OC4H8-n
UV-4	-CH(CH3)-CO-O-C2H5	-C2H5
			UV-5	R3=R1=-CH (CH3)-CO-C2H5
UV-6	-C2H5	-C2H5
			UV-7	-CH2CH(OH)CH3OC4H8-n	-CH(CH3)2
UV-8	-CH2CH(OH)CH2OC4H8-n	-CH(CH3)-C2H5
			UV-9	R3=R1=-CH2CH(C2H3)-C4H8-n
UV-10	-C8H17-n	-C8H17-n
			UV-11	-C3H7-n	-CH3
UV-12	-C2H7-n	-C2H5
			UV-13	-C3H7-n	-C3H7-n
UV-14	-C3H7It is different	-CH3
			UV-15	-C3H7It is different	-C2H5
UV-16	-C3H7It is different	-C3H5It is different
			UV-17	-C4H8-n	-CH3
UV-18	-C4H8-n	-C2H5
			UV-19	-C4H8-n	-C4H8-n

[chemical formula 24]

Compound N c.	R3	R1
			UV-20	-CH2CH(CH3)2	-CH3
UV-21	-CH2CH(CH3)2	-C2H5
			UV-22	-CH2CH(CH3)2	-CH2CH(CH3)2
UV-23	N- hexyl	-CH3
			UV-24	N- hexyl	-C2H5
UV-25	N- hexyl	N- hexyl
			UV-26	-C7H15-n	-CH2
UV-27	-C7H15-n	-C2H5
			UV-28	-C7H15-n	-C7H15-n
UV-29	-C8H17-n	-CH3
			UV-30	-C8H17-n	-C2H5
UV-31	-CH2CHCH(CH3)2	-CH2CHCH(CH3)2
			UV-32	-C5H11-n	-C5H11-n
UV-33	-C12H26-n	-C12H26-n
			UV-34	-C16H36-n	-C2H5
UV-35	-CH2-CO-O-C2H8	-CH2-CO-O-C2H5

Apart from the above, for example, further preferably salt compounds etc. are complexed in oxo benzophenone compound, benzotriazole compound, salicylic acid ester type compound, cyanoacrylate compound, nickel.

As Benzotriazole Ultraviolet Stabilizer, 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole can be enumerated, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) benzotriazole, 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydro phenol acid imide methyl) -5 '-aminomethyl phenyls) benzotriazole, 2, 2- di-2-ethylhexylphosphine oxide (4- (1, 1, 3, 3- tetramethyl butyl) -6- (2H- benzotriazole -2- base) phenol), 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) -5- chlorobenzotriazole, 2, 4- dihydroxy benaophenonel, 2, 2 '-dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -5- diphenylsulfone ketone, bis- (2- methoxyl group -4- hydroxyl -5- Benzoylbenzene methylmethanes), (2, 4- is bis--(n- octylthio) -6- (4- hydroxyl -3, 5- di-t-butyl anilino-) -1, 3, 5- triazine, 2 (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) -5- chlorobenzotriazole, (2 (2 '-hydroxyls -3 ', 5 '-two-tertiary pentyl phenyl) -5- chlorobenzotriazole, 2, 6- di-t-butyl-p- cresols, (the 3- (3 of pentaerythrite four, 5- di-t-butyl -4- hydroxy phenyl) propionic ester), bis- (3- (3- tert-butyl -5- methyl -4- the hydroxyls of triethylene glycol - Base phenyl) propionic ester), 1, 6- hexylene glycol-bis- (3- (3, 5- di-t-butyl -4- hydroxy phenyl) propionic ester), 2, 4- is bis--(n- octylthio) -6- (4- hydroxyl -3, 5- di-t-butyl anilino-) -1, 3, 5- triazine, 2, bis- (the 3- (3 of 2- sulfenyl-diethylene, 5- di-t-butyl -4- hydroxy phenyl) propionic ester), octadecyl -3- (3, 5- di-t-butyl -4- hydroxy phenyl) propionic ester, N, N '-hexamethylene bis (3, 5- di-t-butyl -4- hydroxy-hydrocineamide), 1, 3, 5- trimethyl -2, 4, 6- tri- (3, 5- di-t-butyl -4- hydroxybenzyl) benzene, three-(3, 5- di-t-butyl -4- hydroxybenzyl)-chlorinated isocyanurates etc..Particularly preferably (2,4- is bis--(n- octylthio) -6- (4- hydroxyl -3,5- di-t-butyl anilino-) -1,3,5- triazine, 2 (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) -5- chlorobenzotriazole, (2 (2 '-hydroxyls -3 ', 5 '-two-tertiary pentyl phenyl) -5- chlorobenzotriazole, 2,6- di-t-butyl-p- cresols, pentaerythrite four (3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester), triethylene glycol-are bis- (3- (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic ester).

In addition such as N, the Phosphorus processing stabilizers such as the agent of hydrazines metal-inert and three (2,4- di-t-butyl phenyl) phosphides such as bis- (3- (3,5- di-t-butyl -4- hydroxy phenyl) propiono) hydrazines of N '-also can be used together.The additional amount of metal-inert agent and Phosphorus processing stabilizers is preferably 1ppm-1.0%, more preferably 10-1000ppm in terms of mass ratio relative to acylated cellulose.

In addition, rising sun electrification, additives for plastics summary, the light stabilizer in the catalogue of " ア デ カ ス タ Block " in addition to this also can be used.Light stabilizer, the ultraviolet absorbing agent in the TINUVIN product guide of Ciba Special Chemicals can also be used.SEESORB, SEENOX, SEETEC etc. in the catalogue of SHIPROKASEI KAISYA can also be used.Also ultraviolet absorbing agent, the antioxidant of north of the city chemical industry can be used.Also the VIOSORB of common drug, the ultraviolet absorbing agent of lucky rich pharmacy can be used.

In addition, ultraviolet absorbing agent of the invention can also be added in pre-production acylated cellulose mixed solution, but can also with the dope of pre-production acylated cellulose, until curtain coating whenever addition.In the latter case; it is added, mixed, it is preferable to use online mixer such as ス タ チ Star Network ミ キ サ mono- (eastern レ エ Application ヂ ニ ア リ Application グ system), SWJ (mixer Hi-Mixer in eastern レ silent oscillation pipe) etc. online to solution of the cellulose dissolution in the dope of solvent, ultraviolet absorbing agent and a small amount of acylated cellulose dissolution will be acidylated.In the ultraviolet absorbing agent of rear addition, delustering agent can be mixed simultaneously, can also be mixed it and be postponed the additives such as controlling agent, plasticizer, anti-deterioration agent, removing promotor.When using online mixer, concentration dissolution is preferably carried out under high pressure, the type of heater is not particularly limited, as long as can be resistant to defined pressure, can heat, stir under elevated pressure.Furthermore pressurizing vessel can be appropriately arranged with the metrical instruments class such as pressure gauge, thermometer.Pressurization can also be such that the vapour pressure rising of solvent carries out with the method for the inert gases such as indentation nitrogen and by heating.Heating is preferably carried out from outside, such as is easy to the temperature controller of preferred jacket type.The heating temperature that solvent is added is preferably to use the boiling point of solvent or more and the temperature of the solvent not boiling range, such as the suitable range for being set to 30-150 DEG C.In addition, pressure is adjusted in such a way that solvent at a set temperature does not boil.From container while cooling down after dissolution and take out, or extracted out with pump etc. and cooled down with heat exchanger etc. from container, is then supplied to film.Cooling temperature at this time can also be cooled to room temperature, but due to being cooled to 5-10 DEG C of low temperature by boiling point, in addition to can still cast in the temperature, viscosity of dope can also be reduced, so more preferably.

Then the manufacturing method of the low latency acylated cellulose film used to the present invention is described in detail.

Low latency acylated cellulose film of the invention can be manufactured with solvent cast method.Solvent cast method manufactures film using acylated cellulose to be dissolved in the solution formed in organic solvent (dope).

Above-mentioned organic solvent preferably comprises solvent chosen from the followings: the halogenated hydrocarbons that the ester and carbon atom number that ketone that ether that carbon atom number is 3-12, carbon atom number are 3-12, carbon atom number are 3-12 are 1-6.

Above-mentioned ether, ketone and ester can have cyclic structure.Alternatively, it is also possible to use with more than two compounds among above-mentioned ether, ketone and ester functional group (it is ,-O- ,-CO- and-COO-) as above-mentioned organic solvent.Above-mentioned organic solvent can also have other functional groups of alcohol hydroxyl group etc.When for the organic solvent of two or more functional groups, carbon atom number is preferably in the above-mentioned preferred carbon atom number range of the solvent with any functional group.

Above-mentioned carbon atom number is that the example of the ethers of 3-12 includes: Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, Isosorbide-5-Nitrae-dioxanes, 1,3- dioxolane, tetrahydrofuran, methyl phenyl ethers anisole and phenetole.

Carbon atom number is that the example of the ketone of 3-12 includes: acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclohexanone and methyl cyclohexanone.

Carbon atom number is that the example of the esters of 3-12 includes: Ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.

In addition, the example of the organic solvent with two or more functional groups includes: 2- ethoxyethyl group acetate, 2-methyl cellosolve and butoxy ethanol.

The carbon atom number for the halogenated hydrocarbons for being 1-6 outside carbon atom number is preferably 1 or 2, more preferably 1.The halogen of halogenated hydrocarbons is preferably chlorine.The ratio that the hydrogen atom of halogenated hydrocarbons is optionally substituted by halogen is preferably 25-75 moles of %, more preferably 30-70 moles of %, further preferably 35-65 moles of %, most preferably 40-60 moles of %.Methylene chloride is representative halogenated hydrocarbons.

In addition it is also possible to which two or more organic solvents is used in mixed way.

Cellulose acylate solutions (dope；Dope the conventional method modulation handled at 0 DEG C or more of temperature (room temperature or high temperature)) can be used.The method and apparatus of the modulation dope in common solvent cast method can be used to implement in the modulation of cellulose acylate solutions.In addition, it is preferable to use halogenated hydrocarbons (especially methylene chloride) is used as organic solvent when for general method.

The amount of acylated cellulose in cellulose acylate solutions (composition) is adjusted so that acylated cellulose containing 10-40 mass % in resulting solution.The amount of acylated cellulose is more preferably 10-30 mass %.In organic solvent (main solvent), aftermentioned arbitrary additive can be added.

Cellulose acylate solutions are prepared and stirring acylated cellulose and organic solvent under room temperature (such as 0-40 DEG C).The solution of high concentration can also be stirred under conditions of pressurization and heating.Specifically acylated cellulose and organic solvent are put into closed in pressurizing vessel, more than the boiling point being heated under the room temperature of solvent under elevated pressure and do not make in the temperature of solvent boiling range, be stirred simultaneously.Heating temperature is preferably 40 DEG C or more, more preferably 60-200 DEG C, further preferably 80-110 DEG C.

Each ingredient can be put into container after thick mixing in advance.Furthermore, it is also possible to successively put into container.Container must have the structure that can be stirred.It can pressurize after the inert gases such as injection nitrogen to container.Furthermore, it is possible to rise the vapour pressure of solvent by heating.Alternatively, adding each ingredient under stress after by container closure.

When heated, it is preferably heated from external container.Jacket type heating device can be used for example.Alternatively, it is also possible to heat liquid circulation integrally to container by piping by the way that baffle heater is arranged in external container.

Stirring slurry is preferably arranged inside container and is carried out using the stirring slurry for stirring.The length of stirring slurry is preferably the length reached near chamber wall.In order to update the liquid film of chamber wall, preferably in the end of stirring slurry setting scraping paddle.

The metrical instruments class such as pressure gauge, thermometer can be set in a reservoir.Each ingredient in container dissolves in a solvent.The dope of preparation takes out from container after cooling, or after taking-up, reuses heat exchanger etc. and is cooled down.

Cellulose acylate solutions can also be prepared using hot-cold lysis method.Hot-cold lysis method can acidylate cellulose and be difficult in the organic solvent dissolved or dissolve in common dissolving method.Even in addition, the solvent that can dissolve acylated cellulose in common dissolving method, which also has the effect that, can obtain rapidly uniform solution using hot-cold lysis method.

In hot-cold lysis method, initially slowly acylated cellulose can be added in organic solvent while agitating at room temperature.

Adjust acylated cellulose of the amount of acylated cellulose preferably in the mixture containing 10-40 mass %.The amount of acylated cellulose is more preferably 10-30 mass %.In addition, aftermentioned arbitrary additive can be added in mixture.

Then, mixture is cooled to preferably -100~-10 DEG C (more preferably -80~-10 DEG C, further preferably -50~-20 DEG C, most preferably -50~-30 DEG C).It is cooling for example to be carried out in dry ice methanol bath (- 75 DEG C) and cooling diethylene glycol solution (- 30~-20 DEG C).The mixture solidification of cellulose and organic solvent can be acidylated by cooling.

Cooling velocity is preferably 4 DEG C/min or more, further preferably 8 DEG C/min or more, most preferably 12 DEG C/min or more.The faster the better for cooling velocity, but substantially 10000 DEG C/sec of the theoretic upper limit, substantially 1000 DEG C/sec of the technology upper limit, and substantially 100 DEG C/sec of practical upper limit.In addition, the ratio that the difference that cooling velocity is the temperature and final cooling temperature when beginning to cool is obtained divided by the time of cooling temperature final from beginning to cool to reaching.

In addition, if cooling mixture is warming up to preferred 0-200 DEG C (more preferably 0-150 DEG C, further preferably 0-120 DEG C, most preferably 0-50 DEG C), then acylated cellulose dissolves in organic solvent.Heating, which can be only placed in room temperature, to be carried out, and can also be heated up in bath temperature.Heating rate is preferably 4 DEG C/min or more, further preferably 8 DEG C/min or more, most preferably 12 DEG C/min or more.The faster the better for heating rate, is theoretically limited to 10000 DEG C/sec, is technically limited to 1000 DEG C/sec, and practical upper limit is 100 DEG C/sec.In addition, heating rate be the temperature and final warming temperature when starting to warm up difference divided by from start to warm up reach final warming temperature time obtained from ratio.

According to the available uniform cellulose acylate solutions of step as above.In addition, the operation of cooling heating can be repeated when dissolving insufficient.The appearance of solution is only observed by visual observation it may determine that whether dissolution is abundant.

In hot-cold lysis method, it is expected that being mixed into moisture using closed container to avoid condensing while cooling.It is depressurized when in addition, pressurizeing, heating up while cooling in cooling warming operation, dissolution time can be shortened.It is expected that using resistance to pressure container to implement to pressurize and depressurize.

In addition; using hot-cold lysis method by cellulose ethanoate (degree of acetylation: 60.9%; viscometric degree of polymerization: 299) it is dissolved in the solution that 20 weight % are formed in methyl acetate; if measured using differential scanning calorimetry (DSC); it then nearby walks around height there are the false appearance of collosol state and gel state at 33 DEG C, in the temperature, the following are uniform gel states.Therefore, which preferably must be held at a temperature of pseudo-phase transition temperature or more, preferably+10 DEG C of gel phase transition temperature or so.But the pseudo-phase transition temperature is different according to the degree of acetylation of cellulose ethanoate, viscometric degree of polymerization, solution concentration and used organic solvent.

Low latency acylated cellulose film is prepared from the cellulose acylate solutions (dope) of preparation by solvent cast method.Dope is cast on roller or conveyer belt, solvent is made to evaporate to form film.It is preferred that adjusting the concentration of the dope before curtain coating so that solid state component amount is 18-35%.It is preferred that the surface of roller or conveyer belt is processed as mirror status.It is preferred that it is on 10 DEG C of rollers or conveyer belt below that dope, which is cast to surface temperature,.

Drying means in solvent cast method is on the books in No. 62-115035 United States Patent (USP) 2336310, United States Patent (USP) 2367603, United States Patent (USP) 2492078, United States Patent (USP) 24922977, United States Patent (USP) 2492978, United States Patent (USP) 2607704, United States Patent (USP) 2739069, United States Patent (USP) 2739070, British patent 640731, each specification of British patent 736892 and examined patent publication 45-4554, examined patent publication 49-5614, tekiaki 60-176834, tekiaki 60-203430, tekiaki each bulletin.Drying on conveyer belt or roller can be carried out by being passed through the inert gases such as air, nitrogen.

After peeling off resulting film from roller or conveyer belt, reuses the high temperature that from 100 to 160 DEG C of temperature gradually changes and air-dry dry so that residual solvent evaporates.Above method is on the books in fairness 5-17844 bulletin.The time for being cast to peeling can be shortened by this method.In order to implement this method, the surface temperature of roller or conveyer belt when curtain coating must be such that dope gelation.

Be cast two layers using cellulose acylate solutions adjusted (dope) or more, it can also be with filming.At this point, it is preferred that manufacturing low latency acylated cellulose film by solvent cast method.After dope is cast to roller or conveyer belt, evaporation solvent can form film.It is preferred that adjusting the concentration of the dope before curtain coating so that the amount of solid state component is in the range of 10-40 mass %.It is preferred that the surface of roller or conveyer belt is processed as mirror status.

In two layers of curtain coating or more of a variety of cellulose acylate solutions; in order to which a variety of cellulose acylate solutions can be cast; multiple curtain coating mouths are set at regular intervals in the direction of advance of supporter, are cast the solution containing acylated cellulose respectively from these curtain coating mouths, then be laminated to prepare film.The method recorded in tekiaki 61-158414, Japanese Laid-Open Patent Publication 1-122419 and Japanese Laid-Open Patent Publication 11-198285 bulletin can be used for example.In addition, filming can also be carried out from 2 curtain coating mouth curtain coating cellulose acylate solutions.The method recorded in examined patent publication 60-27562, tekiaki 61-94724, tekiaki 61-947245, tekiaki 61-104813, tekiaki 61-158413 and Japanese Laid-Open Patent Publication 6-134933 bulletin can be used for example.In addition; the casting method for the following low latency acylated cellulose film recorded in tekiaki 56-162617 bulletin can also be used: encasing highly viscous cellulose acylate solutions fluid with the cellulose acylate solutions of low viscosity; and the cellulose acylate solutions of the high and low viscosity are squeezed out simultaneously.

Furthermore it is also possible to manufacture film as follows: using two curtain coating mouths, after the film that mouth removing is formed on supporter is cast by first, carries out second on contact intermediate layer side and prolong.Such as the method recorded in examined patent publication 44-20235 bulletin can be enumerated.

Identical solution can be used in the cellulose acylate solutions of curtain coating, and two kinds or more different cellulose acylate solutions also can be used.In order to make multiple acylated cellulose layers that there is function, cellulose acylate solutions corresponding with its function can be squeezed out from each curtain coating mouth.In addition, cellulose acylate solutions of the invention can be cast simultaneously with other functional layers (such as adhesive layer, dye coating, antistatic backing, anti-blooming shadow layer, UV-absorbing layer, polarizing layer etc.).

For past single layer solution, in order to assign film necessary thickness, it is necessary to squeeze out highly viscous cellulose acylate solutions in higher concentrations.In this case, the poor generation solid matter of the stability of cellulose acylate solutions, so that it is bad largely to lead to the problem of point failure, flatness.It may is that as the way to solve the problem by being cast a variety of cellulose acylate solutions from curtain coating mouth; highly viscous solution can be expressed on supporter simultaneously; thus the excellent planar film that not only available flatness optimizes; and drying load can be reduced by using sticky cellulose acylate solutions, thus the speed of production of the film more improved.

Anti-deterioration agent (such as antioxidant, peroxide decomposer, free radical inhibitors, metal-inert agent, sour capturing agent, amine etc.) can be added in low latency acylated cellulose film.Anti-deterioration agent is on the books in No. 6-107854 Japanese Laid-Open Patent Publication 3-199201, Japanese Laid-Open Patent Publication 5-1907073, Japanese Laid-Open Patent Publication 5-194789, Japanese Laid-Open Patent Publication 5-271471, Japanese Laid-Open Patent Publication each bulletin.In addition, the additive amount of above-mentioned anti-deterioration agent is preferably the 0.01-1 mass %, further preferably 0.01-0.2 mass % of the solution (dope) prepared.If additive amount is 0.01 mass % or more, the effect of anti-deterioration agent can be fully played, it is advantageous to.If additive amount be 1 mass % hereinafter, if anti-deterioration agent be difficult to film surface generate exudation (infiltration), it is advantageous to.Example as particularly preferred anti-deterioration agent can enumerate butylated hydroxytoluene (BHT), tribenzyl amine (TBA).

These dry processes after being cast to can be carried out under air atmosphere or be carried out under the inert atmospheres such as nitrogen.Common machine can be used in up- coiler used in the manufacture of low latency acylated cellulose film in the present invention, can determine tension method, determine to be wound in the winding method such as the fixed process control tension method of calibrated wrench method, gradient tension method, internal stress.

(thermal contraction processing)

Low latency acylated cellulose film of the invention can also make through overheat contraction processing.It is handled by thermal contraction, the free volume of cellulosic molecule interchain can be reduced, to increase acylated cellulose and postpone the interaction of depressant, more improve the retention of delay depressant.

Thermal contraction processing can be carried out with various methods, it is preferred that using in the state of only by either party of width direction and conveying direction fixation by film (glass transition temperature (Tg) -20) DEG C or more at a temperature of processing certain time method.Residual solvent levels when heat treatment starts in film are preferably 30 mass % hereinafter, more preferably 10 mass % are hereinafter, most preferably 5 mass % or less.If be heat-treated in the state of residual solvent levels height, film is crystallized, mist degree rising poor so as to cause brittleness etc. and bad variation.

As above-mentioned heat-treating methods, following method can particularly preferably be used: the devices margin width direction such as tenter clip gap of the film after removing side is dried, after residual solvent levels sufficiently reduce, by decontroling the limitation of width direction, the height temperate zone of Tg or more is made it through in the state of only applying tension to conveying direction.

[stretch processing]

The low latency acylated cellulose film that the present invention uses can also carry out stretch processing, to keep the degree of orientation of acylated cellulose of width direction and conveying direction close uniform.

The draw direction of low latency acylated cellulose film either width direction, length direction which is all preferred.

The method stretched in width direction, such as recorded in each bulletins such as tekiaki 62-115035, Japanese Laid-Open Patent Publication 4-152125, Japanese Laid-Open Patent Publication 4-284211, Japanese Laid-Open Patent Publication 4-298310, Japanese Laid-Open Patent Publication 11-48271.The stretching of low latency acylated cellulose film can carry out under conditions of room temperature or heating.Heating temperature is preferably the Tg or less of the low latency acylated cellulose film.Low latency acylated cellulose film can be stretched in drying process, in the case where residual solvent especially effectively.When being stretched to length direction; such as low latency acylated cellulose film can be stretched as follows: the speed of the conveying roller of low latency acylated cellulose film is adjusted, so that the winding speed of low latency acylated cellulose film is also faster than the peeling speed of low latency acylated cellulose film.When width (cross) direction stretches, low latency acylated cellulose film can be stretched as follows: keep the width of low latency acylated cellulose film to be conveyed with stenter, and slowly expand the width of stenter.(it is preferable to use being uniaxially stretched for long stretching-machine) can also be stretched using stretching-machine after low latency acylated cellulose film is dry.The stretching ratio of low latency acylated cellulose film is preferably 1-30%, further preferably 1%-15%.

[delay]

In this specification, Re (λ), Rth (λ) respectively indicate the delay postponed in the face under wavelength X with thickness direction.Re (λ) can be measured in KOBRA 21ADH or WR (prince's measuring instrument (strain) system) by making the light emission of wavelength X nm enter film normal direction.When the film of measurement is the substance indicated with uniaxially or biaxially indicatrix, Rth (λ) is calculated with the following method.

Rth (λ) is calculated as follows: using above-mentioned Re (λ) relative to using the slow phase axis (being judged by KOBRA 21ADH or WR) in face as the film normal direction of sloping shaft (rotary shaft) (in no slow phase axis any direction in pellicular front as rotary shaft), inject the light of wavelength X nm from its respective inclined direction according to 10 degree of steps from normal direction to unilateral 50 degree, 6 points of total measurement calculate KOBRA 21ADH or WR based on the film thickness value of the assumed value and input of the length of delay of its measurement and mean refractive index.

Among the above, from normal direction using the slow phase axis in face as rotary shaft, in the case where the film in the direction for being zero with length of delay under a certain tilt angle, after the symbol of length of delay becomes negative under the tilt angle bigger than its tilt angle, KOBRA 21ADH or WR are calculated.

And, it can also be using slow phase axis as sloping shaft (rotary shaft) (in no slow phase axis using any direction in pellicular front as rotary shaft), length of delay is measured from any inclined both direction, based on the film thickness value of the assumed value and input of the value and mean refractive index, Rth is calculated by following formula (1) and formula (2).

[chemical formula 25]

$\mathrm{Re}\left(\mathrm{\&theta;}\right)=[\mathrm{nx}-\frac{\mathrm{ny}\&times;\mathrm{nz}}{\sqrt{{\left(\mathrm{ny}\sin \left({\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\right)\right)}^2+{\left(\mathrm{nz}\cos \left({\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\right)\right)}^2}}]\&times;\frac{d}{\cos \left({\sin }^{-1}\left(\frac{\sin (-\mathrm{\&theta;})}{\mathrm{nx}}\right)\right)}$

Formula (1)

Annotation:

Above-mentioned Re (θ) indicates the length of delay in the direction at cant angle theta angle from normal direction.

The refractive index of the slow phase axis direction in the expression face nx in formula (1), ny indicate the refractive index in face with nx vertical direction, and nz indicates the refractive index with nx and ny vertical direction.

Rth=((nx+ny)/2-nz) xd formula (2)

When the film of measurement cannot be indicated with uniaxially or biaxially indicatrix, without so-called optic axis (optic axis) film when calculate Rth (λ) in the following method.

Rth (λ) is calculated as follows: by above-mentioned Re (λ) relative to using the slow phase axis (being judged by KOBRA 21ADH or WR) in face as the film normal direction of sloping shaft (rotary shaft), inject the light of wavelength X nm from its respective inclined direction according to 10 degree of steps from -50 degree to+50 degree, 11 points are measured, calculate KOBRA 21ADH or WR based on the film thickness value of the assumed value and input of the length of delay of its measurement and mean refractive index.

In above-mentioned measurement, the Directory Value of polymer handbook (JOHNWILEY & SONS, INC), respective optical thin film is can be used in the assumed value of mean refractive index.Value for mean refractive index is not that known substance can be measured with Abbe refractometer.It is listed below the value of the mean refractive index of main optical thin film: acylated cellulose (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).When inputting the assumed value and film thickness of these mean refractive indexs, nx, ny, nz of KOBRA 21ADH or WR can be calculated.Nz=(nx-nz)/(nx-ny) is further calculated by nx, ny, nz of the calculating.

The Re of low latency film of the invention under 25 DEG C of 60% relative humidity meets formula (1) and formula (2) by the range of measurement wavelength 400nm~700nm.

In formula (1), the more preferable Re of Re (λ)≤5nm, most preferably Re (λ)≤3nm.

In formula (2), Rth more preferably -10nm≤Rth (λ)≤10nm, most preferably -5nm≤Rth (λ)≤5nm.

In addition, the Rth (446) and Rth (628) of low latency film of the invention under 25 DEG C of 60% relative humidity meet the relationship of following formula (17).

-10nm≤Rth(446)-Rth(628)≤10nm            (17)

Rth (446)-Rth (628) more preferably -9nm≤Rth (446)-Rth (628)≤9nm, most preferably -7nm≤Rth (446)-Rth (628)≤7nm in formula (17).

By achieving the effect that above range, it can be achieved that as follows: reducing contrast variation, the variation of color degree that liquid crystal display device of the invention is generated by field angle.

[thickness of low latency acylated cellulose film]

The thickness of low latency acylated cellulose film of the invention is preferably 10~200 μm, more preferably 20~150 μm, further preferably 30~100 μm.

(optical compensating film)

Optical compensating film used in liquid crystal display device of the invention is illustrated below.

Optical compensating film of the invention preferably takes following two structure.

1st kind is the structure with the optical compensating film for meeting formula (3)~(8) relationship.In formula (3), more preferable 25nm < Re (548) < 135nm, most preferably 30nm < Re (548) < 120nm.

In formula (4), more preferable 80nm < Rth (548) < 350nm, most preferably 100nm < Rth (548) < 300nm.

In formula (5), more preferable 0.55 < Re (446)/Re (548) < 0.95, most preferably 0.6 < Re (446)/Re (548) < 0.9.

In formula (6), more preferable 1.05 < Re (628)/Re (548) < 1.75, most preferably 1.1 < Re (628)/Re (548) < 1.5.

In formula (7), more preferable 1.05 < Rth (446)/Rth (548) < 1.75, most preferably 1.10 < Rth (446)/Rth (548) < 1.5.

In formula (8), more preferable 0.6 < Rth (628)/Rth (548) < 0.95, most preferably 0.7 < Rth (628)/Rth (548) < 0.90.

2nd kind of preferred structure of optical compensating film of the invention, which has, to be met formula (9)~(12) relationship optical compensating film and meets formula (13)~(16) optical compensating film.

50nm < Re (548) < 200nm (9)

30nm < Rth (548) < 150nm (10)

0.5 < Re (446)/Re (548) < 1 (11)

1.0 < Re (628)/Re (548) < 2.0 (12)

0nm≤Re (548) < 10nm (13)

100nm < Rth (548) < 300nm (14)

1.0 < Rth (446)/Rth (548) < 2.0 (15)

0.5 < Rth (628)/Rth (548) < 1.0 (16)

In formula (9), more preferable 70nm < Re (548) < 175nm, most preferably 90nm < Re (548) < 150nm.

In formula (10), more preferable 40nm < Rth (548) < 120nm, most preferably 50nm < Rth (548) < 100nm.

In formula (11), more preferable 0.55 < Re (446)/Re (548) < 0.95, most preferably 0.6 < Re (446)/Re (548) < 0.9.

In formula (12), more preferable 1.05 < Re (628)/Re (548) < 1.50, most preferably 1.08 < Re (628)/Re (548) < 1.30.

In formula (13), more preferable 0≤Re (548) < 5nm, most preferably 0≤Re (548) < 3nm.

In formula (14), more preferable 120nm < Rth (548) < 250nm, most preferably 140nm < Rth (548) < 230nm.

In formula (15), more preferable 1.03 < Rth (446)/Rth (548) < 1.50, most preferably 1.05 < Rth (446)/Rth (548) < 1.3.

In formula (16), more preferable 0.7 < Rth (628)/Rth (548) < 1.00, most preferably 0.85 < Rth (628)/Rth (548) < 0.97.

Optical compensating film of the invention is also possible to the laminated body of multiple films and/or overlay.In addition, can be various configurations when using above-mentioned multiple films and/or overlay.Such as it is preferable to use only concentrate the method for optical compensating film in unilateral side relative to liquid crystal cells or distribute both methods of optical compensating film in the two sides of liquid crystal cells.

In addition, when distributing optical compensating film in the two sides of liquid crystal cells, any one of the method and the method being configured in such a way that the optical compensating film of liquid crystal cells two sides has different delays that are configured according to the substantially uniform mode of delay of the optical compensating film of liquid crystal cells two sides is further preferably used.

In addition, the protective film in polarizing film close to liquid crystal cell side is also possible to the structure as optical compensating film.

In the following, being illustrated to the preferred configuration example of the protective film in optical compensating film and polarizing film of the invention close to liquid crystal cell side, but the present invention is not limited to these in Fig. 1.

In the structure 1 of Fig. 1; the laminated body of biaxial films and phase difference film is an example for meeting formula (3)~formula (8) relationship optical compensating film, and the low latency in structure 1 and structure 2 is the protective film for meeting the relationship of formula (1) and formula (2) respectively.In addition, the laminated body of A piece and C piece is equivalent to optical compensating film in structure 2.Furthermore, optical compensating film A is an example for meeting formula (9)~formula (12) relationship optical compensating film in structure 3, and optical compensating film B is an example for meeting formula (13)~(16) relationship optical compensating film.

In addition, adhesive phase, adhesive layer, oriented layer etc. can also arbitrarily be arranged between each component (layer) in structure 1, structure 2 and structure 3.

(structure 1)

(phase difference film)

Phase difference film in structure 1 shows slow phase axis in length direction.

As the method for making length direction show as slow phase axis, can enumerate method that polymer stretches along its length, the method for being orientated polymerizable liquid crystal compound etc..

It is absorbed in addition, the phase difference film of structure 1 preferably has in long wavelength side compared with the material for constituting biaxial films.By using this structure, the wavelength dispersion of the delay of optical compensating film can be controlled as desired figure.The maximum absorption of material used in the phase difference film of structure 1 ranges preferably from 200nm~370nm, more preferably 220nm~350nm, most preferably 240nm~330nm.By the way that maximum absorption is defined as 370nm hereinafter, the end of absorption can more efficiently be inhibited to fall in degree of the optical compensating film with yellow of visible area.

Phase difference film used in structure 1 preferably comprises non-liquid crystal property polymer or liquid crystal compounds.

(delay of phase difference film)

The Re of the phase difference film of structure 1 is preferably 0~300nm, more preferably 0~200nm.The absolute value of Rth is preferably 0~400nm, more preferably 0~200nm.

(phase difference film containing non-liquid crystal property polymer)

Herein, the phase difference film to non-liquid crystal property polymer and containing the non-liquid crystal property polymer is illustrated.

The non-liquid crystal property polymer for the phase difference film that the present invention uses is formed preferably using the polyethylene oxide for using solvent dimethylformamide to obtain as standard sample, the weight average molecular weight (Mw) with gel permeation chromatography (GPC) measurement is the substance of 10,000~400,000 ranges.The polymer for being 10,000 or more by using this weight average molecular weight can get the birefringent layers with more high birefringence, so as to prevent the generation of crackle.In addition, being 400,000 polymer below by using weight average molecular weight, the offset of phase difference can be more effectively prevented from.This is because weight average molecular weight is that the viscosity of 400,000 polymer solutions below will not become excessively high when forming above-mentioned phase difference film by applying polymer solution, it is easy to apply polymer solution to basis material etc., as a result can forms uniform phase difference film.In addition, when the use of weight average molecular weight being 400,000 polymer modulation polymer solution below, since the solubility of polymer is high, it is possible to reduce the quantity of solvent used.As a result the thickness of overlay can be made thinning, accurate coating can be carried out.The weight average molecular weight (Mw) for forming the polymer of phase difference film is more preferably 10,000~300,000, further preferably 10,000~200,000.

Non-liquid crystal property polymer is for example different from liquid-crystalline polymer, unrelated with the orientation of substrate, can form nX > nz, this film for showing optically uniaxial property of ny > nz according to the property for playing itself.Thus, for example, the supporter used can not also be limited by orientation base, for example, it can be non-oriented films, it is convenient to omit the process of coated with orientation film and the process etc. of stacking alignment films.

Non-liquid crystal property polymer used in the present invention, is preferably selected from least one polymer of polyamide, polyimides, polyester, polyether-ketone, polyaryletherketone, polyamidoimide and polyesterimide.The material of these polymer is not particularly limited, and known polymer material can be used, can individually or be used in any combination.

In addition, these polymer are excellent from heat resistance, chemical resistance, it is imbued with rigidity, the reasons such as excellent transparency are set out, and the material of aftermentioned biaxiality film is also adaptable as.

As above-mentioned polyimides, preferably orientation is high for example in face, dissolves in the polyimides of organic solvent.Specifically, such as, it is included in disclosed in special table 2000-511296 bulletin, the condensation polymer of 9,9- bis- (aminoaryl) fluorenes and aromatic tetracarboxylic dianhydride, the polymer including repetitive unit shown in more than one following formula (46) can be used.

[chemical formula 26]

Formula (46)

In above-mentioned formula (46), R⁴⁶³~R⁴⁶⁶Respectively be selected from hydrogen, halogen atom, phenyl, by 1~4 halogen atom or carbon atom number be 1~10 alkyl-substituted phenyl and carbon atom number be 1~10 alkyl group.It is preferred that R⁴⁶³~R⁴⁶⁶It is selected from halogen atom, phenyl respectively, is 1~10 alkyl-substituted phenyl by 1~4 halogen atom or carbon atom number and carbon atom number is the group of 1~10 alkyl.

In above-mentioned formula (46), Z is that have carbon atom number be the group of the aromatic series of 6~20 4 valences, preferably pyromellitic acid base, polycycle aromatic series base, the derivative of polycycle aromatic series base or the group that is indicated with following formula (47).

[chemical formula 27]

Formula (47)

In above-mentioned formula (7), Z ' be covalent bond ,-C (R⁴⁷⁷)₂-、-CO-、-O-、-S-、-SO₂-、-Si(C₂H₅)₂Or-NR⁴⁷⁸, when Z ' is 2 or more, may be the same or different each other.In addition, w indicates 1~10 integer.R⁴⁷⁷It is hydrogen atom or-C (R each other⁴⁷⁹)₃。R⁴⁷⁸It is the alkyl that hydrogen atom, carbon atom number are 1~20 or the aryl that carbon atom number is 6~20, works as R⁴⁷⁸When being 2 or more, it may be the same or different each other.R⁴⁷⁹It is hydrogen atom, fluorine atom or chlorine atom, R each other⁴⁷⁹When being 2 or more, it may be the same or different each other.

As above-mentioned polycycle aromatic series base, such as quaternary groups as derived from naphthalene, fluorenes or benzfluorene or anthracene can be enumerated.In addition, as the substitutive derivative of above-mentioned polycycle aromatic series base, can enumerate such as carbon atom number be 1~10 alkyl, carbon atom number be 1~10 alkyl fluorinated derivatives and by the above-mentioned polycycle aromatic series base that replaces of at least one group selected from halogen atom (fluorine atom, chlorine atom).

In addition, can also enumerate such as record in special table level 8-511812 bulletin, repetitive unit is the homopolymer indicated with following formula (48) or formula (49) and repetitive unit is the polyimides indicated with following formula (410).In addition, the polyimides of following formula (410) is the preferred form of the homopolymer of following formula (48).

[chemical formula 28]

Formula (48)

[chemical formula 29]

Formula (49)

[chemical formula 30]

Formula (410)

In above-mentioned formula (48)~formula (410), G and G ' are respectively indicated selected from covalent bond ,-CH₂-、-C(CH₃)₂-、-C(CF₃)₂-、-C(CX₃)₂(wherein, X is halogen atom.),-CO-,-O-,-S-,-SO₂-、-Si(CH₂CH₃)₂And-N (CH₃)-group.

In above-mentioned formula (48) and formula (410), L indicates substituent group.Halogenated alkyl that L is preferably halogen atom, carbon atom number is 1~3 alkyl, carbon atom number are 1~3, substituted or unsubstituted phenyl may be the same or different each other when L is 2 or more.As above-mentioned substituted-phenyl, the substituted-phenyl of the substituent group for the halogenated alkyl for being for example 1~3 with the alkyl and carbon atom number that are 1~3 selected from halogen atom, carbon atom number can be enumerated as preferred example.In addition, such as fluorine atom, chlorine atom, bromine atom or iodine atom can be enumerated as preferred example as above-mentioned halogen atom.D is 0~2 integer, and e is 0~3 integer.

In above-mentioned formula (48)~formula (410), Q indicates hydrogen atom or substituent group.As Q, it is atom or group selected from halogen atom, substituted or unsubstituted alkyl, nitro, cyano, alkylthio, alkoxy, substituted or unsubstituted aryl and substituted or unsubstituted alkyl ester group, when Q is 2 or more, may be the same or different each other.As above-mentioned halogen atom, such as fluorine atom, chlorine atom, bromine atom and iodine atom can be enumerated.As above-mentioned substitution alkyl, such as halogenated alkyl can be enumerated.Additionally as above-mentioned substituted aryl, such as halogenated aryl can be enumerated.F is 0~4 integer, and g is 0~3 integer, and h is 1~3 integer.Furthermore it is preferred that g and h are respectively greater than 1.

In above-mentioned formula (49), R⁴⁹¹Be each other selected from hydrogen atom or halogen atom, substituted or unsubstituted phenyl, substituted or unsubstituted alkyl group.Wherein, R⁴⁹¹It is further preferably halogenated alkyl each other.

In above-mentioned formula (410), M¹And M²Substituent group each other, preferably halogen atom, carbon atom number be 1~3 alkyl, carbon atom number be 1~3 halogenated alkyl or substituted or unsubstituted phenyl.As above-mentioned halogen atom, such as fluorine, chlorine, bromine and iodine can be enumerated as preferred example.In addition, the substituted-phenyl of the group for the halogenated alkyl for being for example 1~3 with the alkyl and carbon atom number that are 1~3 selected from halogen atom, carbon atom number can be enumerated as above-mentioned substituted-phenyl.

As the specific example of polyimides shown in above-mentioned formula (48), can enumerate such as the substance indicated with following formula (411).N is preferably 100~1000.

[chemical formula 31]

Formula (411)

In addition, further preferably for example making acid dianhydride and diamines other than skeleton as described above (repetitive unit) suitably be copolymerized the copolymer of formation as above-mentioned polyimides.

As above-mentioned acid dianhydride, such as aromatic tetracarboxylic dianhydride can be enumerated.As above-mentioned aromatic tetracarboxylic dianhydride, such as benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic acid dianhydride, hetero ring type aromatic tetracarboxylic dianhydride, 2,2 '-substituted biphenyl base tetracarboxylic dianhydrides etc. can be enumerated.

As above-mentioned benzenetetracarboxylic dianhydride, such as bis- (trifluoromethyl) benzenetetracarboxylic dianhydrides of benzenetetracarboxylic dianhydride, 3,6- diphenyl benzenetetracarboxylic dianhydride, 3,6-, 3,6- dibromo benzenetetracarboxylic dianhydride, 3,6- dichloro benzenetetracarboxylic dianhydride etc. can be enumerated.As above-mentioned benzophenone tetracarboxylic dianhydride, such as 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides etc. can be enumerated.As above-mentioned naphthalene tetracarboxylic acid dianhydride, such as 2 can be enumerated, 3,6,7- naphthalenes-tetracarboxylic dianhydride, 1,2,5,6- naphthalenes-tetracarboxylic dianhydride, the chloro- naphthalene-Isosorbide-5-Nitrae of 2,6- bis-, 5,8- tetracarboxylic dianhydrides etc..As above-mentioned hetero ring type aromatic tetracarboxylic dianhydride, such as thiophene -2,3,4,5- tetracarboxylic dianhydrides, pyridine -2,3,5,6- tetracarboxylic dianhydrides, pyridine -2,3,5,6- tetracarboxylic dianhydrides etc. can be enumerated.As above-mentioned 2,2 '-substituted biphenyl base tetracarboxylic dianhydrides, such as 2 can be enumerated, 2 '-two bromo- 4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydrides, 2,2 '-two chloro- 4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydrides, 2,2 '-bis- (trifluoromethyl) -4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydrides etc..

In addition, other examples as above-mentioned aromatic tetracarboxylic dianhydride, 3 can be enumerated, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydrides, bis- (2, 3- dicarboxyphenyi) methane dianhydride, bis- (2, 5, 6- tri- fluoro- 3, 4- dicarboxyphenyi) methane dianhydride, 2, 2- bis- (3, 4- dicarboxyphenyi) -1, 1, 1, 3, 3, 3- hexafluoro propane dianhydride, 4, 4 '-bis- (3, 4- dicarboxyphenyi) -2, 2- diphenylprop dianhydride, bis- (3, 4- dicarboxyphenyi) ether dianhydride, 4, 4 '-oxa-, two phthalandione dianhydride, bis- (3, 4- dicarboxyphenyi) sulfonic acid dianhydride, 3, 3 ', 4, 4 '-diphenyl sulfone tetracarboxylic dianhydrides, 4, 4 '-[4, 4 '-isopropylidenes-two (p- penylene oxo)] bis- (anhydride phthalic acids), N, N- (3, 4- dicarboxyphenyi) it is-N- methylamine dianhydride, double

(3,4- dicarboxyphenyi) diethylsilane dianhydride etc..

Wherein, as above-mentioned aromatic tetracarboxylic dianhydride, further preferably 2,2 '-substituted biphenyl base tetracarboxylic dianhydrides, more preferable 2,2 '-bis- (trihalomethyl groups) -4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydrides, into-step preferably 2,2 '-bis- (trifluoromethyls) -4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydrides.

As above-mentioned diamines, such as aromatic diamine can be enumerated, as specific example, phenylenediamine, diaminobenzophenone, naphthylenediamine, hetero ring type aromatic diamine and other aromatic diamines can be enumerated.

As above-mentioned phenylenediamine, can enumerate for example selected from such as o-, m- and p-PDA, 2,4- diaminotoluene, Isosorbide-5-Nitrae-diamino -2- methoxybenzene, Isosorbide-5-Nitrae-diamino -2- phenyl benzene and 1, the diamines etc. of the phenylenediamine of 3- diamino -4- chlorobenzene etc.

As the example of above-mentioned diaminobenzophenone, 2,2 '-diaminobenzophenones and 3,3 '-diaminobenzophenones etc. can be enumerated.

As above-mentioned naphthylenediamine, such as 1,8- diaminonaphthalene and 1,5-diaminonaphthalene etc. can be enumerated.

As the example of above-mentioned hetero ring type aromatic diamine, 2,6-diaminopyridine, 2,4- diamino-pyridine and 2,4- diamino-S- triazine etc. can be enumerated.

In addition, as above-mentioned aromatic diamine, in addition to this, 4 can also be enumerated, 4 '-benzidines, 4, 4 '-diaminodiphenyl-methanes, 4, 4 '-(9- fluorenes fork)-diphenylamines, 2, 2 '-bis- (trifluoromethyls) -4, 4 '-benzidines, 3, 3 '-two chloro- 4, 4 '-diaminodiphenyl-methanes, 2, 2 '-two chloro- 4, 4 '-benzidines, 2, 2 ', 5, 5 '-tetrachloro benzidines, 2, bis- (4- aminophenoxy phenyl) propane of 2-, 2, bis- (4- aminophenyl) propane of 2-, 2, bis- (the 4- aminophenyls) -1 of 2-, 1, 1, 3, 3, 3- hexafluoropropane, 4, 4 '-diamino-diphenyl ethers, 3, 4 '-diamino-diphenyl ethers, 1, bis- (3- amino-benzene oxygen) benzene of 3-, 1, 3 Bis- (4- amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 2, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2-, bis- [4- (4- amino-benzene oxygen) phenyl] -1,1 of 2,2-, 1,3,3,3- hexafluoropropane, 4,4 '-diamino diphenyl sulfides, 4,4 '-diamino diphenyl sulfones etc..

As above-mentioned polyether-ketone, polyaryletherketone recording in such as special open 2001-49110 bulletin, indicating with following formula (412) can be enumerated.

[chemical formula 32]

Formula (412)

In above-mentioned formula (412), X⁴¹²Indicate substituent group.X⁴¹²Preferably halogen atom, low alkyl group, halogenated alkyl, lower alkoxy or halogenated alkoxy, work as X⁴¹²When being multiple, it may be the same or different each other.

As above-mentioned halogen atom, such as fluorine atom, bromine atom, chlorine atom and iodine atom can be enumerated, wherein preferred fluorine atom.As above-mentioned low alkyl group, preferably for example carbon atom number be 1~6 linear chain or branched chain low alkyl group, more preferable carbon atom number be 1~4 linear chain or branched chain alkyl.And specifically, it is preferable to methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl and tert-butyl, particularly preferred methyl and ethyl.As above-mentioned halogenated alkyl, the halide of the above-mentioned low alkyl group such as trifluoromethyl can be enumerated.As above-mentioned lower alkoxy, preferably for example carbon atom number be 1~6 linear chain or branched chain alkoxy, more preferable carbon atom number be 1~4 linear chain or branched chain alkoxy.Specifically, more preferable methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, particularly preferred methoxyl group and ethyoxyl.As above-mentioned halogenated alkoxy, the halide of the above-mentioned lower alkoxy such as trifluoromethoxy can be enumerated.

In above-mentioned formula (412), q412 and a412 are 0~4 integer respectively.In above-mentioned formula (412), q412=0, also, it is preferred that mutually existing in contraposition in the carbonyl of the both ends of phenyl ring combination and the oxygen atom of ether.In addition, in above-mentioned formula (412), R⁴¹²It is the group indicated with following formula (413), m412 is 0 or 1 integer.

[chemical formula 33]

Formula (413)

In above-mentioned formula (413), X⁴¹³Indicate substituent group, such as with the X in formula (412)⁴¹²It is identical.In above-mentioned formula (413), work as X⁴¹³When being multiple, it may be the same or different each other.Q413 is 0~4 integer, preferably q413=0.In addition, p413 is 0 or 1.B413 indicates the substitution number of fluorine atom F, is 0~4 integer.

In above-mentioned formula (413), R⁴¹³Indicate the aromatic series base of divalent.As the aromatic series base of the divalent, can enumerate such as o-, m- or p- phenylene or the bivalent group as derived from naphthalene, biphenyl, anthracene, o-, m- or p- terphenyl, phenanthrene, dibenzofurans, xenyl ether or xenyl sulfone.In the aromatic series base of these divalent, the hydrogen bound directly with aromatic series can also be replaced by halogen atom, low alkyl group or lower alkoxy.Wherein, as above-mentioned R⁴¹³, further preferably it is selected from the aromatic series base of following (9)~(15).

[chemical formula 34]

In above-mentioned formula (412), as above-mentioned R⁴¹², the group more preferably indicated with following formula (21), in following formula (21), R⁴¹³And p⁴¹³Synonymous with above-mentioned formula (413), preferred range is also synonymous.

[chemical formula 35]

Formula (21)

In addition, in above-mentioned formula (412), the n412 expression degree of polymerization, preferably 2~5000, more preferably 5~500.In addition, the polymerization can be made of mutually isostructural repetitive unit, can also be made of the repetitive unit of different structure.In the latter case, the polymerized form of repetitive unit can be block polymerization, be also possible to atactic polymerization.

In addition, the preferred p- tetrafluoro benzoyl support group side in the end of the polyaryletherketone indicated with formula (412) is fluorine, oxyalkylene side is hydrogen atom, and such polyaryletherketone can for example be indicated with following formula (22).In addition, n412 is indicated and above-mentioned formula (412) identical degree of polymerization in following formula.X⁴¹²、q412、R⁴¹², m412 and formula (412) it is synonymous, preferred scope is also synonymous.

[chemical formula 36]

Formula (22)

As the specific example of the polyaryletherketone indicated with above-mentioned formula (12), the substance etc. indicated with following (23)~(26) can be enumerated, it is following it is various in, n is indicated and above-mentioned formula (412) identical degree of polymerization.

[chemical formula 37]

In addition, in addition to this, as above-mentioned polyamide or polyester, the polyamide and polyester recorded in such as special table level 10-508048 bulletin can be enumerated, these repetitive unit can for example be indicated with following formula (27).

[chemical formula 38]

Formula (27)

In above-mentioned formula (27), Y²⁷It is-O- or-NH-.In addition, E²⁷It is to be selected from the alkylidene, CH that covalent bond, the alkylidene that carbon atom number is 2, halogenated carbon atom number are 2₂Base, C (CX²⁷ ₃)₂Base (wherein, X²⁷It is halogen or hydrogen.), CO base, O atom, S atom, SO₂Base, Si (R²⁷)₂Base and N (R²⁷) base at least one group, can be the same or different each other.Above-mentioned E²⁷In, R²⁷It is at least one of the alkyl that carbon atom number is 1~3 and the halogenated alkyl that carbon atom number is 1~3, relative to Carbonyl functional group or Y²⁷Positioned at meta or para position.

In addition, in above-mentioned formula (27), A²⁷And A '²⁷It is substituent group, t271 and t272 are 0~4 integer respectively, and z271 and z272 are 0~4 integer respectively, and p27 is 0~3 integer, and q27 is 1~3 integer, and r27 is 0~3 integer.

Above-mentioned A²⁷Selected from such as hydrogen, halogen, carbon atom number be 1~3 alkyl, carbon atom number be 1~3 halogenated alkyl, with OR²⁷(wherein, R²⁷It is substance defined above.) indicate alkoxy, aryl, be 1~9 by the substituted aryl of the generations such as halogenated, carbon atom number alkoxy carbonyl, carbon atom number be 1~9 alkyl carbonyl oxy, carbon atom number be 1~12 aryloxycarbonyl, carbon atom number be 1~12 aryl-carbonyl oxygen and its substitutive derivative, carbon atom number be 1~12 aryl-amino-carbonyl and carbon atom number be 1~12 aryl-amino-carbonyl and its substitutive derivative; when to be multiple; it may be the same or different each other.Above-mentioned A '²⁷Selected from halogen atom, carbon atom number be 1~3 alkyl, carbon atom number be 1~3 halogenated alkyl, phenyl and substituted-phenyl may be the same or different each other when to be multiple.As the substituent group on the phenyl ring of above-mentioned substituted-phenyl, can enumerate alkyl, carbon atom number that such as halogen atom, carbon atom number are 1~3 is 1~3 halogenated alkyl and combinations thereof.

In the repetitive unit of the polyamide or polyester that are indicated with above-mentioned formula (27), the substance that is preferably indicated with following formula (28).

[chemical formula 39]

Formula (28)

In above-mentioned formula (28), A²⁸、A’²⁸And Y²⁸Respectively with the A in formula (27)²⁷、A’²⁷And Y²⁷Synonymous, preferred scope is also synonymous.V28 is 0~3 integer, preferably 0~2 integer.V28 and y28 is 0 or 1 respectively, but is not simultaneously 0.

The preparation of phase difference film comprising non-liquid crystal property polymer can for example be carried out according to as follows.Coating forms the above-mentioned defined polymer of phase difference film and forms precursor layer first on basis material.It as coating method, is not particularly limited, can enumerate such as the method for the polymer solution that the method and coating for applying polymer as described above heating fusing make above-mentioned polymer be dissolved in solvent and are formed.Wherein, excellent from operability, it controls optically anisotropic viewpoint and sets out, the method for the above-mentioned polymer solution of preferred coated.

By the working procedure of coating of above-mentioned polymer, the thickness of the phase difference film of adjustable manufacture.For example, apply in the method for above-mentioned polymer solution, it can be by adjusting basis material unit area (cm²) above-mentioned polymer coating amount, adjust the thickness of phase difference film.

The thickness of phase difference film comprising non-liquid crystal property polymer of the invention is preferably 0.1~50 μm, and more preferably 1~20 μm.

Solvent as polymer solution, as long as polymer can be made to dissolve, it is not particularly limited, the halogenated hydrocarbon such as chloroform, methylene chloride, carbon tetrachloride, dichloroethanes, tetrachloroethanes, trichloro ethylene, tetrachloro-ethylene, chlorobenzene, o-dichlorohenzene can be enumerated；The phenols such as phenol, parachlorophenol；Benzene,toluene,xylene, methoxybenzene, 1,2- dimethoxy benzene etc. are aromatic hydrocarbon；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, cyclopentanone, 2-Pyrrolidone, n-methyl-2-pyrrolidone；The esters such as ethyl acetate, butyl acetate；As the tert-butyl alcohol, glycerol, ethylene glycol, triethylene glycol, glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2- methyl -2,4- pentanediol alcohols；Such as dimethylformamide, the amides of dimethyl acetamide；Such as acetonitrile, the nitrile of butyronitrile；As diethyl ether, butyl oxide, tetrahydrofuran ethers；Or carbon disulfide, ethyl cellosolve, butyl cellosolve etc..These solvents can be used alone or as a mixture.

The viscosity that the viscosity of above-mentioned polymer solution preferably readily applies.This is because uniform phase difference film as described above can be formed if coating is easy.The viscosity is preferably 0.1~12Pas, more preferably 1~10Pas, further preferably 1~5Pas.The concentration of above-mentioned polymer is not particularly limited in above-mentioned polymer solution, it is contemplated that the weight average molecular weight of the non-liquid crystal property polymer used, preferably according to the viscosity of above-mentioned range adjustment solution.The concentration of above-mentioned polymer is relative to 100 mass parts of solvent, preferably 5~50 mass parts, more preferably 10~40 mass parts.

Above-mentioned polymer solution, which for example also can according to need, remixes the various additives such as stabilizer, plasticizer, metal class.In addition, above-mentioned polymer solution for example can also contain different other resins in the range for significantly reducing above-mentioned polymer orientation etc..As above-mentioned other resins, can enumerate such as various resins for universal use, engineering plastics, thermoplastic resin, heat-curing resin.

As above-mentioned resins for universal use, can enumerate such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene resin (ABS resin) and acrylonitrile-styrene resin (AS resin).As above-mentioned engineering plastics, can enumerate such as poly- acetic acid esters (POM), polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).As above-mentioned thermoplastic resin, can enumerate such as polyphenylene sulfide (PPS), polyether sulfone (PES), polyketone (PK), polyimides (PI), poly- cyclohexanedimethanol terephthalate (PCT), polyallyl esters (PAR) and liquid crystal polymer (LCP).As above-mentioned heat-curing resin, can enumerate such as epoxy resin, phenol resol resins.

So, when above-mentioned other resins etc. are mixed in above-mentioned polymer solution, combined amount is relative to above-mentioned polymer, preferably 0~50 mass %, more preferably 0~30 mass %.

In addition the method that coating processing can be suitble to according to spin-coating method and rolling method, flow coat method and print process, dip coating and casting filming therapy, stick coating method and gravure printing method etc. carries out.When coating, the stacked system etc. for taking polymeric layer also can according to need.

In addition, can also applied while applying stress in one direction on basis material, or applied whiles from a direction to wind etc. relative to basis material when applying above-mentioned polymer.

Then, above-mentioned precursor layer is made to solidify and form phase difference film on basis material.As cured method, there are as below methods: after coating, spontaneously drying (air-dried), or the method heated at preferably 25~180 DEG C, more preferably 80~170 DEG C, further preferably 60~150 DEG C.Dry or heating time according to its temperature and whether there is or not being determined in precursor layer using solvent, type of its solvent etc., it is preferred that 0.5~30 minute, more preferably 1~20 minute, further preferably 1~15 minute can be carried out.

In the method for preparing phase difference film of the invention, the process for stretching the laminated body of basis material and phase difference film can also be also comprised.It as the drawing process of above-mentioned laminated body, is not particularly limited, is stretched and known method for example, can be properly used fixing end.It is preferred that biaxial stretch-formed also smaller than the stretching ratio of short-axis direction of the stretching ratio of stenter cross directional stretch and long axis direction.Biaxial stretch-formed gradually biaxial stretch-formed any one biaxial stretch-formed, with roll-type tenter frame process while be also possible to according to full stenter mode.Stretching ratio is different according to the difference of drawing process, but above-mentioned laminated body is for example made to stretch 1-200%.Heating temperature when stretching is suitably selected according to the Tg of the basis material used and the type of additive, it is preferred that be 80~250 DEG C, more preferably 120~220 DEG C, particularly preferably 140~200 DEG C.Particularly, it is best to use basis material Tg nearby or Tg or more.

Then, it is preferably carried out process: engaging the phase difference film directly formed on basis material according still further to the mode opposed with low latency thin polymer film, then only remove the process of basis material.It in this way can also be by the way that above-mentioned phase difference film be transferred to low latency thin polymer film, the laminated body of above-mentioned phase difference film and above-mentioned low latency thin polymer film that manufacture is formed by the above-mentioned basis material of removing, to obtain optical laminate of the invention.

As above-mentioned basis material, suitable material can be used, there is no limit.For example, the line that can enumerate the high macromolecule membrane of the low macromolecule membrane of glass transition point (Tg), modulus and material expands the thin basis material etc. of the high basis material of same or the basis material bigger than its, pyroconductivity high basis material, length-width ratio, thickness.To make above-mentioned basis material that there is retractility, following method can be used: being dried in a manner of being not fixed basis material, thus the contractile method of comprehensive tool；It is at least above fixed in one direction, additionally assign the method for shrinkage；The method expanded using the line of metal tape；Pass through the fixed method to control contraction of stenter in film conveying；It expands basis material in advance and passes through the dry method for improving shrinking percentage；Basis material is stretched before drying process, to make the method for its cure shrinkage；The method etc. that basis material is stretched in drying process or after process.It is not limited to this method.

The thickness of above-mentioned basis material can be according to using purpose etc. suitably to determine, but from intensity and the viewpoints, preferably 5~500 μm, more preferably 10~200 μm, further preferably 15~150 μm such as thin layer.

(phase difference film comprising liquid crystal compounds)

Below to the phase difference film as structure 1 it is preferable to use polymerizable liquid crystal layer be described in detail.

Polymerizable liquid crystal layer of the invention is preferably orientated liquid crystal compounds by using alignment films, fixes its state of orientation to be formed.In order to fix the state of orientation of liquid crystal compounds, preferably liquid crystal compounds have polymerizable group.

(rod-shaped liquid crystalline compound)

Rod-shaped liquid crystalline compound used in polymerizable liquid crystal layer of the invention is illustrated first.

As rod-shaped liquid crystalline compound, preferably azomethine type, azoxy class, cyanobiphenyl class, cyano-phenyl esters, benzoic acid esters, cyclohexanecarboxylic acid's esters, cyanophenylcyclohexanes class, cyano substituted-phenyl miazines, alkoxy substituted phenyl miazines, phenyl dioxanes class, dibenzenyl class and alkenyl ring cyclohexyl benzonitrile class.Low molecular liquid crystal compounds not only can be used, but also high molecule liquid crystal compound can be used.It is particularly preferably using, as the rod-shaped liquid crystalline compound with low molecular polymerism base, be the rod-shaped liquid crystalline compound of following formula (I)s.

Formula (I)

        Q¹¹-L¹-Cy¹-L²-(Cy²-L³)_n111-Cy³-L⁴-Q²²

In formula (I), Q¹¹And Q²²It is polymerism base, L respectively¹And L⁴It is the linking group of divalent, L respectively²And L³It is the linking group of singly-bound or divalent, Cy respectively¹、Cy²And Cy³It is the cyclic group of divalent, n111 is 0,1 or 2.

Q¹¹And Q²²In, the polymerization reaction of polymerism base is preferably addition polymerization (including ring-opening polymerisation) or polycondensation.In other words, polymerism base can preferably carry out the functional group of polyaddition reaction or polycondensation reaction.It shown below the example of polymerism base.

[chemical formula 40]

L¹And L⁴It is the linking group of divalent respectively.L¹And L⁴It is preferably selected from-O- ,-S- ,-CO- ,-NR respectively²²², the chain-like groups of divalent, the cyclic group of divalent and its these combination divalent linking group.Above-mentioned R²²²It is the alkyl or hydrogen atom that carbon atom number is 1~7.

It shown below the linking group for the divalent that combination is formed.Wherein, left side and Q (Q¹¹Or Q²²) combine, right side and Cy (Cy¹Or Cy³) combine.

Chain base-the O- of L-1:-CO-O- divalent

Chain base-the O-CO- of L-2:-CO-O- divalent

Chain base-the O-CO-O- of L-3:-CO-O- divalent

The cyclic group-of the chain base-O- divalent of L-4:-CO-O- divalent

Cyclic group-the CO-O- of the chain base-O- divalent of L-5:-CO-O- divalent

Cyclic group-the O-CO- of the chain base-O- divalent of L-6:-CO-O- divalent

Cyclic group-divalent chain base-of the chain base-O- divalent of L-7:-CO-O- divalent

Cyclic group-divalent chain base-CO-O- of the chain base-O- divalent of L-8:-CO-O- divalent

Cyclic group-divalent chain base-O-CO- of the chain base-O- divalent of L-9:-CO-O- divalent

The cyclic group-of the chain base-O-CO- divalent of L-10:-CO-O- divalent

Cyclic group-the CO-O- of the chain base-O-CO- divalent of L-11:-CO-O- divalent

Cyclic group-the O-CO- of the chain base-O-CO- divalent of L-12:-CO-O- divalent

Cyclic group-divalent chain base-of the chain base-O-CO- divalent of L-13:-CO-O- divalent

Cyclic group-divalent chain base-CO-O- of the chain base-O-CO- divalent of L-14:-CO-O- divalent

Cyclic group-divalent chain base-O-CO- of the chain base-O-CO- divalent of L-15:-CO-O- divalent

The cyclic group-of the chain base-O-CO-O- divalent of L-16:-CO-O- divalent

Cyclic group-the CO-O- of the chain base-O-CO-O- divalent of L-17:-CO-O- divalent

Cyclic group-the O-CO- of the chain base-O-CO-O- divalent of L-18:-CO-O- divalent

Cyclic group-divalent chain base-of the chain base-O-CO-O- divalent of L-19:-CO-O- divalent

Cyclic group-divalent chain base-CO-O- of the chain base-O-CO-O- divalent of L-20:-CO-O- divalent

Cyclic group-divalent chain base-O-CO- of the chain base-O-CO-O- divalent of L-21:-CO-O- divalent

The chain base of divalent refers to alkylidene, substituted alkylene, alkenylene, replaces alkenylene, alkynylene (ア Le キ ニ レ Application base), replaces alkynylene.It is preferred that alkylidene, substituted alkylene, alkenylene, substitution alkenylene, more preferable alkylidene and alkenylene.

Alkylidene also can have branch.The carbon atom number of alkylidene is preferably 1~12, and more preferably 2~10, most preferably 2~8.

The alkylene moiety of substituted alkylene is identical as above-mentioned alkylidene.Example as substituent group includes halogen atom.

Alkenylene also can have branch.The carbon atom number of alkenylene is preferably 2~12, and more preferably 2~10, most preferably 2~8.

The alkylene moiety of substituted alkylene is identical as above-mentioned alkylidene.Example as substituent group includes halogen atom.

Alkynylene also can have branch.The carbon atom number of alkynylene is preferably 2~12, and more preferably 2~10, most preferably 2~8.

Replace the alkynylene part of alkynylene identical as above-mentioned alkynylene.The example of substituent group includes halogen atom.

The specific example of chain base as divalent can enumerate ethylidene, trimethylene, propylidene, tetramethylene, 1- methyl-tetramethylene, pentamethylene, hexa-methylene, eight methylene, 2- butenylidene, 2- butenylidene, 2- butynelene etc..

The definition of the cyclic group of divalent and example and aftermentioned Cy¹、Cy²And Cy³Definition it is identical with example.

R²²²Preferably carbon atom number be 1~4 alkyl or hydrogen atom, more preferable methyl, ethyl or hydrogen atom, most preferably hydrogen atom.

L²Or L³It is the linking group of singly-bound or divalent respectively.L²And L³It is preferred that being respectively to be selected from-O- ,-S- ,-CO- ,-NR²²², the chain base of divalent, divalent cyclic group and combinations thereof divalent linking group or singly-bound.Above-mentioned R²²²Be carbon atom number be 1~7 alkyl or hydrogen atom, preferably carbon atom number be 1~4 alkyl or hydrogen atom, more preferable methyl, ethyl or hydrogen atom, most preferably hydrogen atom.The cyclic group and L of chain base and divalent for divalent¹And L⁴Definition it is synonymous.

In formula (I), n111 be 0,1 or 2.When n is 2, two L³It can be the same or different, two Cy²It can be the same or different.N111 is preferably 1 or 2, more preferably 1.

In formula (I), Cy¹、Cy²And Cy³It is the cyclic group of divalent respectively.

The ring contained in cyclic group is preferably 5 member rings, 6 member rings or 7 member rings, more preferably 5 member rings or 6 member rings, most preferably 6 member rings.

The ring contained in cyclic group is also possible to condensed ring.But the more preferable monocycle compared with condensed ring.

The ring contained in cyclic group is also possible to any one of aromatic ring, aliphatic ring and heterocycle.The example of aromatic ring includes phenyl ring and naphthalene nucleus.The example of aliphatic ring includes cyclohexane ring.The example of heterocycle includes pyridine ring and pyrimidine ring.

As the cyclic group with phenyl ring, preferably Isosorbide-5-Nitrae-phenylene.As the cyclic group with naphthalene nucleus, preferably naphthalene -1,5- diyl and naphthalene -2,6- diyl.As the preferred Isosorbide-5-Nitrae of the cyclic group with cyclohexane ring-hexamethylene support group.As preferred pyridine -2, the 5- diyl base of cyclic group with pyridine ring.As the cyclic group with pyrimidine ring, preferably pyrimidine -2,5- diyl.

Cyclic group also can have substituent group.The example of substituent group include halogen atom, cyano, nitro, carbon atom number be 1~5 alkyl, carbon atom number be 1~5 halogen-substituted alkyl, carbon atom number be 1~5 alkoxy, carbon atom number be 1~5 alkyl sulfenyl, carbon atom number be 2~6 acyloxy, carbon atom number be 2~6 alkoxy carbonyl, carbamoyl, carbon atom number be 2~6 alkyl-substituted amino formoxyl and carbon atom number be 2~6 amide groups.

In the following, showing the example of the polymerizable liquid crystal compound indicated with formula (I).The present invention is not limited to these.

[chemical formula 41]

[chemical formula 42]

[chemical formula 43]

[chemical formula 44]

Polymerizable liquid crystal layer can by by include liquid crystal compounds and as needed just include polymerization initiator, average slope angle regulator and arbitrary additive (for example, plasticizer, monomer, surfactant, orientation temperature depressant, chiral agent) coating liquid coated in being formed in alignment films.

(polymerization initiator)

The liquid crystal compounds of orientation can be by keeping state of orientation to be fixed.Immobilization is preferably carried out by polymerization reaction.As polymerization reaction, including using the heat polymerization of thermal polymerization and using the photopolymerization reaction of Photoepolymerizationinitiater initiater.It is preferred that photopolymerization reaction.

Example as Photoepolymerizationinitiater initiater, including alpha-carbonyl compound (United States Patent (USP) 2367661, United States Patent (USP) 2367670 each specifications are recorded), asioinether (No. 2448828 specifications of United States Patent (USP) are recorded), α-hydrocarbon substituted aromatic acyloin com (No. 2722512 specifications of United States Patent (USP) are recorded), multicore naphtoquinone compounds (United States Patent (USP) 3046127, United States Patent (USP) 2951758 each specifications are recorded), the combination of triarylimidazoles dimer and p- aminophenyl ketone (No. 3549367 specifications of United States Patent (USP) are recorded), bifurcation pyridine and compound phenazine (tekiaki 60-105667 bulletin, No. 4239850 specifications of United States Patent (USP) are recorded) and oxadiazole compound (United States Patent (USP) 4212970 are said Bright secretary carries).

The usage amount of Photoepolymerizationinitiater initiater is preferably the range of 0.01~20 mass % of the solid component of coating liquid, the more preferably range of 0.5~5 mass %.

It is preferable to use ultraviolet lights for the irradiation light polymerizeing for liquid crystal compounds.

Irradiation energy is preferably 20mJ/cm²~50J/cm²Range, more preferably 20~5000mJ/cm²Range, further preferably 100~800mJ/cm²Range.In addition, light irradiation can also be performed under heating conditions in order to promote photopolymerization reaction.

(average slope angle controlling agent)

Phase difference film of the invention can adjust the average slope angle of liquid crystal compounds by the compound with specific surface-active.

The low-grade fatty acid ester of cellulose, fluorine-containing surfactant or compound with 1,3,5-triazines ring can be enumerated as the compound for reducing average slope angle.

(low-grade fatty acid ester of cellulose)

So-called " lower fatty acid " in the low-grade fatty acid ester of cellulose refers to, carbon atom number is 6 fatty acid below.Carbon atom number is preferably 2~5, and more preferably 2~4.Substituent group (for example, hydroxyl) can also be combined in fatty acid.Two kinds or more of fatty acid can also form cellulose and ester.The example of low-grade fatty acid ester as cellulose, including cellulose ethanoate, cellulose propionate, cellulose butylate, cellulose hydroxyl group propionic ester, cellulose acetate propionate and cellulose acetate butyrate.Particularly preferred cellulose acetate butyrate.The Butyrylation degree of cellulose acetate butyrate is preferably 30% or more, and more preferably 30~80%.The degree of acetylation of cellulose acetate butyrate is preferably 30% hereinafter, more preferably 1~30%.The low-grade fatty acid ester of cellulose is used with the amount of 0.01~1 mass % of the amount of liquid crystal compounds.Usage amount is preferably 0.1~1 mass % of the amount of liquid crystal compounds, more preferably 0.3~0.9 mass %.

The compound that compound with 1,3,5-triazines ring is preferably indicated with following formula (III-I).

[chemical formula 45]

Formula (III-I)

In formula (III-I), X¹、X²And X³It is singly-bound ,-NR respectively³³³-(R³³³The alkyl or hydrogen atom that carbon atom number is 1~30) ,-O- or-S-, R³¹、R³²And R³³It is alkyl, alkenyl, aryl or heterocycle respectively.

Melamine compound is particularly preferably with the compound that formula (III-I) indicates.In melamine compound, in formula (III-I), X¹、X²Or X³It is-NR³³³Or X¹、X²Or X³It is singly-bound, and R³¹、R³²And R³³It is the heterocycle on nitrogen-atoms with free valence.For melamine compound, quotes formula (IV) and be explained in more detail.-NR³³³R³³³Particularly preferably hydrogen atom.R³¹、R³²And R³³Particularly preferably aryl.

Abovementioned alkyl more preferable chain-like alkyl compared with cyclic alkyl.The further preferably straight-chain alkyl compared with the chain-like alkyl with branch.The carbon atom number of alkyl is preferably 1~30, and more preferably 2~30, further preferably 4~30, most preferably 6~30.Alkyl also can have substituent group.As the example of substituent group, including halogen atom, alkoxy (such as methoxyl group, ethyoxyl, epoxy ethyoxyl) and acyloxy (for example, acryloxy, methacryloxy).Above-mentioned alkenyl more preferable chain alkenyl compared with cyclic alkenyl radical.The more preferable straight-chain alkenyl compared with the chain alkenyl with branch.The carbon atom number of alkenyl is preferably 2~30, and more preferably 3~30, further preferably 4~30, most preferably 6~30.Alkenyl also can have substituent group.Example example as substituent group includes halogen atom, alkoxy (such as methoxyl group, ethyoxyl, epoxy ethyoxyl) and acyloxy (such as acryloxy, methacryloxy).

Above-mentioned aryl is preferably phenyl or naphthyl, particularly preferred phenyl.Aryl also can have substituent group.Replace sulfamoyl, alkenyl that sulfamoyl, aryl is replaced to replace sulfamoyl, sulfoamido, carbamoyl, alkyl-substituted amino formoxyl, alkenyl substituted-amino formoxyl, aryl substituted-amino formoxyl, amide groups, alkylthio group, alkenylthio group, arylthio and acyl group as the example of substituent group, including halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl, alkenyl, aryl, alkoxy, alkenyloxy group, aryloxy group, acyloxy, alkoxy carbonyl, allyloxycarbonyl, aryloxycarbonyl, sulfamoyl, alkyl.Abovementioned alkyl has definition identical with abovementioned alkyl.Alkoxy, acyloxy, alkoxy carbonyl, alkyl replace the moieties of sulfamoyl, sulfoamido, alkyl-substituted amino formoxyl, amide groups, alkylthio group and acyl group also identical as aforesaid alkyl.Above-mentioned alkenyl has definition identical with above-mentioned alkenyl.Alkenyloxy group, acyloxy, allyloxycarbonyl, alkenyl replace the alkenyl part of sulfamoyl, sulfoamido, alkenyl substituted-amino formoxyl, amide groups, alkenylthio group and acyl group also identical as above-mentioned alkenyl.As the example of above-mentioned aryl, including phenyl, Alpha-Naphthyl, betanaphthyl, 4- methoxyphenyl, 3,4- diethoxy phenyl, 4- octyloxyphenyl and 4- dodecyloxy phenyl.Aryloxy group, acyloxy, aryloxycarbonyl, aryl replace the example of the part of sulfamoyl, sulfoamido, aryl substituted-amino formoxyl, amide groups, arylthio and acyl group identical as the example of above-mentioned aryl.

X¹、X²Or X³It is-NR³³³,-O- or heterocycle when-S- preferably there is aromatic series.Heterocycle with aromatic series is usually unsaturated heterocycle, preferably has up to the heterocycle of double bond.Heterocycle is preferably 5 member rings, 6 member rings or 7 member rings, more preferable 5 member ring or 6 member rings, most preferably 6 member rings.The hetero atom of heterocycle is preferably N, S or O, particularly preferred N.As the heterocycle with aromatic series, particularly preferred pyridine ring (being 2- pyridine ring or 4- pyridine ring as heterocycle).Heterocycle also can have substituent group.The example of the substituent group of heterocycle is identical as the example of the substituent group of above-mentioned aryl moiety.X¹、X²Or X³Heterocycle when for singly-bound is preferably the heterocycle on nitrogen-atoms with free valence.The heterocycle on nitrogen-atoms with free valence is preferably 5 member rings, 6 member rings or 7 member rings, more preferable 5 member ring or 6 member rings, most preferably 5 member rings.Heterocycle also can have multiple nitrogen-atoms.In addition, heterocycle also can have the hetero atom (such as O, S) other than nitrogen-atoms.Heterocycle also can have substituent group.The example of the substituent group of heterocycle is identical as the example of the substituent group of above-mentioned aryl moiety.In the following, showing the example on nitrogen-atoms with the heterocycle of free valence.

[chemical formula 46]

[chemical formula 47]

[chemical formula 48]

[chemical formula 49]

R³¹、R³²And R³³At least one preferably include carbon atom number be 9~30 alkylene moiety or alkenylene moieties.The alkylene moiety or alkenylene moieties that carbon atom number is 9~30 are preferably straight-chain.Alkylene moiety or alkenylene moieties preferably are contained in the substituent group of aryl.In addition, R³¹、R³²And R³³At least one preferably have polymerism base as substituent group.Compound with 1,3,5-triazines ring preferably has at least two polymerism bases.In addition, polymerism base is preferably placed at R³¹、R³²Or R³³End.By introducing polymerism base into the compound with 1,3,5-triazines ring, can with 1,3,5-triazines ring compound and liquid crystal compounds, for example discotic mesogenic molecule is polymerize in the state of make that it includes in phase difference film.R with polymerism base as substituent group³¹、R³²Or R³³It is indicated with following formula (Rp).

Formula (Rp)

-L⁵(-P)_n333

In formula (Rp), L⁵It is the linking group of (n333+1) valence, P is polymerism base, and n333 is 1~5 integer.In formula (Rp), the linking group (L of (n333+1) valence⁵) preferably alkylidene, alkenylene, the aromatic series base of n333+1 valence, the heterocycle residue of divalent ,-CO- ,-NR are selected from by least two³³⁴-(R³³⁴The alkyl or hydrogen atom that carbon atom number is 1~30) ,-O- ,-S- and-SO₂Moiety combinations formed linking group.The carbon atom number of alkylidene is preferably 1~12.The carbon atom number of alkenylene is preferably 2~12.The carbon atom number of aromatic series base is preferably 6~10.It shown below the L of formula (Rp)⁵Example.The X in left side and formula (III-I)¹、X²Or X³In conjunction with (X¹、X²Or X³When being singly-bound, it is directly connected to 1,3,5-triazines ring), right side and (L⁵³~L⁵⁹Middle n) polymerism base (P) combination.AL refers to that alkylidene or alkenylene, Hc refer to the heterocycle residue of divalent, and AR refers to aromatic series base.In addition, alkylidene, alkenylene, heterocycle residue and aromatic series base also can have substituent group (such as alkyl, halogen atom).

L⁵¹:-AL-O-CO-

L⁵²:-AL-O-

L⁵³:-AR (- O-AL-O-CO-)_n

L⁵⁴:-AR (- O-AL-O-)_n

L⁵⁵:-AR (- O-CO-AL-O-CO-)_n

L⁵⁶:-AR (- CO-O-AL-O-CO-)_n

L⁵⁷:-AR (- O-CO-AR-O-AL-O-CO-)_n

L⁵⁸:-AR (- NR-SO₂-AL-O-CO-)_n

L⁵⁹:-AR (- SO₂-NR-AL-O-CO-)_n

As the polymerism base (P) in formula (Rp), it is preferable to use following structures.

[chemical formula 50]

(P1)             (P2)               (P3)

- CH=CH₂       -C≡CH           -CH₂-C≡CH

[chemical formula 51]

(P4)             (P5)               (P6)

-NH₂           -SO₃H           

[chemical formula 52]

(P7)             (P8)               (P9)

- CH=CH-CH₃- N=C=S

[chemical formula 53]

(P10)            (P11)              (P12)

-SH            -CHO              -OH

[chemical formula 54]

(P13)                (P14)                (P15)

-CO₂H-N=C=O-CH=CH-C₂H₅

[chemical formula 55]

(P16)                (P17)                (P18)

- CH=CH-n-C₃H₇  

The preferred unsaturated polymerism base (P1, P2, P3, P7, P8, P15, P16, P17) of polymerism base (P) or epoxy group (P6, P18), more preferably unsaturation polymerism base, most preferably ethylenic bond unsaturation polymerism base (P1, P7, P8, P15, P16, P17).In formula (Rp), n is 4~12 integer.Specific number is determined according to the type of liquid crystal compounds.

It shown below (except melamine compound) specific example of the compound with 1,3,5-triazines ring.

[chemical formula 56]

(TR-1~13)

TR-1:R³¹、R³²、R³³:-(CH₂)₉- O-CO-CH=CH₂

TR-2:R³¹、R³²、R³³:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

TR-3:R³¹、R³²:-(CH₂)₉- O-CO-CH=CH₂；R³³:-(CH₂)₁₂-CH₃

TR-4:R³¹、R³²:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R³³:-(CH₂)₁₂-CH₃

TR-5:R³¹:-(CH₂)₉- O-CO-CH=CH₂；R³²、R³³:-(CH₂)₁₂-CH₃

TR-6:R³¹:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R³²、R³³:-(CH₂)₁₂-CH₃

TR-7:R³¹、R³²:-(CH₂)₄- O-CO-CH=CH₂；R³³:-(CH₂)₁₂-CH₃

TR-8:R³¹:-(CH₂)₄- O-CO-CH=CH₂；R³²、R³³:-(CH₂)₁₂-CH₃

TR-9:R³¹、R³²、R³³:-(CH₂)₉-O-EpEt

TR-10:R³¹、R³²、R³³:-(CH₂)₄- CH=CH- (CH₂)₄-O-EpEt

TR-11:R³¹、R³²:-(CH₂)₉-O-EpEt；R³³:-(CH₂)₁₂-CH₃

TR-12:R³¹、R³²、R³³:-(CH₂)₉- O-CH=CH₂

TR-13:R³¹、R³²:-(CH₂)₉- O-CH=CH₂；R³³:-(CH₂)₁₂-CH₃

EpEt indicates epoxy ethyl (same as below).

[chemical formula 57]

(TR-14~65)

TR-14:X¹、X²、X³:-O-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-15:X¹、X²、X³:-O-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-16:X¹、X²、X³:-O-；R³²、R³⁵、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

TR-17:X¹、X²、X³:-O-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

TR-18:X¹、X²、X³:-O-；R³¹、R³³、R³⁴、R³⁶、R³⁷、R³⁹:-O- (CH₂)₉-O-CO-CH-CH₂

TR-19:X¹、X²、X³:-O-；R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹:-O- (CH₂)₉- O-CO-CH=CH₂

TR-20:X¹、X²:-O-；X³:-NH-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-21:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O- (CH₂)₁₂-CH₃

TR-22:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁷、R³⁸:-O- (CH₂)₁₂-CH₃

TR-23:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-24:X¹:-O-；X²、X³:-NH-；R³¹、R³³:-O- (CH₂)₁₂-CH₃；R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-25:X¹:-O-；X²、X³:-NH-；R³¹、R³²:-O- (CH₂)₆- O-CO-CH=CH₂；R³⁵、R³⁸:-O- (CH₂)₁₁

-CH ₃

TR-26:X¹:-O-；X²、X³:-NH-；R³¹、R³²、R³³:-O- (CH²)⁶- O-CO-CH=CH₂；R³⁵、R³⁸:-O- (CH₂)₁₁-CH₃

TR-27:X¹、X²:-NH-；X³:-S-；R³²、R³⁵:-O- (CH₂)⁹- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-28:X¹、X²:-NH-；X³:-S-；R³¹、R³²、R³⁴、R³⁵:-O- (CH₂)₉- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-29:X¹、X²:-NH-；X³:-S-；R³²、R³⁵:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-30:X¹、X²:-NH-；X³:-S-；R³¹、R³²、R³⁴、R³⁵:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-31:X¹、X²:-NH-；X³:-S-；R³¹、R³³、R³⁴、R³⁶:-O- (CH₂)₉- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-32:X¹、X²:-NH-；X³:-S-；R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶:-O- (CH₂)₉- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-33:X¹、X²:-O-；X³:-S-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-34:X¹、X²:-O-；X³:-S-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O- (CH₂)₁₂-CH₃

TR-35:X¹、X²:-O-；X³:-S-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁷、R³⁸:-O- (CH₂)₁₂-CH₃

TR-36:X¹、X²:-O-；X³:-S-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-37:X¹:-O-；X²、X³:-S-；R³¹、R³³:-O- (CH₂)₁₂-CH₃；R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-38:X¹:-O-；X²、X³:-S-；R³¹、R³²:-O- (CH₂)₆- O-CO-CH=CH₂；R³⁵、R³⁸:-O- (CH₂)₁₁-CH₃

TR-39:X¹:-O-；X²、X³:-S-；R³¹、R³²、R³³:-O- (CH₂)₆- O-CO-CH=CH₂；R³⁵、R³⁸:-O- (CH₂)₁₁-CH₃

TR-40:X¹、X²、X³:-S-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-41:X¹、X²、X³:-S-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-42:X¹、X²、X³:-S-；R³²、R³⁵、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

TR-43:X¹、X²、X³:-S-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄-O-CO-

CH=CH ₂

TR-44:X¹、X²、X³:-S-；R³¹、R³³、R³⁴、R³⁶、R³⁷、R³⁹:-O- (CH₂)₉- O-CO-CH=CH₂

TR-45:X¹、X²、X³:-S-；R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷、R³⁸、R³⁹:-O- (CH₂)₉- O-CO-CH=CH₂

TR-46:X¹、X²:-S-；X³:-NH-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CO-CH=CH₂

TR-47:X¹、X²:-S-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O- (CH₂)₁₂-CH₃

TR-48:X¹、X²:-S-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁷、R³⁸:-O- (CH₂)₁₂-CH₃

TR-49:X¹、X²:-S-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄- O-CO-CH=CH₂；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-50:X¹:-O-；X²:-NH-；X³:-S-；R³¹、R³³:-O- (CH₂)₁₂-CH₃；R³⁵:-O- (CH₂)₉- O-CO-CH=CH₂；R³⁸:-O- (CH₂)₁₂-CH₃

TR-51:X¹；-O-；X²:-NH-；X³:-S-；R³¹、R³²:-O- (CH₂)₆- O-CO-CH=CH₂；R³⁵:-O- (CH₂)₁₁-CH₃；R³⁸:-O- (CH₂)₁₂-CH₃

TR-52:X¹:-O-；X²:-NH-；X³:-S-；R³¹、R³²、R³³:-O- (CH₂)₆- O-CO-CH=CH₂；R³⁵:-O- (CH₂)₁₁-CH₃；R³⁸:-O- (CH₂)₁₂-CH₃

TR-53:X¹、X²、X³:-O-；R³²、R³⁵、R³⁸:-O- (CH₂)₉-O-EpEt

TR-54:X¹、X²、X³:-O-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₉-O-EpEt

TR-55:X¹、X²、X³:-O-；R³²、R³⁵、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄-O-EpEt

TR-56:X¹、X²、X³:-O-；R³¹、R³²、R³⁴、R³⁵、R³⁷、R³⁸:-O- (CH₂)₄- CH=CH- (CH₂)₄-O-EpEt

TR-57:X¹、X²、X³:-O-；R³¹、R³³、R³⁴、R³⁶、R³⁷、R³⁹:-O- (CH₂)₉-O-EpEt

TR-58:X¹、X²、X³:-O-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CH=CH₂

TR-59:X¹、X²:-O-；X³:-NH-；R³²、R³⁵、R³⁸:-O- (CH₂)₉-O-EpEt

TR-60:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄-O-EpEt；R³⁸:-O- (CH₂)₁₂-CH₃

TR-61:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄-O-EpEt；R³⁷、R³⁸:-O- (CH₂)₁₂-CH₃

TR-62:X¹、X²:-O-；X³:-NH-；R³²、R³⁵:-O- (CH₂)₄-O-EpEt；R³⁸:-O-CO- (CH₂)₁₁-CH₃

TR-63:X¹:-O-；X²、X³:-NH-；R³¹、R³³:-O- (CH₂)₁₂-CH₃；R³⁵、R³⁸:-O- (CH₂)₉-O-EpEt

TR-64:X¹:-O-；X²、X³:-NH-；R³¹、R³²:-O- (CH₂)₆-O-EpEt；R³⁵、R³⁸:-O- (CH₂)₁₁-CH₃

TR-65:X¹、X²:-O-；X³:-NH-；R³²、R³⁵、R³⁸:-O- (CH₂)₉- O-CH=CH₂

The melamine compound that compound with 1,3,5-triazines ring is preferably indicated with following formula (IV-I).

[chemical formula 58]

Formula (IV-I)

In formula (IV-I), R⁴¹、R⁴³And R⁴⁵It is the alkyl or hydrogen atom that carbon atom number is 1~30, R respectively⁴²、R⁴⁴And R⁴⁶It is alkyl, alkenyl, aryl or heterocycle or R respectively⁴¹And R⁴²、R⁴³And R⁴⁴Or R⁴⁵And R⁴⁶Respectively in connection with formation heterocycle.R⁴¹、R⁴³And R⁴⁵Preferably carbon atom number is 1~20 alkyl or hydrogen atom, and the alkyl or hydrogen atom that more preferable carbon atom number is 1~10, further preferred carbon atom number is 1~6 alkyl or hydrogen atom, most preferably hydrogen atom.R⁴²、R⁴⁴And R⁴⁶Particularly preferably aryl.Abovementioned alkyl, alkenyl, the definition of aryl and heterocycle and substituent group are identical as the definition of each group and substituent group that illustrate in above-mentioned formula (III-I).R⁴¹And R⁴²、R⁴³And R⁴⁴Or R⁴⁵And R⁴⁶By combining the heterocycle formed to have the free heterocycle of valence identical on nitrogen-atoms with what is illustrated in above-mentioned formula (III-I).

R⁴²、R⁴⁴And R⁴⁶At least one preferably comprise carbon atom number be 9~30 alkylene moiety or alkenylene moieties.The alkylene moiety or alkenylene moieties that carbon atom number is 9~30 are preferably straight-chain.Alkylene moiety or alkenylene moieties preferably are contained in the substituent group of aryl.In addition, R⁴²、R⁴⁴And R⁴⁶At least one preferably have polymerism base as substituent group.Melamine compound preferably has at least two polymerism bases.In addition, polymerism base is preferably placed at R⁴²、R⁴⁴And R⁴⁶End.By introducing polymerism base into melamine compound, can melamine compound and liquid crystal compounds, for example discotic mesogenic molecule is polymerize in the state of make that it includes in optical anisotropic layer.R with polymerism base as substituent group⁴²、R⁴⁴And R⁴⁶It is identical as the group indicated with above-mentioned formula (Rp).

It shown below the specific example of melamine compound.

[chemical formula 59]

(MM-1~46)

MM-1:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₉-CH₃

MM-2:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₁₁-CH₃

MM-3:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₁₅-CH₃

MM-4:R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₉-CH₃

MM-5:R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₁₅-CH₃

MM-6:R⁴³、R⁵³、R⁶³:-O-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₁₇-CH₃

MM-7:R⁴⁴、R⁵⁴、R⁶⁴:-CO-O- (CH₂)₁₁-CH₃

MM-8:R⁴⁴、R⁵⁴、R⁶⁴:-SO₂-NH-(CH₂)₁₇-CH₃

MM-9:R⁴³、R⁵³、R⁶³:-O-CO- (CH₂)₁₅-CH₃

MM-10:R⁴²、R⁵²、R⁶²:-O- (CH₂)₁₇-CH₃

MM-11:R⁴²、R⁵²、R⁶²:-O-CH₃；R⁴³、R⁵³、R⁶³:-CO-O- (CH₂)₁₁-CH₃

MM-12:R⁴²、R⁵²、R⁶²:-Cl；R⁴³、R⁵³、R⁶³:-CO-O- (CH₂)₁₁-CH₃

MM-13:R⁴²、R⁵²、R⁶²:-O- (CH₂)₁₁-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-SO₂The iso- C of-NH-₃H⁷

MM-14:R⁴²、R⁵²、R⁶²:-Cl；R⁴⁵、R⁵⁵、R⁶⁵:-SO₂-NH-(CH₂)₁₅-CH₃

MM-15:R⁴²、R⁴⁶、R⁵²、R⁵⁶、R⁶²、R⁶⁶:-Cl；R⁴⁵、R⁵⁵、R⁶⁵:-SO₂-NH-(CH₂)₁₉-CH₃

MM-16:R⁴³、R⁵⁴:-O- (CH₂)₉-CH₃；R⁴⁴、R⁵³、R⁶³、R⁶⁴:-O- (CH₂)₁₁-CH₃

MM-17:R⁴⁴:-O- (CH₂)₁₁-CH₃；R⁵⁴:-O- (CH₂)₁₅-CH₃；R⁶⁴:-O- (CH₂)₁₇-CH₃

MM-18:R⁴²、R⁴⁵、R⁵²、R⁵⁵、R⁶²、R⁶⁵:-O-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-NH-CO- (CH₂)₁₄-CH₃

MM-19:R⁴²、R⁴⁵、R⁵²、R⁵⁵、R⁶²、R⁶⁵:-O- (CH₂)₃-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₁₅-CH₃

MM-20:R⁴²、R⁵²、R⁶²:-NH-SO₂-(CH₂)₁₅-CH₃；R⁴⁴、R⁴⁵、R⁵⁴、R⁵⁵、R⁶⁴、R⁶⁵:-Cl

MM-21:R⁴²、R⁴³、R⁵²、R⁵³、R⁶²、R⁶³:-F；R⁴⁴、R⁵⁴、R⁶⁴:-CO-NH- (CH₂)₁₅-CH₃；R⁴⁵、R⁴⁶、R⁵⁵、R⁵⁶、R⁶⁵、R⁶⁶:-Cl

MM-22:R⁴²、R⁵²、R⁶²:-Cl；R⁴⁴、R⁵⁴、R⁶⁴:-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-NH-CO- (CH₂)₁₂-CH₃

MM-23:R⁴²、R⁵²、R⁶²:-OH；R⁴⁴、R⁵⁴、R⁶⁴:-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₁₅-CH₃

MM-24:R⁴²、R⁴⁵、R⁵²、R⁵⁵、R⁶²、R⁶⁵:-O-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-(CH₂)₁₁-CH₃

MM-25:R⁴²、R⁵²、R⁶²:-NH-SO₂-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-CO-O- (CH₂)₁₁-CH₃

MM-26:R⁴²、R⁵²、R⁶²:-S- (CH₂)₁₁-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-SO₂-NH₂

MM-27:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₁₂- O-CO-CH=CH₂

MM-28:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₈- O-CO-CH=CH₂

MM-29:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O-CO- (CH₂)₇- O-CO-CH=CH₂

MM-30:R⁴⁴、R⁵⁴、R⁶⁴:-CO-O- (CH₂)₁₂-O-CO-C(CH₃)=CH₂

MM-31:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O-CO-p-Ph-O- (CH₂)₄- O-CO-CH=CH₂

MM-32:R⁴²、R⁴⁴、R⁵²、R⁵⁴、R⁶²、R⁶⁴:-NH-SO₂-(CH₂)₈- O-CO-CH=CH₂；R⁴⁵、R⁵⁵、R⁶⁵:-Cl

MM-33:R⁴²、R⁵²、R⁶²:-NH-SO₂-CH₃；R⁴⁵、R⁵⁵、R⁶⁵:-CO-O- (CH₂)₁₂- O-CO-CH=CH₂

MM-34:R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₉- O-CO-CH=CH₂

MM-35:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₉- O-CO-CH=CH₂

MM-36:R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

MM-37:R⁴³、R⁴⁴、R⁵³、R⁵⁴、R⁶³、R⁶⁴:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

MM-38:R⁴³、R⁴⁵、R⁵³、R⁵⁵、R⁶³、R⁶⁵:-O- (CH₂)₉- O-CO-CH=CH₂

MM-39:R⁴³、R⁴⁴、R⁴⁵、R⁵³、R⁵⁴、R⁵⁵、R⁶³、R⁶⁴、R⁶⁵:-O- (CH₂)₉- O-CO-CH=CH₂

MM-40:R⁴⁴、R⁵⁴:-O- (CH₂)₄- O-CO-CH=CH₂；R⁶⁴:-O- (CH₂)₉- O-CO-CH=CH₂

MM-41:R⁴⁴、R⁵⁴:-O- (CH₂)₄- O-CO-CH=CH₂；R⁶⁴:-O- (CH₂)₁₂-CH₃

MM-42:R⁴⁴、R⁵⁴:-O- (CH₂)₄- O-CO-CH=CH₂；R⁶³、R⁶⁴:-O- (CH₂)₁₂-CH₃

MM-43:R⁴⁴、R⁵⁴:-O- (CH₂)₄- O-CO-CH=CH₂；R⁶³、R⁶⁴:-O-CO- (CH₂)₁₁-CH₃

MM-44:R⁴³、R⁴⁵:-O- (CH₂)₁₂-CH₃；R⁵⁴、R⁶⁴:-O- (CH₂)₉- O-CO-CH=CH₂

MM-45:R⁴³、R⁴⁴:-O- (CH₂)₆- O-CO-CH=CH₂；R⁵⁴、R⁶⁴:-O- (CH₂)₁₁-CH₃

MM-46:R⁴³、R⁴⁴、R⁴⁵:-O- (CH₂)₆- O-CO-CH=CH₂；R⁵⁴、R⁶⁴:-O- (CH₂)₁₁-CH₃P-Ph indicates p- phenylene (same as below).

[chemical formula 60]

(MM-47~59)

MM-47:R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₅-CH₃；R⁴⁸、R⁵⁸、R⁶⁸:-O- (CH₂)₁₁-CH₃

MM-48:R⁴⁵、R⁵⁵、R⁶⁵:-SO₂-NH-(CH₂)₁₇-CH₃

MM-49:R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₅-CH6₃

MM-50:R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₁₇-CH₃；R⁴⁷、R⁵⁷、R⁶⁷:-SO₂-NH-CH₃

MM-51:R⁴³、R⁵³、R⁶³:-O- (CH₂)₁₅-CH₃

MM-52:R⁴¹、R⁵¹、R⁶¹:-O- (CH₂)₁₇-CH₃

MM-53:R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-Ph；R⁴⁸、R⁵⁸、R⁶⁸:-O- (CH₂)₁₁-CH₃

MM-54:R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₂₁-CH₃；R⁴⁷、R⁵⁷、R⁶⁷:-SO₂-NH-Ph

MM-55:R⁴¹、R⁵¹、R⁶¹:-p-Ph- (CH₂)₁₁-CH₃

MM-56:R⁴⁶、R⁴⁸、R⁵⁶、R⁵⁸、R⁶⁶、R⁶⁸:-SO₂-NH-(CH₂)₇-CH₃

MM-57:R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₀- O-CO-CH=CH₂；R⁴⁸、R⁵⁸、R⁶⁸:-O- (CH₂)₁₂-CH₃

MM-58:R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₁₂- O-CO-CH=CH₂；R⁴⁷、R⁵⁷、R⁶⁷:-SO₂-NH-Ph

MM-59:R⁴³、R⁵³、R⁶³:-O- (CH₂)₁₆- O-CO-CH=CH₂

[chemical formula 61]

(MM-60~71)

MM-60:R⁴⁵、R⁵⁵、R⁶⁵:-NH-CO- (CH₂)₁₄-CH₃

MM-61:R⁴²、R⁵²、R⁶²:-O- (CH₂)₁₇-CH₃MM-62:R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₁₅-CR₃

MM-63:R⁴⁵、R⁵⁵、R⁶⁵:-SO₂-NH-(CH₂)₁₅-CH₃

MM-64:R⁴³、R⁵³、R⁶³:-CO-NH- (CH₂)₁₇-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-OH

MM-65:R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₁₅-CH₃；R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₁-CH₃

MM-66:R⁴⁷、R⁵⁷、R⁶⁷:-O- (CH₂)₂₁-CH₃MM-67:R⁴⁴、R⁵⁴、R⁶⁴:-O-p-Ph- (CH₂)₁₁-CH₃

MM-68:R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₅-CH₃

MM-69:R⁴³、R⁵³、R⁶³:-CO-NH- (CH₂)₁₇-CH₃；R⁴⁴、R⁵⁴、R⁶⁴:-O- (CH₂)₁₂- O-CO-CH=CH₂

MM-70:R⁴⁵、R⁵⁵、R⁶⁵:-O- (CH₂)₈- O-CO-CH=CH₂；R⁴⁶、R⁵⁶、R⁶⁶:-SO₂-NH-(CH₂)₁₁-CH₃

MM-71:R⁴³、R⁴⁶、R⁵³、R⁵⁶、R⁶³、R⁶⁶:-SO₂-NH-(CH₂)₈- O-CO-CH=CH₂

[chemical formula 62]

(MM-72~75)

MM-72:R⁴¹、R⁴³、R⁴⁵:-CH₃

MM-73:R⁴¹、R⁴³、R⁴⁵:-C₂H₅

MM-74:R⁴¹、R⁴³:-C₂H₅；R⁴⁵:-CH₃

MM-75:R⁴¹、R⁴³、R⁴⁵:-(CH₂)₃-CH₃

[chemical formula 63]

(MM-76~88)

MM-76:R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₉- O-CO-CH=CH₂

MM-77:R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

MM-78:R⁴²、R⁴⁴:-(CH₂)₉- O-CO-CH=CH₂；R⁴⁶:-(CH₂)₁₂-CH₃

MM-79:R⁴²、R⁴⁴:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R⁴⁶:-(CH₂)₁₂-CH₃

MM-80:R⁴²:-(CH₂)₉- O-CO-CH=CH₂；R⁴⁴、R⁴⁶:-(CH₂)₁₂-CH₃

MM-81:R⁴²:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R⁴⁴、R⁴⁶:-(CH₂)₁₂-CH₃

MM-82:R⁴²、R⁴⁴:-(CH₂)₄- O-CO-CH=CH₂；R⁴⁶:-(CH₂)₁₂-CH₃

MM-83:R⁴²:-(CH₂)₄- O-CO-CH=CH₂；R⁴⁴、R⁴⁶:-(CH₂)₁₂-CH₃

MM-84:R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₉-O-EpEt

MM-85:R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₄- CH=CH- (CH₂)₄-O-EpEt

MM-86:R⁴²、R⁴⁴:-(CH₂)₉-O-EpEt；R⁴⁶:-(CH₂)₁₂-CH₃

MM-87:R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₉- O-CH=CH₂

MM-88:R⁴²、R⁴⁴:-(CH₂)₉- O-CH=CH₂；R⁴⁶:-(CH₂)₁₂-CH₃

[chemical formula 64]

(MM-89~95)

MM-89:R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶:-(CH₂)₉-CH₃

MM-90:R⁴¹、R⁴³、R⁴⁵:-CH₃；R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₁₇-CH₃

MM-91:R⁴¹、R⁴²、R⁴³、R⁴⁴:-(CH₂)₇-CH₃；R⁴⁵、R⁴⁶:-(CH₂)₅-CH₃

MM-92:R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶:-CyHx

MM-93:R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶:-(CH₂)₂-O-C₂H₅

MM-94:R⁴¹、R⁴³、R⁴⁵:-CH₃；R⁴²、R⁴⁴、R⁴⁶:-(CH₂)₁₂- O-CO-CH=CH₂

MM-95:R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶:-(CH₂)₈- O-CO-CH=CH₂

CyHx indicates cyclohexyl.

[chemical formula 65]

(MM-96)

As melamine compound, melamine polymer also can be used.Melamine polymer is preferably synthesized by the polymerization reaction of the melamine compound and carbonyls that are indicated with following formula (V-I).

Formula (V-I)

[chemical formula 66]

In formula (V-I), R⁷¹、R⁷²、R⁷³、R⁷⁴、R⁷⁵And R⁷⁶It is hydrogen atom, alkyl, alkenyl, aryl or heterocycle respectively.Abovementioned alkyl, alkenyl, the definition of aryl and heterocycle and substituent group are identical as the definition of each base and substituent group that illustrate in above-mentioned formula (III-I).The polymerization reaction of melamine compound and carbonyls is identical as the synthetic method of common melamine resin (such as melamino-formaldehyde resin).Also commercially available melamine polymer (melamine resin) can be used.The molecular weight of melamine polymer is preferably 2,000~400,000.

R⁷¹、R⁷²、R⁷³、R⁷⁴、R⁷⁵And R⁷⁶At least-it is a preferably comprise carbon atom number be 9~30 alkylene moiety or alkenylene moieties.The alkylene moiety or alkenylene moieties that carbon atom number is 9~30 are preferably straight-chain.Alkylene moiety or alkenylene moieties preferably are contained in the substituent group of aryl.In addition, R⁷¹、R⁷²、R⁷³、R⁷⁴、R⁷⁵And R⁷⁶At least-it is a preferably have polymerism base as substituent group.In addition, polymerism base is preferably placed at R⁷¹、R⁷²、R⁷³、R⁷⁴、R⁷⁵And R⁷⁶End.By introducing polymerism base to melamine polymer, it can be made to be included in phase difference film (optical anisotropic layer) in the state that melamine polymer and discotic mesogenic molecule are polymerize.R with polymerism base as substituent group⁷¹、R⁷²、R⁷³、R⁷⁴、R⁷⁵And R⁷⁶It is identical as the group indicated with above-mentioned formula (Rp).Polymerism base can also introduce carbonyls (R⁷¹、R⁷²) and melamine compound (R⁷³、R⁷⁴、R⁷⁵、R⁷⁶)-side in.When melamine compound has polymerism base, it is preferable to use the compounds of chemical structure simple as formaldehyde for carbonyls.When carbonyls has polymerism base, it is preferable to use the compounds of chemical structure simple as (unsubstituted) melamine for melamine compound.

It shown below the example of the carbonyls with polymerism base.

[chemical formula 67]

(CO-1~11)

CO-1:R⁷²:-H；R⁸²:-O- (CH₂)₉- O-CO-CH=CH₂

CO-2:R⁷²:-H；R⁸¹、R⁸²:-O- (CH₂)₉- O-CO-CH=CH₂

CO-3:R⁷²:-H；R⁸²:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

CO-4:R⁷²:-H；R⁸¹、R⁸²:-O- (CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

CO-5:R⁷²:-H；R⁸¹、R⁸³:-O- (CH₂)₉- O-CO-CH=CH₂

CO-6:R⁷²:-H；R⁸¹、R⁸²、R⁸³:-O- (CH₂)₉- O-CO-CH=CH₂

CO-7:R⁷²:-CH₃；R⁸²:-O- (CH₂)₉- O-CO-CH=CH₂

CO-8:R⁷²:-(CH₂)₁₁-CH₃；R⁸²:-O- (CH₂)₄- O-CO-CH=CH₂

CO-9:R⁷²:-(CH₂)₉- O-CO-CH=CH₂；R⁸²:-O- (CH₂)₄- O-CO-CH=CH₂

CO-10:R⁷²:-(CH₂)₉-O-CO-EpEt；R⁸²:-O- (CH₂)₄- O-CO-CH=CH₂

CO-11:R⁷²:-(CH₂)₄- O-CO-CH=CH；R⁸¹、R⁸³:-O- (CH₂)₁₂-CH₃

[chemical formula 68]

(CO-12~13)

CO-12:R⁸¹、R⁸²、R⁸³、R⁸⁴:-O- (CH₂)₆- O-CO-CH=CH₂

CO-13:R⁸²、R⁸³:-O- (CH₂)₉- O-CO-CH=CH₂

[chemical formula 69]

(CO-14~26)

CO-14:R⁷¹:-(CH₂)₉- O-CO-CH=CH₂；R⁷²:-H

CO-15:R⁷¹:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R⁷²:-H

CO-16:R⁷¹:-(CH₂)₉- O-CO-CH=CH₂；R⁷²:-CH₃

CO-17:R⁷¹:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R⁷²:-CH₃

CO-18:R⁷¹:-(CH₂)₉- O-CO-CH=CH₂；R⁷²:-Ph

CO-19:R⁷¹:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂；R⁷²:-Ph

CO-20:R⁷¹:-(CH₂)₄- O-CO-CH=CH₂；R⁷²:-(CH₂)₉- O-CO-CH=CH₂

CO-21:R⁷¹:-(CH₂)₄- O-CO-CH=CH₂；R⁷²:-(CH₂)₁₂-CH₃

CO-22:R⁷¹:-(CH₂)₉-O-EpEt；R⁷²:-H

CO-23:R⁷¹:-(CH₂)₄- CH=CH- (CH₂)₄-O-EpEt；R⁷²:-H

CO-24:R⁷¹、R⁷²:-(CH₂)₉-O-EpEt

CO-25:R⁷¹、R⁷²:-(CH₂)₉- O-CO-CH=CH₂

CO-26:R⁷¹、R⁷²:-(CH₂)₄- CH=CH- (CH₂)₄- O-CO-CH=CH₂

Ph indicates phenyl (same as below).

It shown below the example for the melamine polymer that there is polymerism base in melamine compound side.

[chemical formula 70]

(MP-1~14)

MP-1:R⁷³、R⁷⁵、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₈-CH₃

MP-2:R⁷¹:-CH₃；R⁷³、R⁷⁵、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₈-CH₃

MP-3:R⁷¹、R⁷²:-CH₃；R⁷³、R⁷⁵、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₈-CH₃

MP-4:R⁷¹:-Ph；R⁷³、R⁷⁵、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₈-CH₃

MP-5:R⁷³、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁵:-CH₂-O-CH₃

MP-6:R⁷³、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-NH-CO-(CH₂)₇- CH=CH- (CH₂ ) ₇ -CH ₃ ；R⁷⁵:-CH₂-OH

MP-7:R⁷³、R⁷⁶:-CH₂-NH-CO-C₂H₅；R⁷⁴:-CH₂-NH-CO-(CH₂)₁₆-CH₃；R⁷⁵:-CH₂-O-CH₃

MP-8:R⁷³、R⁷⁶:-CH₂-NH-CO-C₂H₅；R⁷⁴:-CH₂-NH-CO-(CH₂)₁₆-CH₃；R⁷⁵:-CH₂-OH

MP-9:R⁷³、R⁷⁶:-CH₂- O-CO-CH=CH₂；R⁷⁴:-CH₂-O-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁵:-CH₂-O-CH₃

MP-10:R⁷³、R⁷⁶:-CH₂- O-CO-CH=CH₂；R⁷⁴:-CH₂-O-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁵:-CH₂-OH

MP-11:R⁷³、R⁷⁶:-CH₂-O-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁴:-CH₂-NH-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁵:-CH₂-O-CH₃

MP-12:R⁷³、R⁷⁶:-CH₂-O-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁴:-CH₂-NH-CO-(CH₂)₇- CH=CH- (CH₂)₇-CH₃；R⁷⁵:-CH₂-OH

MP-13:R⁷³、R⁷⁴、R⁷⁵、R⁷⁶:-CH₂-O-(CH₂)₁₁- O-CO-CH=CH₂

MP-14:R⁷³、R⁷⁵、R⁷⁶:-CH₂- NH-CO-CH=CH₂；R⁷⁴:-CH₂-O-(CH₂)₁₆-CH₃

(fluorine-containing surfactant)

Polymerizable liquid crystal layer of the invention can keep liquid crystal compounds stable and be uniformly directed by the way that fluorine-containing surfactant is added.

The linking group that fluorine-containing surfactant of the invention is arranged by the hydrophobicity base containing fluorine atom, nonionic, anionic property, cationic or the hydrophily of both sexes base and arbitrarily forms.It is indicated by the fluorine-containing surfactant that a hydrophobicity base and a hydrophily base form with following formula (II).

Formula (II)

Rf-L²³-Hy

In formula, Rf is the hydrocarbon residue for 1 valence being replaced by fluorine atoms；L²³It is the linking group of singly-bound or divalent；Moreover, Hy is hydrophily base.The Rf of formula (II) plays hydrophobicity base.Hydrocarbon residue is preferably alkyl or aryl.The carbon atom number of alkyl is preferably 3~30, and the carbon atom number of aryl is preferably 6~30.Part or all of the hydrogen atom contained in hydrocarbon residue is replaced by fluorine atoms.It is preferred that more preferably replacing 60% or more with 50% or more of the hydrogen atom contained in fluorine atom substituted hydrocarbon residue, further preferably replaces 70% or more, most preferably replace 80% or more.Remaining hydrogen atom can also be replaced by other halogen atoms (such as chlorine atom, bromine atom) again.It shown below the example of Rf.

Rf¹: n-C₈F₁₇-

Rf²: n-C₆F₁₃-

Rf³: Cl- (CF₂-CFCl)₃-CF₂-

Rf⁴: H- (CF₂)₈-

Rf⁵: H- (CF₂)₁₀-

Rf⁶: n-C₉F₁₉-

Rf⁷: pentafluorophenyl group

Rf⁸: n-C₇F₁₅-

Rf⁹: Cl- (CF₂-CFCl)₂-CF₂-

Rf¹⁰: H- (CF₂)₄-

Rf¹¹: H- (CF₂)₆-

Rf¹²: Cl- (CF₂)₆-

Rf¹³: C₃F₇-

In formula (II), the linking group of divalent is preferably selected from alkylidene, arlydene, the heterocycle residue of divalent ,-CO- ,-NR²²²-(R²²²Be carbon atom number be 1~5 alkyl or hydrogen atom) ,-O- ,-SO₂And the divalent linking group of their combination.It shown below the L of formula (II)²³Example.Left side and hydrophobicity base (Rf) are combined, and right side and hydrophily base (Hy) are combined.AL refers to that alkylidene, AR refer to that arlydene, Hc refer to the heterocycle residue of divalent.In addition, the heterocycle residue of alkylidene, arlydene and divalent also can have substituent group (such as alkyl).

L³⁰: singly-bound

L³¹:-SO₂-NR-

L³²:-AL-O-

L³³:-CO-NR-

L³⁴:-AR-O-

L³⁵:-SO₂-NR-AL-CO-O-

L³⁶:-CO-O-

L³⁷:-SO₂-NR-AL-O-

L³⁸:-SO₂-NR-AL-

L³⁹:-CO-NR-AL-

L⁴⁰:-AL¹-O-AL²-

L⁴¹:-Hc-AL-

L⁴²:-SO₂-NR-AL¹-O-AL²-

L⁴³:-AR-

L⁴⁴:-O-AR-SO₂-NR-AL-

L⁴⁵:-O-AR-SO₂-NR-

L⁴⁶:-O-AR-O-

The Hy of formula (II) is any one of non-ionic hydrophilic nature base, anionic hydrophilic base, cationic hydrophily base or a combination thereof (both sexes hydrophily base).Non-ionic hydrophilic nature base is particularly preferred.It shown below the example of the Hy of formula (II).

Hy¹:-(CH₂CH₂O)_n- H (n is 5~30 integer)

Hy²:-(CH₂CH₂O)_n-R¹(n is 5~30 integer, R¹It is the alkyl that carbon atom number is 1~6)

Hy³:-(CH₂CHOHCH₂)_n- H (n is 5~30 integer)

Hy⁴:-COOM (M is hydrogen atom, alkali metal atom or dissociated state)

Hy⁵:-SO₃M (M is hydrogen atom, alkali metal atom or dissociated state)

Hy⁶:-(CH₂CH₂O)_n-CH₂CH₂CH₂-SO₃M (integer that n is 5~30, M are hydrogen atom or alkali metal atom)

Hy⁷:-OPO (OH)₂Hy⁸:-N⁺(CH₃)₃·X^-(X is halogen atom)

Hy⁹:-COONH₄

It is preferred that non-ionic hydrophilic nature base (Hy¹、Hy²、Hy³, the hydrophily base (Hy that is most preferably made of polyethylene oxide¹).More than reference Rf, L²³The specific example of the fluorine-containing surfactant indicated with formula (II) is indicated with the example of Hy.

FS-1:Rf¹-L³¹(R=C₃H₇)-Hy¹(n=6)

FS-2:Rf¹-L³¹(R=C₃H₇)-Hy¹(n=11)

FS-3:Rf¹-L³¹(R=C₃H₇)-Hy¹(n=16)

FS-4:Rf¹-L³¹(R=C₃H₇)-Hy¹(n=21)

FS-5:Rf¹-L³¹(R=C₂H₅)-Hy¹(n=6)

FS-6:Rf¹-L³¹(R=C₂H₅)-Hy¹(n=11)

FS-7:Rf¹-L³¹(R=C₂H₅)-Hy¹(n=16)

FS-8:Rf¹-L³¹(R=C₂H₇)-Hy¹(n=21)

FS-9:Rf²-L³¹(R=C₃H₇)-Hy¹(n=6)

FS-10:Rf²-L³¹(R=C₃H₇)-Hy¹(n=11)

FS-11:Rf²-L³¹(R=C₃H₇)-Hy¹(n=16)

FS-12:Rf²-L³¹(R=C₃H₇)-Hy¹(n=21)

FS-13:Rf³-L³²(AL=CH₂)-Hy¹(n=5)

FS-14:Rf³-L³²(AL=CH₂)-Hy¹(n=10)

FS-15:Rf³-L³²(AL=CH₂)-Hy¹(n=15)

FS-16:Rf³-L³²(AL=CH₂)-Hy¹(n=20)

FS-17:Rf⁴-L³³(R=C₃H₇)-Hy¹(n=7)

FS-18:Rf⁴-L³³(R=C₃H₇)-Hy¹(n=13)

FS-19:Rf⁴-L³³(R=C₃H₇)-Hy¹(n=19)

FS-20:Rf⁴-L³³(R=C₃H₇)-Hy¹(n=25)

FS-21:Rf⁵-L³²(AL=CH₂)-Hy¹(n=11)

FS-22:Rf⁵-L³²(AL=CH₂)-Hy¹(n=15)

FS-23:Rf⁵-L³²(AL=CH₂)-Hy¹(n=20)

FS-24:Rf⁵-L³²(AL=CH₂)-Hy¹(n=30)

FS-25:Rf⁶-L³⁴(AR=p- phenylene)-Hy¹(n=11)

FS-26:Rf⁶-L³⁴(AR=p- phenylene)-Hy¹(n=17)

FS-27:Rf⁶-L³⁴(AR=p- phenylene)-Hy¹(n=23)

FS-28:Rf⁶-L³⁴(AR=p- phenylene)-Hy¹(n=29)

FS-29:Rf¹-L³⁵(R=C₃H₇, AL=CH₂)-Hy¹(n=20)

FS-30:Rf¹-L³⁵(R=C₃H₇, AL=CH₂)-Hy¹(n=30)

FS-31:Rf¹-L³⁵(R=C₃H₇, AL=CH₂)-Hy¹(n=40)

FS-32:Rf¹-L³⁶-Hy¹(n=5)

FS-33:Rf¹-L³⁶-Hy¹(n=10)

FS-34:Rf¹-L³⁶-Hy¹(n=15)

FS-35:Rf¹-L³⁶-Hy¹(n=20)

FS-36:Rf⁷-L³⁶-Hy¹(n=8)

FS-37:Rf⁷-L³⁶-Hy¹(n=13)

FS-38:Rf⁷-L³⁶-Hy¹(n=18)

FS-39:Rf⁷-L³⁶-Hy¹(n=25)

FS-40:Rf¹-L0-Hy¹(n=6)

FS-41:Rf¹-L0-Hy¹(n=11)

FS-42:Rf¹-L0-Hy¹(n=16)

FS-43:Rf¹-L0-Hy¹(n=21)

FS-44:Rf¹-L³¹(R=C₃H₇)-Hy²(n=7, R¹=C₂H₅)

FS-45:Rf¹-L³¹(R=C₃H₇)-Hy²(n=13, R¹=C₂H₅)

FS-46:Rf¹-L³¹(R=C₃H₇)-Hy²(n=20, R¹=C₂H₅)

FS-47:Rf¹-L³¹(R=C₃H₇)-Hy²(n=28, R¹=C₂H₅)

FS-48:Rf⁸-L³²(AL=CH₂)-Hy¹(n=5)

FS-49:Rf⁸-L³²(AL=CH₂)-Hy¹(n=10)

FS-50:Rf⁸-L³²(AL=CH₂)-Hy¹(n=15)

FS-51:Rf⁸-L³²(AL=CH₂)-Hy¹(n=20)

FS-52:Rf¹-L³⁷(R=C₃H₇, AL=CH₂CH₂)-Hy³(n=5)

FS-53:Rf¹-L³⁷(R=C₃H₇, AL=CH₂CH₂)-Hy³(n=7)

FS-54:Rf¹-L³⁷(R=C₃H₇, AL=CH₂CH₂)-Hy³(n=9)

FS-55:Rf¹-L³⁷(R=C₃H₇, AL=CH₂CH₂)-Hy³(n=12)

FS-56:Rf⁹-L0-Hy⁴(M=H)

FS-57:Rf³- L0-Hy4 (M=H)

FS-58:Rf¹-L³⁸(R=C₃H₇, AL=CH₂)-Hy4 (M=K)

FS-59:Rf⁴-L³⁹(R=C₃H₇, AL=CH₂)-Hy⁴(M=Na)

FS-60:Rf¹-L0-Hy⁵(M=K)

FS-61:Rf¹⁰-L⁴⁰(AL¹=CH₂、AL²=CH₂CH₂)-Hy⁵(M=Na)

FS-62:Rf¹¹-L⁴⁰(AL¹=CH₂、AL²=CH₂CH₂)-Hy⁵(M=Na)

FS-63:Rf⁵-L⁴⁰(AL¹=CH₂、AL²=CH₂CH₂)-Hy⁵(M=Na)

FS-64:Rf¹-L³⁸(R=C₃H₇, AL=CH₂CH₂CH₂)-Hy⁵(M=Na)

FS-65:Rf¹-L³¹(R=C₃H₇)-Hy⁶(n=5, M=Na)

FS-66:Rf¹-L³¹(R=C₃H₇)-Hy⁶(n=10, M=Na)

FS-67:Rf¹-L³¹(R=C₃H₇)-Hy⁶(n=15, M=Na)

FS-68:Rf¹-L³¹(R=C₃H₇)-Hy⁶(n=20, M=Na)

FS-69:Rf¹-L³⁸(R=C₂H₅, AL=CH₂CH₂)-Hy⁷

FS-70:Rf¹-L³⁸(R=H, AL=CH₂CH₂CH₂)-Hy⁸(X=I)

FS-71:Rf¹¹-L⁴¹(following Hc, AL=CH₂CH₂CH₂)-Hy⁶(M is dissociation)

[chemical formula 71]

The Hc of FS-71

FS-72:Rf¹-L⁴²(R=C₃H₇、AL¹=CH₂CH₂、AL²=CH₂CH₂CH₂)-Hy6 (M=Na)

FS-73:Rf¹²-L0-Hy⁵(M=Na)

FS-74:Rf¹³-L⁴³(AR=o- phenylene)-Hy⁶(M=K)

FS-75:Rf¹³-L⁴³(AR=m- phenylene)-Hy⁶(M=K)

FS-76:Rf¹³-L⁴³(AR=p- phenylene)-Hy⁶(M=K)

FS-77:Rf⁶-L⁴⁴(R=C₂H₅, AL=CH₂CH₂)-Hy⁵(M=H)

FS-78:Rf⁶-L⁴⁵(AR=p- phenylene, R=C₂H₅)-Hy¹(n=9)

FS-79:Rf⁶-L⁴⁵(AR=p- phenylene, R=C₂H₅)-Hy¹(n=14)

FS-80:Rf⁶-L⁴⁵(AR=p- phenylene, R=C₂H₅)-Hy¹(n=19)

FS-81:Rf⁶-L⁴⁵(AR=p- phenylene, R=C₂H₅)-Hy¹(n=28)

FS-82:Rf⁶-L⁴⁶(AR=p- phenylene)-Hy¹(n=5)

FS-83:Rf⁶-L⁴⁶(AR=p- phenylene)-Hy¹(n=10)

FS-84:Rf⁶-L⁴⁶(AR=p- phenylene)-Hy¹(n=15)

FS-85:Rf⁶-L⁴⁶(AR=p- phenylene)-Hy¹(n=20)

Also the fluorine-containing surfactant with more than two hydrophobicity bases containing fluorine atom or hydrophily base can be used.It shown below the example of the fluorine-containing surfactant with more than two hydrophobicity bases or hydrophily base.

[chemical formula 72]

(FS-86~88)

FS-86:n1+n2=12,

FS-87:n1+n2=18,

FS-88:n1+n2=24

[chemical formula 73]

(FS-89~91)

FS-89:n1+n2=20,

FS-90:n1+n2=30,

FS-91:n1+n2=40

[chemical formula 74]

(FS-92~95)

FS-92:n=5,

FS-93:n=10,

FS-94:n=15,

FS-95:n=20

[chemical formula 75]

(FS-96)

Also two kinds or more of fluorine-containing surfactant can be used together.For surfactant, various documents (such as, great write " new surface active agents " three of hole mouth publish (1975), M.J.Schick altogether, Nonionic Surfactants, Marcell Dekker Inc., New York, (1967), Japanese Laid-Open Patent Publication 7-13293 bulletin) in it is on the books.Fluorine-containing surfactant is used with the amount of 2~30 mass % of the amount of liquid crystal compounds.Usage amount is preferably 3~25 mass % of the amount of liquid crystal compounds, more preferably 5~10 mass %.

Also two kinds or more of the compound (including melamine compound and melamine polymer) with 1,3,5-triazines ring can be used together.Compound with 1,3,5-triazines ring is used with the amount of 0.01~20 mass % of the amount of liquid crystal compounds.Usage amount is preferably 0.1~15 mass % of the amount of liquid crystal compounds, more preferably 0.5~10 mass %.

Polymerizable liquid crystal layer is by carrying out coating formation in biaxial films or alignment films of the invention.The solvent used when as modulation coating liquid is, it is preferable to use organic solvent.Example as organic solvent, including amide (such as dimethylformamide), sulfoxide (such as dimethyl sulfoxide), heterocyclic compound (such as pyridine), hydrocarbon (such as benzene, hexane), alkyl halide (such as chloroform, methylene chloride), ester (such as methyl acetate, butyl acetate), ketone (such as acetone, methyl ethyl ketone), ether (such as tetrahydrofuran, 1,2- dimethoxy-ethane).Optimizing alkyl halide and ketone.Also two kinds or more of organic solvent can be used together.Coating liquid can be carried out with well known method (such as curtain coating, extrusion coating process, rolling method, spin-coating method, dip coating, printing coating process, spray coating method, ramp type coating process).It is preferred that forming optical anisotropic layer by continuously coating.Curtain coating, rolling method and ramp type coating process (slide coating) are suitable for continuously coating.

The thickness of polymerizable liquid crystal layer is preferably 0.5~100 μm, and more preferable 0.5~30 μm.

(alignment films)

Alignment films have the function of determining the differently- oriented directivity of liquid crystal compounds.

Alignment films can be configured by the friction treatments of such as organic compound (preferred polymers), the rectangle vapor deposition of inorganic compound, the formation of layer with fine groove or with the accumulation means of ラ Application グ ミ ユ ア-Block ロ ニ エ Star ト method (LB film) organic compound (such as ω-tricosanic acid, octacosane methyl ammonium, methyl stearate).In addition, it is also known that by assigning electric field, assigning magnetic field or light irradiation, generate the alignment films of orientation function.

The friction treatment that alignment films preferably pass through polymer is formed.Friction treatment is preferably actually carried out along the direction vertical with the slow phase axis of biaxial films.It is possible thereby to make biaxial films slow phase axis and phase difference film slow phase axis it is vertical.

By make biaxial films slow phase axis and phase difference film slow phase axis it is vertical, the Re of the Re and phase difference film that can obtain this biaxial films are offset, and can easily be accommodated the effect of the wavelength dispersion of the Re of optical compensating sheet.

The preferred polyvinyl alcohol of polymer.Particularly preferably combine the modified polyvinylalcohol of hydrophobicity base.Hydrophobicity base is due to affinity with the liquid crystal compounds of phase difference film, it is possible to by the way that hydrophobicity base is introduced polyvinyl alcohol, be uniformly directed liquid crystal compounds.Hydrophobicity base is in conjunction with the main chain terminal of polyvinyl alcohol or side chain.

Hydrophobicity base is preferably the fatty group (optimizing alkyl or alkenyl) or aromatic series base that carbon atom number is 6 or more.

When the main chain terminal combination hydrophobicity base in polyvinyl alcohol, linking group preferably is introduced between hydrophobicity base and main chain terminal.As the example of linking group, including-S- ,-C (CN) R⁴⁴⁴-、-NR⁵⁵⁵,-CS- and combinations thereof.Above-mentioned R⁴⁴⁴And R⁵⁵⁵It is hydrogen atom respectively or alkyl that carbon atom number is 1~6 (preferably carbon atom number be 1~6 alkyl).

When the side chain of polyvinyl alcohol introduces hydrophobicity base, the acyl group (- CO-R that can be 7 or more with carbon atom number⁶⁶⁶) displacement polyvinyl alcohol vinyl acetate units acetyl group (- CO-CH₃) a part.R⁶⁶⁶It is the fatty group or aromatic series base that carbon atom number is 6 or more.

Also commercially available modified polyvinylalcohol (such as MP103, MP203, R1130, Network ラ レ (strain) system) can be used.

The saponification degree of (modification) polyvinyl alcohol for alignment films is preferably 80% or more.The degree of polymerization of (modification) polyvinyl alcohol is preferably 200 or more.

Friction treatment is carried out by being rubbed in a certain direction for several times on the surface of alignment films with paper and cloth.It is preferable to use the cloth that the uniform fiber of length and thickness is carried out to uniform flocking.

In addition, making the liquid crystal compounds of polymerizable liquid crystal layer after being orientated orientation on membranes, even if removing alignment films, the state of orientation of liquid crystal compounds can also be kept.That is, since alignment films are orientated liquid crystal compounds, so need to manufacture optical compensating sheet, but the optical compensating sheet manufactured is not required.

When alignment films are arranged between biaxial films and polymerizable liquid crystal layer, bonding layer (priming coat) in addition can also be set between transparent supporting body and alignment films.

Phase difference film of the invention can also adjust the average slope angle of liquid crystal compounds by the inclusion of the oriented layer for the modified polyvinylalcohol that special open 2000-155216 bulletin is recorded.

(biaxial films)

The thickness of biaxial films of the invention is preferably 10~200 μm, more preferably 20~150 μm, most preferably 30~100 μm.

The substance that biaxial films of the invention are preferably formed polymer thin film stretching.As polymer can it is preferable to use norbornene-based polymer, polycarbonate, acylated celluloses.Wherein, orbornene-based film and acylated cellulose film are made of aliphatic structure due to main chain, and because wavelength dispersion caused by main chain is small, so particularly preferably.

As norbornene-based polymer can it is preferable to use special open 2004-020823, special open 2004-309979, special open 2005-008698 each bulletin in the polymer recorded etc..

In the following, in biaxial films of the invention it is preferable to use acylated cellulose film (hereinafter referred to as " twin shaft acylated cellulose film ") be described in detail.

(acylated cellulose)

The degree of substitution of the acylated cellulose of twin shaft acylated cellulose film of the invention refers to, be present in the structural unit (glucose that β 1 → 4- glucosides combines) of cellulose, three hydroxyls carry out acylated ratio.Degree of substitution (acylation degree) can be calculated with method identical with above-mentioned low latency film.

The cellulose ethanoate that the preferred acylation degree of acylated cellulose of the invention is 2.00~2.90.More preferable acylation degree is 2.2~2.8.Furthermore 6 acylation degrees are preferably 0.25 or more relative to the ratio of total acylation degree, and more preferably 0.3 or more.

In addition, it is 2~2.9 that another currently preferred acylated cellulose, which is acylation degree, the mixed aliphatic ester with the acyl group that acetyl group and carbon number are 3~4.More preferable acylation degree is 2.2~2.85, most preferably 2.4~2.8.In addition, degree of acetylation is preferably 2.5 hereinafter, more preferably 1.9 or less.Furthermore 6 acylation degrees are preferably 0.25 or more relative to the ratio of total acylation degree, and more preferably 0.3 or more.

In addition, as acylated cellulose of the invention, further preferably with the mixed ester of acetyl group and the acyl group indicated with the following general formula (B).

[chemical formula 76]

General formula (B)

Firstly, being illustrated to above-mentioned general formula (B).In general formula (B), X indicates substituent group.As the example of above-mentioned substituent group, including halogen atom, cyano, alkyl, alkoxy, aryl, aryloxy group, acyl group, carbonamido, sulfoamido, uride base, aralkyl, nitro, alkoxy carbonyl, aryloxycarbonyl, aralkyloxycarbonyl, carbamoyl, sulfamoyl, acyloxy, alkenyl, alkynyl, alkyl sulphonyl, aryl sulfonyl, alkyloxysulfonyl, aryloxy sulfonyl, alkylsulfonyloxy and aryloxy sulfonyl ,-S-R ,-NH-CO-OR ,-PH-R ,-P (- R)₂、-PH-O-R、-P(-R)(-O-R)、-P(-O-R)₂,-PH (=O)-R-P (=O) (- R)₂,-PH (=O)-O-R ,-P (=O) (- R) (- O-R) ,-P (=O) (- O-R)₂,-O-PH (=O)-R ,-O-P (=O) (- R)₂- O-PH (=O)-O-R ,-O-P (=O) (- R) (- O-R) ,-O-P (=O) (- O-R)₂,-NH-PH (=O)-R ,-NH-P (=O) (- R) (- O-R) ,-NH-P (=O) (- O-R)₂、-SiH₂-R、-SiH(-R)₂、-Si(-R)₃、-O-SiH₂-R、-O-SiH(-R)₂With-O-Si (- R)₃.Above-mentioned R is fatty group, aromatic series base or heterocycle.

In above-mentioned general formula (B), n is the quantity of substituent group, indicates 0~5 integer.The quantity (n) of above-mentioned substituent group is preferably 1~5, and more preferably 1~4, further preferably 1~3, most preferably 1 or 2.As substituent group shown in above-mentioned; it is preferred that halogen atom, cyano, alkyl, alkoxy, aryl, aryloxy group, acyl group, carbonamido, sulfoamido and uride base; more preferable halogen atom, cyano, alkyl, alkoxy, aryloxy group, acyl group and carbonamido; further preferred halogen atom, cyano, alkyl, alkoxy and aryloxy group, most preferably halogen atom, alkyl and alkoxy.

As above-mentioned halogen atom, including fluorine atom, chlorine atom, bromine atom and iodine atom.Abovementioned alkyl also can have cyclic structure or branch.The carbon atom number of alkyl is preferably 1~20, and more preferably 1~12, further preferably 1~6, most preferably 1~4.As the example of alkyl, including methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, octyl and 2- ethylhexyl.Above-mentioned alkoxy also can have cyclic structure or branch.The carbon atom number of alkoxy is preferably 1~20, and more preferably 1~12, further preferably 1~6, most preferably 1~4.Alkoxy can also be replaced by other alkoxies again.As the example of alkoxy, including methoxyl group, ethyoxyl, 2- methoxy ethoxy, 2- methoxyl group -2- ethoxy ethoxy, butoxy, hexyloxy and octyloxy.

The carbon atom number of above-mentioned aryl is preferably 6~20, and more preferably 6~12.As the example of aryl, including phenyl and naphthalene.The carbon atom number of above-mentioned aryloxy group is preferably 6~20, and more preferably 6~12.As the example of aryloxy group, including phenoxy group and naphthoxy.The carbon atom number of above-mentioned acyl group is preferably 1~20, and more preferably 1~12.As the example of acyl group, including formoxyl, acetyl group and benzoyl.The carbon atom number of above-mentioned carbonamido is preferably 1~20, and more preferably 1~12.As the example of carbonamido, including acetamido and benzamido.The carbon atom number of above-mentioned sulfoamido is preferably 1~20, and more preferably 1~12.As the example of sulfoamido, including methylsulfonyl amido, benzene sulfonamido and p- tosyl amido.The carbon atom number of above-mentioned uride base is preferably 1~20, and more preferably 1~12.As the example of uride base, including (unsubstituted) uride.

The carbon atom number of above-mentioned aralkyl is preferably 7~20, and more preferably 7~12.As the example of aralkyl, including benzyl, phenethyl and menaphthyl.The carbon atom number of above-mentioned alkoxy carbonyl is preferably 2~20, and more preferably 2~12.As the example of alkoxy carbonyl, including methoxycarbonyl.The carbon atom number of above-mentioned aryloxycarbonyl is preferably 7~20, and more preferably 7~12.As the example of aryloxycarbonyl, including phenyloxycarbonyl.The carbon atom number of above-mentioned aromatic alkoxy carbonyl is preferably 8~20, and more preferably 8~12.As the example of aromatic alkoxy carbonyl, including benzyloxycarbonyl.The carbon atom number of above-mentioned carbamoyl is preferably 1~20, and more preferably 1~12.As the example of carbamoyl, including (unsubstituted) carbamoyl and N- methylcarbamoyl.The carbon atom number of above-mentioned sulfamoyl is preferably 20 hereinafter, more preferably 12 or less.As the example of sulfamoyl, including (unsubstituted) sulfamoyl and N- Methylsulfamoyl.The carbon atom number of above-mentioned acyloxy is preferably 1~20, and more preferably 2~12.As the example of acyloxy, including acetoxyl group and benzoyloxy.

The carbon atom number of above-mentioned alkenyl is preferably 2~20, and more preferably 2~12.As the example of alkenyl, including vinyl, allyl and isopropenyl.The carbon atom number of above-mentioned alkynyl is preferably 2~20, and more preferably 2~12.As the example of alkynyl, including thianthrene group.The carbon atom number of abovementioned alkyl sulfonyl is preferably 1~20, and more preferably 1~12.The carbon atom number of above-mentioned aryl sulfonyl is preferably 6~20, and more preferably 6~12.The carbon atom number of above-mentioned alkyloxysulfonyl is preferably 1~20, and more preferably 1~12.The carbon atom number of above-mentioned aryloxy sulfonyl is preferably 6~20, and more preferably 6~12.The carbon atom number of abovementioned alkyl sulfonyloxy is preferably 1~20, and more preferably 1~12.The carbon atom number of above-mentioned aryloxy sulfonyl is preferably 6~20, and more preferably 6~12.

In addition, the quantity (n) of the substituent X replaced in aromatic ring in general formula (B) is 0 or 1~5, preferably 1~3, particularly preferably 1 or 2.

In addition, when the number of the substituent group replaced in aromatic ring is 2 or more, the substituent group can be the same or different each other, can also be by being interconnected to form condensation polycyclic compound (such as naphthalene, indenyl, indanyl, phenanthryl, quinolyl, isoquinolyl, chromene base, Chromanyl, phthalazinyl, bifurcation piperidinyl, indyl, indolinyl etc.).The specific example of the aromatic acyl indicated with general formula (B) is for example following shown.

[chemical formula 77]

[chemical formula 78]

[chemical formula 79]

[chemical formula 80]

Total acyl substitution of mixed ester with acetyl group and the acyl group indicated with Formula B is preferably 2.0~2.90, and more preferably 2.2~2.70.The degree of substitution of the substituent group indicated with Formula B is preferably 0.1~1.0, and more preferably 0.3~0.9.

The degree of substitution of the substituent group indicated with Formula B respectively provides 2,3 and 6 degree of substitution for DS_B2、DS_B3、DS_B6, preferably satisfy DS_B6/(DS_B2+DS_B3+DS_B6)≤0.60.More preferable DS_B6/(DS_B2+DS_B3+DS_B6)≤0.70, most preferably DS_B6/(DS_B2+DS_B3+DS_B6)≤0.80。

The acylated cellulose of twin shaft acylated cellulose film of the invention can be prepared with method identical with the acylated cellulose of above-mentioned low latency film.

Particularly as the method for obtaining cellulose mixing acylate, mixing can be used or the method that two kinds of carboxylic acid anhydrides react it as acylating agent is gradually added；Use the method for the mixed acid anhydride (such as acetic acid, propionic acid mixed acid anhydride) of two kinds of carboxylic acids；The method that the acid anhydrides (such as acetic acid and propionic andydride) of carboxylic acid and other carboxylic acid is synthesized mixed acid anhydride (such as acetic acid, propionic acid mixed acid anhydride) as raw material in the reaction system and reacts it with cellulose；After synthesizing acylated cellulose of the degree of substitution less than 3, using acid anhydrides and acyl halide, then make the method etc. of remaining acylated hydroxy.

The acylated cellulose of twin shaft acylated cellulose film of the invention preferably has 100~800 matter homopolymerization right, and the more preferably matter homopolymerization with 200~550 is right.In addition acylated cellulose of the invention preferably has 70000~230000 number-average molecular weight, more preferably has 75000~230000 number-average molecular weight, most preferably has 78000~120000 number-average molecular weight.

In addition, cellulose bodies used in the present invention are preferably according to the narrow molecular weight distribution of the Mw/Mn of gel permeation chromatography (it is number-average molecular weight that Mw, which is weight average molecular weight, Mn).As the value of specific Mw/Mn, preferably 1.0~5.0, more preferably 1.5~3.5, most preferably 2.0~3.0.

Furthermore the ratio (Mw/Mn) of weight average molecular weight (Mw) and number-average molecular weight (Mn) is preferably 2.0-5.0, more preferably 2.0-4.0.

Twin shaft acylated cellulose film of the invention preferably comprises delay visualization reagent.Delay visualization reagent of the invention is described in detail below.

From the perspective of delay visualization reagent of the invention never causes the unwanted coloring of film, preferably the molar absorption coefficient of 360nm-750nm wave-length coverage is 1000 below.The molar absorption coefficient of more preferable 330nm-750nm wave-length coverage is 1000 below.

Molar absorption coefficient can be used commercially available spectrophotometer (such as (strain) Shimadzu Seisakusho Ltd. UV3400 etc.) and measure.

Delay visualization reagent of the compound indicated with the following general formula (1) particularly preferable as twin shaft acylated cellulose film of the invention.

General formula (1): Ar¹-L¹-Ar²

In above-mentioned general formula (1), Ar¹And Ar²It is separately aromatic series base.

In this specification, aromatic series base includes aryl (aromatic series alkyl), substituted aryl, aromatic series heterocycle and substituted aromatic heterocycle.

Aryl and substituted aryl are more preferable compared with aromatic series heterocycle and substituted aromatic heterocycle.The heterocycle of aromatic series heterocycle is usually unsaturated.Aromatic series heterocycle is preferably 5 member rings, 6 member rings or 7 member rings, more preferable 5 member ring or 6 member rings.Aromatic series heterocycle generally has most double bonds.As hetero atom, preferably nitrogen-atoms, oxygen atom or sulphur atom, more preferable nitrogen-atoms or sulphur atom.

As the aromatic ring of aromatic series base, preferably phenyl ring, furan nucleus, thiphene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring and pyridine ring, particularly preferred phenyl ring.

Example as substituted aryl and the substituent group of substituted aromatic heterocycle, including halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkyl amino (such as methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo group, carbamoyl, alkyl-carbamoyl (such as N- methylcarbamoyl, N- ethylaminocarbonyl, N, N- formyl-dimethylamino), sulfamoyl, alkylsulfamoyl group (such as N- Methylsulfamoyl, N- ethylsulfamovl, N, N- DimethylsuIfamoyl), uride base, alkyl uride base (such as N- methyl uride base, N, N- dimethyl uride base, N, N, N '-trimethyl uride base), alkyl (such as methyl, ethyl, propyl, butyl, amyl, heptyl, octyl, it is different Propyl, s- butyl, tertiary pentyl, cyclohexyl, cyclopenta), alkenyl (such as, vinyl, allyl, hexenyl), alkynyl (such as acetenyl, butynyl), acyl group (such as formoxyl, acetyl group, bytyry, caproyl, lauroyl), acyloxy (such as acetoxyl group, butyryl acyloxy, hexylyloxy, laurel acyloxy), alkoxy (such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, heptan oxygroup, octyloxy), aryloxy group (such as phenoxy group), alkoxy carbonyl (such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl, pentyloxy carbonyl, heptan Epoxide carbonyl), aryloxycarbonyl (such as phenyloxycarbonyl), alkoxycarbonyl amino (such as butoxycarbonylamino group, hexyloxy carbonyl amino), alkylthio group (such as methyl mercapto, ethylmercapto group, Rosickyite base, butylthio, penta sulfenyl, sulfenyl in heptan, pungent sulfenyl), arylthio (such as thiophenyl), alkyl sulphonyl (such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl, pentylsulfonyl, heptyl sulfonyl, octyl sulfonyl), amide groups (such as acetamido, amide-based small, hexanoyl amido, lauroyl amido) and non-aromatic heterocycle (such as morpholinyl, pyrazinyl).

As the substituent group of substituted aryl and substituted aromatic heterocycle, preferably halogen atom, cyano, carboxyl, hydroxyl, amino, alkyl-substituted amino, acyl group, acyloxy, amide groups, alkoxy carbonyl, alkoxy, alkylthio group and alkyl.

Alkyl amino, alkoxy carbonyl, alkoxy and alkylthio group moieties and alkyl can also in addition have substituent group.As the example of moieties and the substituent group of alkyl, including halogen atom, hydroxyl, carboxyl, cyano, amino, alkyl amino, nitro, sulfo group, carbamoyl, alkyl-carbamoyl, sulfamoyl, alkylsulfamoyl group, uride, alkyl uride base, alkenyl, alkynyl, acyl group, acyloxy, acylamino-, alkoxy, aryloxy group, alkoxy carbonyl, aryloxycarbonyl, alkoxycarbonyl amino, alkylthio group, arylthio, alkyl sulphonyl, amide groups and non-aromatic heterocycle.As the substituent group of moieties and alkyl, preferably halogen atom, hydroxyl, amino, alkyl amino, acyl group, acyloxy, acylamino-, alkoxy carbonyl and alkoxy.

In general formula (1), L¹It is the linking group of the divalent selected from alkylidene, alkenylene, alkynylene ,-O- ,-CO- and combinations thereof.

Alkylidene also can have cyclic structure.As cyclic alkylidene, preferably cyclohexylene, particularly preferred Isosorbide-5-Nitrae-cyclohexylene.As chain alkylidene, straight-chain alkylidene is more preferable compared with the alkylidene with branch.

The carbon atom number of alkylidene is preferably 1~20, and more preferably 1~15, further preferably 1~10, further preferably 1~8, most preferably 1~6.

Alkenylene and alkynylene preferably have chain structure compared with cyclic structure, more preferably have straight chain structure compared with the chain structure with branch.

The carbon atom number of alkenylene and alkynylene is preferably 2~10, more preferably 2~8, further preferably 2~6, further preferably 2~4, most preferably 2 (ethenylidene or ethynylenes).

The preferred carbon atom number of arlydene is 6~20, more preferably 6~16, further preferably 6~12.

In the molecular structure of general formula (1), L is clamped¹When, Ar¹And Ar²Being formed by angle is preferably 140 degree or more.

As rod-shaped compound, the compound that is more preferably indicated with following formula general formula (2).

General formula (2): Ar¹-L²-X-L³-Ar²

In above-mentioned general formula (2), Ar¹And Ar²It is separately aromatic series base.The Ar of the definition of aromatic series base and example and general formula (1)¹And Ar²It is identical.

In general formula (2), L²And L³It is separately the linking group of the divalent selected from alkylidene ,-O- ,-CO- and combinations thereof.

Alkylidene preferably has chain structure compared with cyclic structure, more preferably has straight chain structure compared with the chain structure with branch.

The carbon atom number of alkylidene is preferably 1~10, and more preferably 1~8, further preferably 1~6, further preferably 1~4, most preferably 1 or 2 (methylene or ethylidene).

L²And L³Particularly preferably-O-CO- or-CO-O-.

In general formula (2), X is Isosorbide-5-Nitrae-cyclohexylene, ethenylidene or ethynylene.

In the following, showing the specific example of the compound indicated with general formula (1) or (2).

[chemical formula 81]

[chemical formula 82]

[chemical formula 83]

[chemical formula 84]

[chemical formula 85]

[chemical formula 86]

[chemical formula 87]

[chemical formula 88]

[chemical formula 89]

There are two asymmetric carbon atoms in 1 of cyclohexane ring and 4 tool for concrete example (1)~(34), (41), (42), but, concrete example (1), (4)~(34), (41), (42) are because of the molecular structure with symmetrical meso-form, so there is only geometric isomer (trans- type and cis types) without optical isomer (optical activity).It shown below the trans- (1- is trans-) and cis- (1- is cis-) of concrete example (1).

[chemical formula 90]

As described above, rod-shaped compound preferably has linearity molecular structure.Therefore, trans- ratio is cis- more preferably.

Concrete example (2) and (3) also have optical isomer (amounting to 4 kinds of isomers) in addition to geometric isomer.For geometric isomer, same trans- type is more more preferable than cis type.Any one of D, L or racemic modification can be without special superiority and inferiority for optical isomer.

In concrete example (43)~(45), there is trans- type and cis type in the ethenylidene key at center.According to reason same as described above, trans- type is more more preferable than cis type.

In addition, shown below preferred compound.

[chemical formula 91]

[chemical formula 92]

The rod-shaped compound that two kinds or more the maximum absorption wavelengths in the ultraviolet absorption spectrum of solution (λ max) are shorter than the wavelength of 250nm can be used together.

The method that rod-shaped compound can be recorded with document synthesizes.As document, Mol.Cryst.Liq.Cryst. can be enumerated, volume 53, page 229 (1979)；Mol.Cryst.Liq.Cryst., volume 89, page 93 (nineteen eighty-two)；Mol.Cryst.Liq.Cryst., volume 145, page 111 (1987)；Mol.Cryst.Liq.Cryst., volume 170, page 43 (1989)；J.Am.Chem.Soc., volume 113, page 1349 (1991)；J.Am.Chem.Soc., volume 118, page 5346 (1996)；J.Am.Chem.Soc., volume 92, page 1582 (1970)；J.Org.Chem., volume 40, page 420 (1975)；Tetrahedron, volume 48 16, page 3437 (1992).

The additional amount of delay visualization reagent of the invention is relative to 100 mass parts of acylated cellulose, preferably 1~30 mass %, more preferably 2~25 mass %.

The Adding Way of delay visualization reagent of the invention can be added after being dissolved in pure and mild methylene chloride, dioxolanes in organic solvent into cellulose acylate solutions (dope), or be directly added in dope composition.

(manufacture for stretching acylated cellulose film)

Twin shaft acylated cellulose film of the invention can be manufactured with solvent cast method.In solvent cast method, film is manufactured using the solution (dope) that cellulose dissolution is formed in organic solvent is acidylated.

Organic solvent preferably comprises solvent chosen from the followings: the halogenated hydrocarbons that the ester and carbon atom number that ketone that ether that carbon atom number is 3-12, carbon atom number are 3-12, carbon atom number are 3-12 are 1-6.

Ether, ketone and ester can have cyclic structure.Also it can be used with the above compound of any two in above-mentioned ether, ketone and ester functional group (it is ,-O- ,-CO- and-COO-) as organic solvent.Organic solvent can also have other functional groups as alcohol hydroxyl group.When for the organic solvent of two or more functional groups, carbon atom number is preferably in the above-mentioned preferred carbon atom number range of the solvent with any functional group.

Carbon atom number is that the example of the ethers of 3-12 includes: Di Iso Propyl Ether, dimethoxymethane, dimethoxy-ethane, Isosorbide-5-Nitrae-dioxanes, 1,3- dioxolane, tetrahydrofuran, methyl phenyl ethers anisole and phenetole.

Carbon atom number is that the example of the ketone of 3-12 includes: acetone, methyl ethyl ketone, metacetone, diisobutyl ketone, cyclohexanone and methyl cyclohexanone.

Carbon atom number is that the example of the esters of 3-12 includes: Ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate and pentyl acetate.

The example of organic solvent with two or more functional groups includes: 2- ethoxyethyl group acetate, 2-methyl cellosolve and butoxy ethanol.

The carbon atom number of halogenated hydrocarbons is preferably 1 or 2, most preferably 1.The halogen of halogenated hydrocarbons is preferably chlorine.The ratio that the hydrogen atom of halogenated hydrocarbons is optionally substituted by halogen is preferably 25-75 moles of %, more preferably 30-70 moles of %, further preferably 35-65 moles of %, most preferably 40-60 moles of %.Methylene chloride is representative halogenated hydrocarbons.

Two or more organic solvents can also be used in mixed way.

The conventional method modulation handled at 0 DEG C or more of temperature (room temperature or high temperature) can be used in cellulose acylate solutions.The method and apparatus of the modulation dope (dope) in common solvent cast method can be used to implement in the modulation of solution.In addition, it is preferable to use halogenated hydrocarbons (especially methylene chloride) is used as organic solvent when for common method.

The amount of acylated cellulose is adjusted so that acylated cellulose containing 10-40 mass % in resulting solution.The amount of acylated cellulose is more preferably 10-30 mass %.In organic solvent (main solvent), aftermentioned arbitrary additive can be added.

Solution is prepared by stirring acylated cellulose and organic solvent under room temperature (0-40 DEG C).The solution of high concentration can also be stirred under conditions of pressurization and heating.Specifically acylated cellulose and organic solvent are put into closed in pressurizing vessel, are heated in the temperature of the boiling point under the room temperature of solvent or more and solvent not boiling range, are stirred simultaneously under elevated pressure.Heating temperature is preferably 40 DEG C or more, more preferably 60-200 DEG C, further preferably 80-110 DEG C.

Each ingredient can be put into container after thick mixing in advance.Furthermore, it is also possible to successively put into container.Container must have the structure that can be stirred.It can pressurize after the inert gases such as injection nitrogen to container.Furthermore, it is possible to rise the vapour pressure of solvent by heating.Alternatively, adding each ingredient under stress after by container closure.

When heated, it is preferably heated from external container.Jacket type heating device can be used for example.Alternatively, it is also possible to heat liquid circulation integrally to container by piping by the way that baffle heater is arranged in external container.

It is preferred that stirring slurry is arranged inside container and is stirred using the stirring slurry.The length of stirring slurry is preferably the length reached near chamber wall.In order to update the liquid film of chamber wall, scraping paddle is preferably provided in the end of stirring slurry.

The metrical instruments class such as pressure gauge, thermometer can be set in a reservoir.Each ingredient in container dissolves in a solvent.The dope of preparation takes out from container after cooling, or after taking-up, and it is cooling to reuse heat exchanger etc..

Solution can also be prepared using hot-cold lysis method.Hot-cold lysis method can acidylate cellulose and be difficult in the organic solvent dissolved or dissolve in common dissolving method.Even in addition, the solvent that can dissolve acylated cellulose in common dissolving method, which also has the effect that, can obtain rapidly uniform solution using hot-cold lysis method.

In hot-cold lysis method, initially slowly acylated cellulose can be added in organic solvent while agitating at room temperature.

The amount of acylated cellulose is adjusted to, so that the acylated cellulose in the mixture containing 10-40 mass %.The amount of acylated cellulose is more preferably 10-30 mass %.In addition, aftermentioned arbitrary additive can be added in mixture.

Then, mixture is cooled to preferably -100~-10 DEG C (preferably -80~-10 DEG C, further preferably -50~-20 DEG C, most preferably -50~-30 DEG C).It is cooling for example to be carried out in dry ice methanol bath (- 75 DEG C) and cooling diethylene glycol solution (- 30~-20 DEG C).The mixture solidification of cellulose and organic solvent can be acidylated by cooling.

Cooling velocity is preferably 4 DEG C/min or more, further preferably 8 DEG C/min or more, most preferably 12 DEG C/min or more.The faster the better for cooling velocity, but the theoretic upper limit is 10000 DEG C/sec, is technically limited to 1000 DEG C/sec, and practical upper limit is 100 DEG C/sec.In addition, the ratio that the difference that cooling velocity is the temperature and final cooling temperature when beginning to cool is obtained divided by the time of cooling temperature final from beginning to cool to reaching.

In addition, if cooling mixture is warming up to 0-200 DEG C (preferably 0-150 DEG C, further preferably 0-120 DEG C, most preferably 0-50 DEG C), then acylated cellulose dissolves in organic solvent.Heating, which can be only placed in room temperature, to be carried out, and can also be heated up in bath temperature.Heating rate is preferably 4 DEG C/min or more, further preferably 8 DEG C/min or more, most preferably 12 DEG C/min or more.The faster the better for heating rate, is theoretically limited to 10000 DEG C/sec, is technically limited to 1000 DEG C/sec, and practical upper limit is 100 DEG C/sec.In addition, heating rate be the temperature and final warming temperature when starting to warm up difference divided by from start to warm up reach final warming temperature time obtained from ratio.

According to the available uniform solution of above-mentioned steps.In addition, the operation of cooling heating can be repeated when dissolving insufficient.The appearance of solution is only observed by visual observation it may determine that whether dissolution is abundant.

In hot-cold lysis method, be mixed into moisture in order to avoid condensing while cooling, it is preferable to use closed container with.It is depressurized when in addition, pressurizeing, heating while cooling in cooling warming operation, dissolution time can be shortened.In order to implement to pressurize and depressurize, it is preferable to use resistance to pressure container.

In addition; using hot-cold lysis method by cellulose ethanoate (degree of acetylation: 60.9%; viscometric degree of polymerization: 299) it is dissolved in the solution that 20 weight % are formed in methyl acetate; if measured using differential scanning calorimetry (DSC); then at 33 DEG C, nearby there are the pseudo phase transition points of collosol state and gel state, and in the temperature, the following are uniform gel states.Therefore, which preferably must be held at a temperature of pseudo-phase transition temperature or more, preferably+10 DEG C of gel phase transition temperature or so.But the pseudo-phase transition temperature is different according to the degree of acetylation of cellulose ethanoate, viscometric degree of polymerization, solution concentration and used organic solvent.

Acylated cellulose film is prepared from the cellulose acylate solutions (dope) of preparation by solvent cast method.It is preferred that delay visualization reagent is added into dope.Dope is cast on roller or conveyer belt, solvent is made to evaporate and form film.It is preferred that adjusting the concentration of the dope before curtain coating so that solid state component amount is 18-35%.It is preferred that the surface of roller or conveyer belt is processed as mirror status.It is preferred that it is on 10 DEG C of rollers or conveyer belt below that dope, which is cast to surface temperature,.

Drying means in solvent cast method is on the books in No. 62-115035 United States Patent (USP) 2336310, United States Patent (USP) 2367603, United States Patent (USP) 2492078, United States Patent (USP) 24922977, United States Patent (USP) 2492978, United States Patent (USP) 2607704, United States Patent (USP) 2739069, each specification of United States Patent (USP) 2739070, British patent 640731, each specification of British patent 736892 and examined patent publication 45-4554, examined patent publication 49-5614, tekiaki 60-176834, tekiaki 60-203430, tekiaki each bulletin.Drying on conveyer belt or roller can be carried out by being passed through the inert gases such as air, nitrogen.

After resulting film can also being peeled off from roller or conveyer belt, reuses the high temperature that from 100 to 160 DEG C of temperature gradually changes and air-dry dry so that residual solvent evaporates.Above method is on the books in fairness 5-17844 bulletin.It can be shortened by this method from the time for being cast to peeling.In order to implement this method, the surface temperature of roller or conveyer belt when curtain coating must be such that dope gelation.

Also it can be used two layers of modulated cellulose acylate solutions (dope) curtain coating or more, thus filming.At this point, it is preferred that manufacturing acylated cellulose film by solvent cast method.After dope is cast to roller or conveyer belt, evaporation solvent can form film.It is preferred that adjusting the concentration of the dope before curtain coating so that the amount of solid state component is in the range of 10-40 mass %.It is preferred that the surface of roller or conveyer belt is processed as mirror status.

In two layers of curtain coating or more of a variety of cellulose acylate solutions; a variety of cellulose acylate solutions can be cast; multiple curtain coating mouths are set at regular intervals in the direction of advance of supporter, are cast the solution containing acylated cellulose respectively from these curtain coating mouths, then be laminated to prepare film.The method recorded in tekiaki 61-158414, Japanese Laid-Open Patent Publication 1-122419 and Japanese Laid-Open Patent Publication 11-198285 bulletin can be used for example.Alternatively, it is also possible to be cast cellulose acylate solutions from 2 curtain coating mouths, to carry out filming.The method recorded in examined patent publication 60-27562, tekiaki 61-94724, tekiaki 61-947245, tekiaki 61-104813, tekiaki 61-158413 and Japanese Laid-Open Patent Publication 6-134933 bulletin can be used for example.In addition; the casting method for the following acylated cellulose film recorded in tekiaki 56-162617 bulletin can also be used: encasing highly viscous cellulose acylate solutions fluid with the cellulose acylate solutions of low viscosity, and squeeze out the cellulose acylate solutions of the high and low viscosity simultaneously.

Furthermore it is also possible to manufacture film as follows: using two curtain coating mouths, after the film that mouth removing is formed on supporter is cast by first, carries out second on contact intermediate layer side and prolong, to manufacture film.Such as the method recorded in examined patent publication 44-20235 bulletin can be enumerated.

Identical solution can be used in the cellulose acylate solutions of curtain coating, and different cellulose acylate solutions also can be used.In order to make multiple acylated cellulose layers that there is function, cellulose acylate solutions corresponding with its function can be squeezed out from each curtain coating mouth.In addition, cellulose acylate solutions of the invention can be cast simultaneously with other functional layers (such as adhesive layer, dye coating, antistatic backing, anti-blooming shadow layer, UV-absorbing layer, polarizing layer etc.).

For past single layer solution, in order to assign film necessary thickness, it is necessary to squeeze out highly viscous cellulose acylate solutions in higher concentrations.In this case, the poor generation solid matter of the stability of cellulose acylate solutions, so that it is bad largely to lead to the problem of point failure, flatness.It may is that as the way to solve the problem by being cast a variety of cellulose acylate solutions from curtain coating mouth; highly viscous solution can be expressed on supporter simultaneously; thus the excellent planar film that not only available flatness optimizes; and drying load can be reduced by using sticky cellulose acylate solutions, to improve the speed of production of film.

Anti-deterioration agent (such as antioxidant, peroxide decomposer, free radical inhibitors, metal-inert agent, sour capturing agent, amine) can be added in acylated cellulose film.Anti-deterioration agent is on the books in No. 6-107854 Japanese Laid-Open Patent Publication 3-199201, Japanese Laid-Open Patent Publication 5-1907073, Japanese Laid-Open Patent Publication 5-194789, Japanese Laid-Open Patent Publication 5-271471, Japanese Laid-Open Patent Publication each bulletin.In addition, the additive amount of above-mentioned anti-deterioration agent is preferably the 0.01-1 mass %, further preferably 0.01-0.2 mass % of the solution (dope) prepared.If additive amount is 0.001 mass % or more, the effect of anti-deterioration agent can be fully played, it is advantageous to.If additive amount be 1 mass % hereinafter, if anti-deterioration agent be difficult to film surface generate exudation (infiltration), it is advantageous to.Example as particularly preferred anti-deterioration agent can enumerate butylated hydroxytoluene (BHT), tribenzyl amine (TBA).

These dry processes after being cast to can be carried out under air atmosphere or be carried out under the inert atmospheres such as nitrogen.Common machine can be used in up- coiler used in the manufacture of acylated cellulose film of the invention, can determine tension method, determine to be wound in the winding method such as the fixed process control tension method of calibrated wrench method, gradient tension method, internal stress.

[stretch processing]

Twin shaft acylated cellulose film of the invention preferably carries out stretch processing.The draw direction of acylated cellulose film is preferably width direction.

The method stretched in width direction, such as recorded in each bulletins such as tekiaki 62-115035, Japanese Laid-Open Patent Publication 4-152125, Japanese Laid-Open Patent Publication 4-284211, Japanese Laid-Open Patent Publication 4-298310, Japanese Laid-Open Patent Publication 11-48271.

The stretching of film can carry out under conditions of room temperature or heating.Film can be stretched in the processing of drying process, be particularly effective in the case where residual solvent.It, can following oriented film when width direction stretches: while keeping the width edge of film to be conveyed with stenter, and slowly expanding the width of stenter.(it is preferable to use being uniaxially stretched for long stretching-machine) can also be stretched using stretching-machine after film drying.

The stretching ratio (extensibility relative to the film before stretching) of film is preferably 1%-200%, more preferably 5%-150%.In particular it is preferred that 1%-200% is stretched in the direction of the width, more preferable 5%-150%.Tensile speed is preferably 1%/minute~100%/minute, more preferably 5%/minute~80%/minute, most preferably 10%/minute~60%/minute.

In addition, stretching acylated cellulose film of the invention preferably after being stretched to maximum tension multiplying power, manufactures under the stretching ratio also lower than maximum tension multiplying power by keeping the process (being below loose process) of certain time.The stretching ratio of loose process is preferably up to the 50%~99% of stretching ratio, more preferably 70%~97%, most preferably 90%~95%.In addition, the time of loose process is preferably 1 second~120 seconds, more preferably 5 seconds~100 seconds.

By making stretching ratio, the time above range of loose process, the degree of orientation for postponing visualization reagent is improved, it is hereby achieved that high latency and the positive acylated cellulose film small with the delay variation of film thickness direction.

(saponification process)

Twin shaft acylated cellulose film of the invention can be assigned by alkali saponified processing and the adaptation of the polarizer material as polyvinyl alcohol, is preferably used as protective film.

(structure 2)

Component used in the structure 2 to liquid crystal display device of the invention is illustrated below.

(A piece)

The modified polycarbonate film that A piece used in the present invention can preferably record such as International Publication WO2003/032060 pamphlet is used as A piece of the invention.

In addition, the norborneol alkenes film recorded in special open 2003-255102 can also be preferably used as A piece of the invention.

(C piece)

As C piece of the invention, it is preferable to use the biaxial stretch-formed thin polymer films recorded in International Publication WO2003/032060 pamphlet and the polymerizable liquid crystal layer etc. recorded in special open 2004-326089 bulletin.

(structure 3)

Component used in the structure 3 to liquid crystal display device of the invention is illustrated below.

(optical compensating film A)

Optical compensating film A of the invention meets above-mentioned formula (9)~(12) relationship.Optical compensating film A of the invention preferably can be used as by the way that the norborneol alkenes film recorded in the modified polycarbonate film recorded in International Publication WO2003/032060 pamphlet and special open 2003-255102 is carried out stretch processing.

Optical compensating film A of the invention can double as polarizer protection film.

The norbornene resin for being preferably used as optical compensating film A of the invention is described in detail below.

It is preferred for the thermoplastic norbornene system resin of optical compensating film A of the invention (hereinafter, sometimes referred to as " resin of the invention ".) it is the copolymer comprising the structural unit a and the structural unit b indicated with the following general formula (2) that are indicated with the following general formula (1), it optionally can also be as needed comprising other structural units.

[chemical formula 93]

[in formula, X and R¹~R⁴As described above, R¹~R⁴Among at least one be the base indicated with the following general formula (1-1) and/or the following general formula (1-2).N is 0 or 1, and m is 0 or 1 or more integer, preferably 0~3, more preferably 0~2, particularly preferably 0.]

[chemical formula 94]

[chemical formula 95]

(in general formula (1-1) and general formula (1-2), R⁵~R¹⁴、Z、R^A、R^B, p and q it is as described above.S is 0 or 1 or more integer, preferably 0~3, more preferably 0~2, particularly preferably 0.〕

[chemical formula 96]

[in formula, X and R¹~R⁴As described above.T is 0 or 1, and u is 0 or 1 or more integer, preferably 0~3, more preferably 0~2, particularly preferably 1.But R in formula (2)¹~R⁴The case where being the group in addition to being indicated with above-mentioned general formula (1-1) or above-mentioned general formula (1-2).]

Wherein, in above-mentioned general formula (1), general formula (1-1), general formula (1-2) and general formula (2), R¹~R¹⁴、Z、R^AAnd R^BIndicate hydrogen atom；Halogen atom；Also it can have the alkyl that the substituted or unsubstituted carbon atom number of the linking group of oxygen, nitrogen, sulphur or silicon is 1~30；Or polar group, these atoms or group are illustrated.As halogen atom, fluorine atom, chlorine atom and bromine atom can be enumerated.The alkyl for being 1~30 as carbon atom number, can enumerate the alkyl such as methyl, ethyl, propyl；The naphthenic base such as cyclopenta, cyclohexyl；The alkenyls such as vinyl, allyl, acrylic；Aromatic series bases such as phenyl, xenyl, naphthalene, anthryl etc..These alkyl can also be replaced, and can enumerate the halogen atom such as fluorine, chlorine, bromine, phenyl sulfonyl etc. as substituent group.

In addition, above-mentioned substituted or unsubstituted alkyl can be directly in conjunction with ring structure, or can also be combined by linking group (linkage).As linking group, bivalent hydrocarbon radical that such as carbon atom number is 1~10 can be enumerated (such as with-(CH₂)_mThe alkylidene that (m is 1~10 integer) indicates)；Linking group (such as carbonyl (- CO-), carbonyloxy group (- COO-), Epoxide carbonyl (- OCO-), sulfonyl (- SO containing aerobic, nitrogen, sulphur or silicon₂), ehter bond (- O-), thioether bond (- S-), imide (- NH-), amido bond (- NHCO- ,-CONH-), siloxanes key (- OSi (R₂In)-(formula, R be the alkyl such as methyl, ethyl))；Or these the two kinds substances formed above by combination connection.

As polar group, can enumerate such as hydroxyl, the alkoxy that carbon atom number is 1~10, acyloxy, alkoxy carbonyl, aryloxycarbonyl, cyano, amide groups, the group containing imide ring, three organosilan oxygroups, three Organosilyls, amino, acyl group, alkoxysilyl, group and carboxyl containing sulfonyl.More specifically, it as above-mentioned alkoxy, can enumerate such as methoxyl group, ethyoxyl；As acyloxy, the aryl-carbonyl oxygens such as the alkyl carbonyl oxy such as acetoxyl group, propionyloxy and benzoyloxy can be enumerated；As alkoxy carbonyl, can enumerate such as methoxycarbonyl, ethoxy carbonyl；As aryloxycarbonyl, can enumerate such as phenyloxycarbonyl, naphthoxycarbonyl, fluorenes Epoxide carbonyl, biphenylyloxy carbonyl；As three organosilan oxygroups, can enumerate such as trimethyl silicane alkoxy, triethylsilane oxygroup；As three Organosilyls, trimethyl silyl, triethylsilyl etc.；As amino, primary amino group can be enumerated, as alkoxysilyl, can be enumerated such as trimethoxysilyl, triethoxysilyl.

Thermoplastic norbornene system resin for optical compensating film A of the invention is the structural unit a comprising being indicated with above-mentioned general formula (1) and the copolymer using the structural unit b that above-mentioned general formula (2) indicates as necessary structural unit, and the copolymer can be by making containing a kind or more of the monomer (hereinafter referred to as " specific monomer A " indicated with the following general formula (3).) and a kind or more of the monomer (hereinafter referred to as " specific monomer B " that is indicated with the following general formula (4).) monomer mixture carry out ring opening copolymer and obtain.

[chemical formula 97]

[in formula, R¹~R⁴As described in being related to the definition of general formula (1), R¹~R⁴At least-it is a be the group indicated with above-mentioned general formula (1-1) and/or above-mentioned general formula (1-2).In addition, v is 0 or 1, w is 0 or 1 or more integer, preferably 0~3, more preferably 0~2, particularly preferred 0.]

[chemical formula 98]

[in formula, R¹~R⁴As described in being related to the definition of general formula (1).But the case where removing the group indicated with above-mentioned general formula (1-1) or above-mentioned general formula (1-2).In addition, x is 0 or 1, y is 0 or 1 or more integer, preferably 0~3, more preferably 0~2, particularly preferably 1.]

The content of structural unit a is 95~5 weight %, preferably 90~10 weight %, more preferably 80~20 weight % in resin of the invention.When the content of structural unit a is 5 weight % or less, the film for optical use for showing positive wavelength dependency cannot be obtained sometimes.In addition, the film for optical use for showing positive wavelength dependency can not be obtained sometimes when the content of structural unit a is 95 weight % or more.As the more specifical example of thermoplastic norbornene system resin of the invention, polymer shown in following (1)~(3) can be enumerated.

(1) ring-opening copolymer of specific monomer A and specific monomer B.

(2) ring-opening copolymer of specific monomer A, specific monomer B and other co-polymerized monomers.

(3) hydride of the ring-opening copolymer of (1) or (2).

<specific monomer A>

Specific example is shown to specific monomer A below, but the present invention is not limited to these.5- benzoyloxy -5- methyl bicyclic [2.2.1] hept-2-ene", two ring of 5- benzoyloxy [2.2.1] hept-2-ene", 5- (1- naphthalene carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (1- naphthalene carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (2- naphthalene carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (2- naphthalene carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (4- xenyl carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (4- xenyl carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (2- xenyl carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (2- xenyl carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (3- xenyl carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (3- xenyl carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (9- fluorenes carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (9- fluorenes carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (2- fluorenes carbonyloxy group) two rings [2.2.1] hept-2-ene", 5- (2- fluorenes carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (9- anthracene carbonyloxy group) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (9- anthracene carbonyloxy group) two rings [2.2.1] hept-2-ene", 8- benzoyloxy - 8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- benzoyloxy Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (1- naphthalene carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (1- naphthalene carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- naphthalene carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- naphthalene carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (4- xenyl carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (4- xenyl carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (3- xenyl carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (3- xenyl carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- xenyl carbonyloxy group) -8- methyl Fourth Ring [44.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- xenyl carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (9- fluorenes carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (9- fluorenes carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- fluorenes carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (2- fluorenes carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (9- anthracene carbonyloxy group) -8- methyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- (9- anthracene carbonyloxy group) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene etc..These can be used alone, and can also be used in combination with two kinds or more.

<specific monomer B>

As the specific example of specific monomer B, substance described below can be enumerated, but be not restricted to that these.Two rings [2.2.1] hept-2-ene", 5- methyl bicyclic [2.2.1] hept-2-ene", two ring of 5- ethyl [2.2.1] hept-2-ene", two ring of 5- isopropyl [2.2.1] hept-2-ene", two ring of 5-n- butyl [2.2.1] hept-2-ene", two ring of 5-n- hexyl [2.2.1] hept-2-ene", two ring of 5- cyclohexyl [2.2.1] hept-2-ene", two ring of 5-n- octyl [2.2.1] hept-2-ene", two ring of 5-n- decyl [2.2.1] hept-2-ene", 5- (1- naphthalene) two rings [2.2.1] hept-2-ene", 5- (2- naphthalene) -5- methyl bicyclic [2.2.1] hept-2-ene", 5- (4- xenyl) two rings [2.2.1] hept-2-ene", 5- (4 Xenyl) -5- methyl bicyclic [2.2.1] hept-2-ene", two ring of 5- methoxycarbonyl [2.2.1] hept-2-ene", 5- methyl -5- methoxycarbonyl two ring [2.2.1] hept-2-ene", two ring of 5- phenyloxycarbonyl [2.2.1] hept-2-ene", 5- methyl -5- phenyloxycarbonyl two ring [2.2.1] hept-2-ene", two ring of 5- cyano [2.2.1] hept-2-ene", two ring of 5- ethidine [2.2.1] hept-2-ene", two ring of 5- phenyl [2.2.1] hept-2-ene", two ring of 5- fluorine [2.2.1] hept-2-ene", two ring of 5- methyl fluoride [2.2.1] hept-2-ene", two ring of 5- trifluoromethyl [2.2.1] hept-2-ene", two ring of 5- pentafluoroethyl group [2.2.1] heptan - 2- alkene, 5, two ring of 5- difluoro [2.2.1] hept-2-ene", 5, two ring of 6- difluoro [2.2.1] hept-2-ene", 5, bis- (trifluoromethyl) two ring [2.2.1] hept-2-ene"s of 5-, 5, bis- (trifluoromethyl) two ring [2.2.1] hept-2-ene"s of 6-, 5- methyl -5- trifluoromethyl two ring [2.2.1] hept-2-ene", 5, 5, two ring of 6- trifluoro [2.2.1] hept-2-ene", 5, 5, 6- tri- (methyl fluoride) two ring [2.2.1] hept-2-ene", 5, 5, 6, two ring of 6- tetrafluoro [2.2.1] hept-2-ene", 5, 5, 6, 6- tetra- (trifluoromethyl) two ring [2.2.1] hept-2-ene", 5, 5- bis- fluoro- 6, two ring [2.2.1 of 6- bis- (trifluoromethyls) ] hept-2-ene", 5, 6- bis- fluoro- 5, bis- (trifluoromethyl) two ring [2.2.1] hept-2-ene"s of 6-, 5, 5, fluoro- two ring of 5- trifluoromethyl [2.2.1] hept-2-ene" of 6- tri-, the fluoro- 5- pentafluoroethyl group -6 of 5-, bis- (trifluoromethyl) two ring [2.2.1] hept-2-ene"s of 6-, 5, bis- fluoro- isopropyl -6- trifluoromethyl two ring [2.2.1] hept-2-ene" of fluoro- 5- seven of 6-, 5- chloro- 5, 6, two ring of 6- trifluoro [2.2.1] hept-2-ene", 5, 6- bis- chloro- 5, bis- (trifluoromethyl) two ring [2.2.1] hept-2-ene"s of 6-, 5, 5, fluoro- two ring of 6- trifluoromethoxy [2.2.1] hept-2-ene" of 6- tri-, 5, 5, fluoro- seven fluorine propoxyl group of 6-, two ring [2. of 6- tri- 2.1] hept-2-ene", 5- (4- phenyl) two rings [2.2.1] hept-2-ene", two ring of 5- amino methyl [2.2.1] hept-2-ene", two ring of 5- trimethoxysilyl [2.2.1] hept-2-ene", two ring of 5- triethoxysilyl [2.2.1] hept-2-ene", 5- tripropoxy-silicane base two ring [2.2.1] hept-2-ene", tri- butoxy silicyl of 5- two ring [2.2.1] hept-2-ene", two ring of 5- chloromethyl [2.2.1] hept-2-ene", tricyclic [5.2.1.0^2,6] -8- decene, tricyclic [4.4.0.1^2,5] -3- endecatylene, Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methoxycarbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- ethoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8-n- propoxycarbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- isopropoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8-n- butoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- phenyloxycarbonyl Fourth Ring [4,4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- methoxycarbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- ethoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8-n- propoxycarbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- isopropoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8-n- butoxy carbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- phenyloxycarbonyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- ethidine Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- phenyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- phenyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- fluorine Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl fluoride Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- difluoromethyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- trifluoromethyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- pentafluoroethyl group Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8- difluoro Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,9- difluoro Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of 8,8-^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of 8,9-^2,5.1^7,10] -3- dodecylene, 8- methyl -8- trifluoromethyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9- trifluoro Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9- tri- (trifluoromethyl) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9,9- tetrafluoro Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9,9- tetra- (trifluoromethyl) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of fluoro- 9, the 9- of 8,8- bis-^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of fluoro- 8, the 9- of 8,9- bis-^2,5.1^7,10] -3- dodecylene, 8,8,9- tri- fluoro- 9- trifluoromethyl Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9- tri- fluoro- 9- trifluoromethoxy Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8,8,9- tri- fluoro- five fluorine propoxyl group Fourth Ring [4.4.0.1 of 9-^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of the fluoro- 8- pentafluoroethyl group -9,9- of 8-^2,5.1^7,10] -3- dodecylene, the fluoro- 8- hepta-fluoroiso-propyl -9- trifluoromethyl Fourth Ring [4.4.0.1 of 8,9- bis-^2,5.1^7,10] -3- dodecylene, chloro- 8,9,9- trifluoro Fourth Ring [4.4.0.1 of 8-^2,5.1^7,10] -3- dodecylene, bis- (trifluoromethyl) Fourth Ring [4.4.0.1 of chloro- 8, the 9- of 8,9- bis-^2,5.1^7,10] -3- dodecylene, 8- (2,2,2- trifluoro ethoxy carbonyl) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene, 8- methyl -8- (2,2,2- trifluoro ethoxy carbonyl) Fourth Ring [4.4.0.1^2,5.1^7,10] -3- dodecylene five rings [6.5.1.1^3,5.0^2,7.0^9,13] -4- pentadecane alkene, five rings [7.4.0.1^2,5.1^9,12.0^8,13] -3- pentadecane alkene, five rings [8.4.0.1^2,5.1^9,12.0^8,13] -3- hexadecene, seven ring [8.7.0.1^3,6.1^10,17.1^12,15.0^2,7.0^11,16] -4- eicosylene, seven ring [8.8.0.1^4,7.1^11,18.1^13,16.0^3,8.0^12,17] -5- heneicosene etc..

These can be used alone, and can also be used in combination with two kinds or more.In these monomers B, in general formula (4), from the viewpoint of the balance of the heat resistance of obtained polymer and toughness, the preferably specific monomer B of x=0 and y=1.I.e., if the use of x being 2 or more or specific monomer B that y is 1, then there is the trend that the glass transition temperature (Tg) of obtained polymer is got higher and heat resistance improves, this is preferred situation, but there is also toughness downward trends sometimes, and when the film is formed processing or using when be easy to crack or be broken the problem of.

Additionally, it is preferred that having the specific monomer B of at least one polar group using intramolecular.That is, in above-mentioned general formula (4), R¹~R⁴Among any three be alkyl that hydrogen atom or carbon number are 1~10, remaining one is polar group other than alkyl, it is preferred that the group with the adaptation of other raw material and zygosity can be improved.In addition, making it easy to for controlling the obtained glass transition temperature of polymer and the viewpoint of absorbability, preferably the polar group is with general formula (5):

-(CH₂)_zCOOR¹⁵    (5)

(wherein, z is usually 0~5 integer, preferably 0~2, and more preferable 0.R¹⁵It is the organic group of monovalence.) indicate polar group specific monomer B.

As in general formula (5) with R¹⁵The organic group of the monovalence of expression can enumerate the alkyl such as methyl, ethyl, propyl；The aryl such as phenyl, naphthalene, anthryl, xenyl；It furthermore can also be the univalent perssad etc. with the heterocycles such as aromatic rings and furan nucleus, acid imide such as fluorenes classes such as diphenyl sulfone, tetrahydro fluorenes.In addition, z is usually 0~5 as described above, but since the value of z is smaller, the glass transition temperature of obtained polymer is higher in general formula (5), it is advantageous to the specific monomer B that particularly preferred z is 0 from the viewpoint of being readily synthesized it.

In addition, alkyl is preferably combined on the carbon atom that the polar group indicated with general formula (5) combines in above-mentioned general formula (4), thus the heat resistance of the polymer made and water suction sexual balance.The carbon atom number of the alkyl is preferably 1~5, and more preferably 1~2, particularly preferably 1.It is enumerated in regard to the specific example of above-mentioned specific monomer B, particularly preferred 8- methyl -8- methoxycarbonyl Fourth Ring (4.4.0.1^2,5.1^7,10) -3- dodecylene because glass transition temperature can be improved hardly by because absorbing the bad influences such as deformation generated, and can keep with the adaptation of other materials and zygosity the water imbibition of good degree.

The content of polar group in polymer is determined according to desired performance etc., is not particularly limited, but the structural unit in total unit with polar group usually contains 1 mole of % or more, preferably 5 moles of % or more, more preferable 10 moles of % or more.Total unit also can have polar group.The content of polar group can be adjusted according to the copolymerization ratio of specific monomer A and specific monomer B (or following " other co-polymerized monomers ") and the type of co-polymerized monomer suitably selected.

<other co-polymerized monomers>

As the other co-polymerized monomers that can play copolymerization with specific monomer A and specific monomer B-, such as cyclobutane, cyclopentene, cycloheptene, cyclo-octene, tricyclic [5.2.1.0 can be enumerated^2,6] cycloolefins such as -3- decene, bicyclopentadiene.As the carbon atom number of cycloolefin, preferably 4~20, more preferably 5~12.In addition specific monomer A and specific monomer B (and other co-polymerized monomers) can also be made to polymerize in the presence ofs the unsaturated hydrocarbons quasi polymer etc. on the main chains such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene with alkene unsaturated bond.However, the copolymer obtained at this time is suitable as the big resin raw material of impact resistance.

<polymerizing condition>

The ring-opening polymerization condition of specific monomer A and specific monomer B and/or other co-polymerized monomers to a kind or more are illustrated.

Catalyst: the ring-opening polymerization carries out in the presence of double decomposition (metathesis) catalyst.The metathesis catalyst is by being selected from W selected from (a), the at least one of the compound of Mo and Re, (b) be moral bright (デ ミ Application グ) periodic law Table I A race element (such as Li, Na, K etc.), Group IIA element (such as Mg, Ca), Group IIB element (such as, Zn, Cd, Hg etc.), IIIB race element (such as B, Al etc.), IVA race element (such as Ti, Zr etc.) or Group IVB element (such as Si, Sn, Pb etc.) compound, and the catalyst being combined into selected from the group at least one element-carbon key or element-hydrogen bond substance.In addition aftermentioned additive (c) can also be added in order to improve the activity of catalyst at this time.

The representative example of the compound of W, Mo or the Re suitable as (a) ingredient, can enumerate WCl₆、MoCl₅、ReOCl₃Etc. the compound recorded in Japanese Laid-Open Patent Publications 1-240517 bulletin.As the specific example of (b) ingredient, n-C can be enumerated₄H₉Li、(C₂H₅)₃Al、(C₂H₅)₂AlCl、(C₂H₅)_1.5AlCl_1.5、(C₂H₅)AlCl₂, methyl oxidation alkyl aluminum, the compound recorded in the Japanese Laid-Open Patent Publications 1-240517 bulletin such as LiH.As the representative example of (c) ingredient, alcohols, aldehydes, ketone, amine etc. can be properly used, it is also possible to use the compound recorded in Japanese Laid-Open Patent Publication 1-240517 bulletin.

As the usage amount of metathesis catalyst, " specific monomer " (hereinafter, as collectively referred to as specific monomer A~D, is only called with above-mentioned (a) ingredient and specific monomer A~D.) molar ratio computing, (a) ingredient: specific monomer is usually 1: 500~1: 50,000 range, preferably 1: 1,000~1: 10,000 range.(a) ratio of ingredient and (b) ingredient " (a): (b) " in terms of metallic atom ratio is 1: 1~1: 50, preferably 1: 2~1: 30 range.(a) ratio of ingredient and (c) ingredient is 0.005: 1~15: 1 with molar ratio computing " (c): (a) ", preferably 0.05: 1~7: 1 range.

Molecular weight regulator: adjusting for the molecular weight of polymer can be carried out according to polymerization temperature, the type of catalyst, the type of solvent, but in the present invention, be preferably adjusted by coexisting in molecular weight regulator in reaction system.As suitable molecular weight regulator, alpha-olefines and styrene such as ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene can be enumerated, wherein preferred 1- butylene, 1- hexene.These molecular weight regulators can be used alone or two kinds or more are used in mixed way.It is 0.005~0.6 mole, preferably 0.02~0.5 mole relative to 1 mole of specific monomer for being provided in polymerization reaction as the usage amount of molecular weight regulator.

Ring-opening polymerization solvent: as solvent used in polymerization reaction, the alkanes such as pentane, hexane, heptane, octane, nonane, decane can be enumerated；The cycloalkanes such as hexamethylene, cycloheptane, cyclooctane, naphthalane, norbornane；The aromatic hydrocarbons such as benzene,toluene,xylene, ethylbenzene, cumene；The halogenated hydrocarbons such as chloro-butane, bromo hexane, methylene chloride, dichloroethanes, hexa-methylene dibromide, chlorobenzene, chloroform, tetrachloro-ethylene；The compounds such as aryl；The saturated carboxylic acids esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, dimethoxy-ethane；The ethers such as dibutyl ethers, tetrahydrofuran, dimethoxy-ethane, these can be used alone or two kinds or more are used in combination.Wherein, preferably above-mentioned aromatic hydrocarbon.As the usage amount of solvent, solvent: specific monomer (weight ratio) is usually 1: 1~10: 1 amount, preferably 1: 1~5: 1 amount.

The hydrogenation of polymer: the polymer obtained as described above can be used as resin of the invention as former state, it is preferred that using after remaining alkene unsaturated bond is hydrogenated.Hydrogenation can be carried out with usual way, i.e., hydrogenation catalyst is added in the solution of polymer, so that it is acted on normal pressure~300 atmospheric pressure at 0~200 DEG C, preferably 20~180 DEG C, the hydrogen of preferably 3~200 atmospheric pressure carries out.

As hydrogenation catalyst, the catalyst of the hydrogenation commonly used in alkene compound can be used.It is well known to have uneven class catalyst and uniform class catalyst as the hydrogenation catalyst.As uneven class catalyst, the solid catalyst that the precious metals such as palladium of sening as an envoy to, platinum, nickel, rhodium, ruthenium are supported on the carriers such as carbon, silica, aluminium oxide, titanium dioxide can be enumerated.In addition, as uniform class catalyst, nickel naphthenate/triethyl aluminum, acetoacetate nickel/triethyl aluminum, octenoic acid cobalt/n-BuLi, titanocene dichloride/monochlor(in)ate diethyl aluminum, rhodium acetate, chlorination three (triphenylphosphine) rhodium, dichloride three (triphenylphosphine) ruthenium, hydrogen chloride carbonyl three (triphenylphosphine) ruthenium, dichloride carbonyl three (triphenylphosphine) ruthenium etc. can be enumerated.The form of catalyst can be powder be also possible to it is granular.These hydrogenation catalysts are according to polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10^-6~1: 2 ratio uses.

There is excellent thermal stability by hydrogenating obtained hydropolymer, its characteristic is difficult to aging due to heating in film film, when using when stretch process and as product.The hydrogenation ratio of alkene unsaturated bond is usually 50% or more, and preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more.

In addition, the aromatic rings in the structural unit a from specific monomer A is needed even across above-mentioned hydrogenation actually also without hydrogenation.As long as such hydrogenation can be carried out using the hydrogenation reaction condition of above-mentioned common alkene compound, but the conditions adjustment such as also need lower to set hydrogen pressure and reaction temperature, or the type and the additional amount that are adjusted hydrogenation catalyst sometimes in the above range.In addition, when the structural unit of the monomer from other co-polymerized monomers with the substituent group comprising aromatic rings includes aromatic rings, it is also preferred that the unsaturated bond of selection aromatic rings is through over hydrogenation actually without the condition of hydrogenation.

(optical compensating film B)

Optical compensating film B of the invention meets above-mentioned formula (13)~(16) relationship.As optical compensating film B of the invention, the optical anisotropic layer that cholesteric crystal is fixed can be used.As cholesteric crystal, the substance recorded in such as Japanese Laid-Open Patent Publication 3-67219 bulletin and Japanese Laid-Open Patent Publication 3-140921 bulletin, Japanese Laid-Open Patent Publication 5-61039 bulletin and Japanese Laid-Open Patent Publication 6-186534 bulletin, Japanese Laid-Open Patent Publication 9-133810 bulletin can be used.

It is also preferable to which the optical anisotropic layer that the disc liquid-crystal compounds of horizontal alignment disclosed in Japanese Laid-Open Patent Publication 11-352328 are fixed is used as optical compensating film B of the invention.

Optical compensating film B of the invention is preferably provided on the protective film for the relationship for meeting above-mentioned formula (1) and (2).Optical compensating film can be directly set on protective film, in addition other functional layers such as oriented layer, sealing layer can also be set between protective film and optical compensating film.

Cholesteric crystal layer in optical compensating film B of the invention is described in detail below.

As the liquid crystal monomer molecule (polymerizable liquid crystal molecule) for cholesteric crystal layer, the mixture with liquid crystal liquid crystal property monomer and chipal compounds.It can will such as include that two kinds or more of compound and following chemical formula (1)~chemical formula (10) compound in following chemical formula (11) are used in mixed way as an example of this polymerizable liquid crystal material.In addition, X is preferably 2~5 (integers) in the case where the liquid crystal liquid crystal property monomer indicated with chemical formula (11).

In addition, can be used for example as chiral agent with chiral agent shown in chemical formula (12)~chemical formula (14).In addition, with chiral agent shown in chemical formula (12), chemical formula (13), X is preferably 2~12 (integers), in addition, with chiral agent shown in chemical formula (14), X is preferably 2~5 (integers).

[chemical formula 99]

Chemical formula (1)

[chemical formula 100]

Chemical formula (2)

[chemical formula 101]

Chemical formula (3)

[chemical formula 102]

Chemical formula (4)

[chemical formula 103]

Chemical formula (5)

[chemical formula 104]

Chemical formula (6)

[chemical formula 105]

Chemical formula (7)

[chemical formula 106]

Chemical formula (8)

[chemical formula 107]

Chemical formula (9)

[chemical formula 108]

Chemical formula (10)

[chemical formula 109]

Chemical formula (11)

[chemical formula 110]

Chemical formula (12)

[chemical formula 111]

Chemical formula (13)

[chemical formula 112]

Chemical formula (14)

<production of polarizing film>

(polarizer)

The polarizer used in polarizing film of the invention is illustrated below.

The polarizer of the invention is preferably made of polyvinyl alcohol (PVA) and bitintability molecule, also can be used as described in Japanese Laid-Open Patent Publication 11-248937 by being dehydrated PVA and polyvinyl chloride, dechlorination forms polyene structure, then the polyethylene kind polarizer for forming its orientation.

As above-mentioned PVA, the polymer material obtained after being preferably saponified polyvinyl acetate, can also contain can be with vinyl acetate copolymerized ingredient such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefines, vinyl ethers.Furthermore it is also possible to use the modified PVA containing acetoacetyl, sulfonic group, carboxyl, alkylidene oxide etc..

From viewpoints such as dissolubilities, there is no particular limitation for the saponification degree of PVA, preferably 80~100mol%, particularly preferably 90~100mol%.And also there is no particular limitation for the degree of polymerization of PVA, and preferably 1000~10000, particularly preferably 1500~5000.

As recording in the specification for speciallyying permit No. 2978219, in order to improve durability, the syndiotactic body of PVA is preferably 55% or more, as described in No. 3317494 bulletin of special permission, further preferably uses 45~52.5%.

It is preferred that introducing bitintability molecule after PVA film and constituting the polarizer.The manufacturing method of PVA film generally preferably uses the method for stoste casting film-forming that PVA resinoid is dissolved in water or organic solvent and is formed.The concentration of polyvinyl alcohol resin in stoste is usually 5~20 mass %, is filmed by the tape casting to the stoste, can manufacture 10~200 μm of film thickness of PVA film.The manufacture of PVA film is referred to No. 3342516 specification of special permission, Japanese Laid-Open Patent Publication 09-328593 bulletin, special open 2001-302817 bulletin, special open 2002-144401 bulletin etc. and carries out.

There is no particular limitation for the crystallization degree of PVA film, the PVA film of 50~75 mass % of average crystallite degree (Xc) recorded in special permission the 3251073rd can be used, and in order to which the color in reduction face unevenly uses the PVA film below of crystallization degree 38% recorded in special open 2002-236214 bulletin.

It is preferred that PVA film it is birefringent (Δ n) it is smaller, it is preferable to use special permission No. 3342516 bulletin in record it is birefringent be 1.0 × 10^-3PVA film below.But as described in special open 2002-228835 bulletin, in order to avoid PVA film is broken and obtains high-polarization when stretching, the birefringent of PVA film can be 0.002-0.01；The value of (nx+ny)/2-nz can also be chosen for 0.0003-0.01 as described in special open 2002-060505 bulletin.The Re (1090) of PVA film is preferably 0nm-100nm, more preferably 0nm-50nm.Moreover, the Rth (1090) of PVA film is preferably 0nm-500nm, more preferably 0nm-300nm.

In addition, the use of the binding capacity of 1,2- glycol recorded in No. 3021494 bulletins of special permission being further preferably 1.5 moles of % PVA films below in polarizing film of the invention；The every 100cm recorded in special open 2001-316492 bulletin²In 5 μm or more of optics impurity be 500 PVA films below；The hot water cutting temperature range in the direction film TD recorded in special open 2002-030163 bulletin is 1.5 DEG C of PVA films below；And make glycerine etc. 3~6 yuan 1~100 mass parts of polyalcohol and mix the plasticizer recorded in the Japanese Laid-Open Patent Publication 06-289225 bulletin of 15 mass % or more and the solution formed, from the PVA film of the solution film-forming of the formation.

There is no particular limitation for film thickness before PVA film stretching, from the viewpoint of the stability of film preservation, the uniformity of stretching, preferably 1 μm~1mm, particularly preferably 20~200 μm.It as described in special open 2002-236212 bulletin, can be used when being stretched to 6 times from 4 times in water, generated stress is 10N relatively thin PVA film below.

It is preferable to use I for bitintability molecule₃ ^-And I₅ ^-Etc. high prices iodide ion or bitintability dyestuff.In the present invention, the iodide ion of high price is particularly preferably used.Such as " application of polarizer " the good volume in field forever, CMC is published and industrial materials, volume 28,7th phase, described in P39~P45, the iodide ion of high price can generate as follows: PVA being impregnated into the liquid and/or boric acid aqueous solution of the potassium iodide aqueous solution dissolved with iodine, is generated in the state of adsorbing and being orientated to PVA.

When using bitintability dyestuff as bitintability molecule, preferred azo pigment, particularly preferred two azo and trisazo- class pigment.The preferably water-soluble substance of bitintability dyestuff, for this purpose, introduce sulfonic group, amino, the hydrophilics such as hydroxyl in the bitintability molecule, and preferably by free acid or alkali metal salt, ammonium salt, amine salt in the form of use.

Specific example as this bitintability dyestuff, such as C.I. directly red 37, the Congo red (diphenyl amines such as C.I. directly red 28), C.I. directly purple 12, C.I. directly indigo plant 90, C.I. directly indigo plant 22, C.I. directly indigo plant 1, C.I. directly indigo plant 151, C.I. direct green 1 can be enumerated, C.I. Direct Yellow 44, C.I. Direct Red 23, the C.I. directly xenyls urea classes such as red 79, C.I. directly yellow 12 diphenylethylenes are waited, C.I. the directly binaphthyls amines such as red 31, the J acids such as C.I. directly red 81, C.I. directly purple 9, C.I. directly indigo plant 78.

Furthermore, further preferably using C.I. directly Huang 8, C.I. direct Huang 28, C.I. direct Huang 86, C.I. direct Huang 87, C.I. direct Huang 142, C.I. direct orange 26, C.I. direct orange 39, C.I. direct orange 72, C.I. direct orange 106, C.I. direct orange 107, C.I. directly red 2, C.I. directly red 39, C.I. directly red 83, C.I. directly red 89, C.I. directly red 240, C.I. directly red 242, C.I. directly red 247, C.I. direct purple 48, C.I. direct purple 51, C.I. direct purple 98, C.I. direct indigo plant 15, C.I. direct indigo plant 67, C.I. direct indigo plant 71, C.I. direct indigo plant 98, C.I. Directly indigo plant 168, C.I. direct indigo plant 202, C.I. direct indigo plant 236, C.I. direct indigo plant 249, C.I. direct indigo plant 270, C.I. direct green 59, C.I. direct green 85, C.I. direct brown 44, C.I. direct brown 106, C.I. direct brown 195, C.I. direct brown 210, C.I. direct brown 223, C.I. direct brown 224, C.I. directly black 1, C.I. directly black 17, C.I. directly black 19, C.I. directly black 54 etc. it is recorded in tekiaki 62-70802, Japanese Laid-Open Patent Publication 1-161202, Japanese Laid-Open Patent Publication 1-172906, Japanese Laid-Open Patent Publication 1-172907, Japanese Laid-Open Patent Publication 1-183602, Japanese Laid-Open Patent Publication 1-248105, The bitintability dyestuff etc. recorded in No. 7-261024 Japanese Laid-Open Patent Publication 1-265205, Japanese Laid-Open Patent Publication each bulletin.Two or more mixing of these bitintability dyestuffs can be manufactured to the bitintability molecule with various colors.When using bitintability dyestuff, if special open 2002-082222 is recorded, adsorption thickness can be 4 μm or more.

If the content of the bitintability molecule in film is very few, degree of polarization is low, and single transmittance also declines when in addition excessive, so the polyvinyl alcohol based polymer relative to the matrix for constituting film, is usually adjusted in the range of 0.01 to 5 quality %.

As the preferred film thickness of the polarizer, preferably 5 μm~40 μm, further preferably 10 μm~30 μm.It is also preferable to make the range of 0.01≤A (polarizer film thickness)/B (protective film film thickness)≤0.16 recorded in the thickness of the polarizer and the ratio special open 2002-174727 bulletin of the thickness of above-mentioned protective film.

In addition, the angle of the absorption axiss of the slow phase axis and polarizer of protective film can be arbitrary value, it is preferred that for parallel or 45 ± 20 ° azimuths.

(manufacturing process of polarizing film)

Then, the manufacturing process of polarizing film of the invention is illustrated.

The manufacturing process of polarizing film in the present invention is preferably made of the drying process after swelling process, dyeing process, dura mater process, stretching process, drying process, the bonding process of protective film, fitting.Dyeing process, dura mater process, the sequence of stretching process can also arbitrarily be changed, or several process step combinations are carried out simultaneously.In addition, can also preferably be washed after dura mater process as described in special permission the 3331615th specification.

In the present invention, it is particularly preferably successively carried out with sequence as the drying process that is swollen after process, dyeing process, dura mater process, stretching process, drying process, the bonding process of protective film, fitting.In addition, online surface shape inspection operation can be set in foregoing sequence or after process.

Above-mentioned swelling process preferably only uses water progress, but as described in Japanese Laid-Open Patent Publication 10-153709 bulletin, in order to ensure optical property stability and avoid polarization plate substrate folding line is generated in production line, can also make polarize plate substrate by boric acid aqueous solution be swollen with control polarize plate substrate swellbility.

In addition, the temperature of swelling process, time can be arbitrarily decided, preferably 10 DEG C~60 DEG C, 5 seconds~2000 seconds.

The method recorded in special open 2002-86554 bulletin can be used in above-mentioned dyeing process.In addition, not only use dipping as colouring method, and it can also be and iodine or dye solution are coated or any means by spraying etc..In addition, the concentration, the temperature of dye bath, the method for the stretching ratio in bath and the bath foam Edge Coloring in the stirring bath of side of control iodine can also be used as described in special open 2002-290025 bulletin.

When the iodide ion for using high price is as bitintability molecule, the polarizing film of high contrast, uses the solution that iodine is dissolved in potassium iodide aqueous solution preferably in dyeing process in order to obtain.The iodine of iodine-potassium iodide aqueous solution at this time is preferably 0.05~20g/l, and potassium iodide is preferably 3~200g/l, and the weight ratio of iodine and potassium iodide is preferably 1~2000.Dyeing time is preferably 10~1200 seconds, and liquid temperature is preferably 10~60 DEG C.It is even more preferred that iodine is 0.5~2g/l, potassium iodide is 30~120g/l, and the weight ratio of iodine and potassium iodide is 30~120, and dyeing time is 30~600 seconds, liquid temperature is 20~50 DEG C.

In addition, the boron compounds such as boric acid, borax can be added in dyeing liquor as described in special permission the 3145747th specification.

Above-mentioned dura mater process impregnates or is coated with solution preferably in cross-linking agent solution to contain crosslinking agent.In addition, dura mater process can divide to be carried out several times as described in Japanese Laid-Open Patent Publication 11-52130 specification.

The substance recorded in United States Patent (USP) 232897 specifications can be used as crosslinking agent, as described in special permission the 3357109th specification, in order to improve dimensional stability, polyaldehyde also can be used as crosslinking agent, but most preferably with boric acid class.When using boric acid as crosslinking agent used in dura mater process, metal ion can be added in boric acid-potassium iodide aqueous solution.As the preferred zinc chloride of metal ion, but zinc chloride can also be replaced using zinc salts such as the zinc halides such as zinc iodide, zinc sulfate, zinc acetates as described in special open 2000-35512 bulletin.

In the present invention, it is preferred to carry out: preparation is added to boric acid-potassium iodide aqueous solution of zinc chloride, and it is made to impregnate PVA film and carry out dura mater.Boric acid is 1~100g/l, and potassium iodide is 1~120g/l, and zinc chloride is 0.01~10g/l, and the dura mater time is preferably 10~1200 seconds, and liquid temperature is preferably 10~60 DEG C.More preferably boric acid is 10~80g/l, and potassium iodide is 5~100g/l, and zinc chloride is 0.02~8g/l, and the dura mater time is 30~600 seconds, and liquid temperature is 20~50 DEG C.

It is preferable to use the longitudinal directions recorded in United States Patent (USP) 2454515 specification etc. to be uniaxially stretched the stenter mode recorded in mode or special open 2002-86554 bulletin for above-mentioned stretching process.Preferred stretching ratio is 2 times~12 times, more preferably 3 times~10 times.In addition; choosing stretching ratio and the relationship of blank material thickness, polarizer thickness is (protective film be bonded after polarizer film thickness/blank material film thickness) × (total stretching ratio) > 0.17 that special open 2002-040256 bulletin is recorded, the width of polarizer when 0.80≤(width of polarizer when being bonded protective film/to record in special open 2002-040247 bulletin of choosing width and the relationship of the width of polarizer when being bonded protective film of polarizer when leaving last bath foam leaves last bath foam)≤0.95.

The known method in special open 2002-86554 bulletin can be used in above-mentioned drying process, it is preferable that temperature range is 30 DEG C~100 DEG C, preferred drying time is 30 seconds~60 points.In addition, the heat treatment that bleaching temperature is 50 DEG C or more in the carry out water described in the specification such as special permission the 3148513rd is further preferably carried out, and as Japanese Laid-Open Patent Publication 07-325215 bulletin and Japanese Laid-Open Patent Publication 07-325218 bulletin are documented under the atmosphere of Temperature and Humidity Control and carry out aging process.

The bonding process of protective film is the process that two surfaces of the aforementioned polarizer of drying process are left with 2 protective film fittings.It is preferably used in front of being just bonded and supplies adhering liquid, the method for reusing a pair of of roller fitting, so that the polarizer is overlapped with protective film.In addition, in order to inhibit the trench of the record as caused by the stretching of the polarizer concave-convex, preferably the moisture content of polarizer when being bonded is adjusted as described in special open 2001-296426 bulletin and special open 2002-86554 bulletin.In the present invention, it is preferable to use 0.1%~30% for moisture content.

There is no particular limitation for the bonding agent of the polarizer and protective film, can enumerate PVA resinoid (containing modified PVAs such as acetoacetyl, sulfonic group, carboxyl, alkylidene oxides) and boron compound aqueous solution etc., wherein particularly preferred PVA resinoid.The thickness of adhesive layer is preferably 0.01~5 μm, particularly preferably 0.05~3 μm after the drying.

In addition, in order to improve the bonding force of the polarizer and protective film, preferably protective film is carried out after surface treatment makes its hydrophiling, then is bonded.There is no particular limitation for the method for surface treatment, method well known to method, sided corona treatment method that can be saponified as described above using aqueous slkali etc..In addition, the adhesive layers such as gelatin priming coat can be set after surface treatment.As described in special open 2002-267839 bulletin, protecting the contact angle of film surface and water is preferably 50 DEG C or less.

For drying condition after fitting using the method recorded in special open 2002-86554 bulletin, preferred temperature range is 30 DEG C~100 DEG C, and preferred drying time is 30 seconds~60 minutes.In addition, further preferably carrying out aging under the atmosphere of control temperature and humidity as described in Japanese Laid-Open Patent Publication 07-325220 bulletin.

Constituent content in the polarizer is preferred are as follows: 0.1~3.0g/m of iodine², 0.1~5.0g/m of boron², 0.1~2.00g/m of potassium², 0~2.00g/m of zinc².In addition, potassium content can be 0.2 weight % hereinafter, the Zn content in the polarizer can choose 0.04 weight of weight %~0.5 % recorded in special open 2000-035512 bulletin as described in special open 2001-166143 bulletin.

As described in the specification for speciallyying permit No. 3323255, in order to assign polarizing film dimensional stability, organic titanic compound and/or organic zirconate can be added in any process of dyeing process, stretching process and dura mater process, can also contain at least one of organic titanic compound and organic zirconate compound.Furthermore it is possible to add bitintability dyestuff to adjust the color (tone) of polarizing film.

(characteristic of polarizing film)

(1) transmitance and degree of polarization

The preferred single transmittance of polarizing film of the invention is 42.5%~49.5%, more preferably 42.8%~49.0%.The preferred range for the degree of polarization that formula 1 defines is 99.900%~99.999%, more preferably 99.940%~99.995%.The preferred scope of parallel transmitance is 36%~42%, and the preferred scope of orthogonal transmitance is 0.001%~0.05%.

(mathematical expression 1)

(formula 4)

Above-mentioned transmitance is based on JISZ8701 and is defined with following formula.

(mathematical expression 2)

T=K ∫ S (λ) y (λ) τ (λ) d λ

Herein, K, S (λ), y (λ), τ (λ) are as described below.

(mathematical expression 3)

$K=\frac{100}{\&Integral;S\left(\mathrm{\&lambda;}\right)y\left(\mathrm{\&lambda;}\right)\mathrm{d\&lambda;}}$

(formula 3)

S (λ): color show used in standard light light splitting distribution

Y (λ): the equal colors function in XYZ system

τ (λ): spectrophotometric transmittance

In addition, the preferred scope of the bitintability ratio defined with following formula 5 is 48~1215, more preferably 53~525.

(mathematical expression 4)

(formula 5)

Iodine concentration and single transmittance can be the range recorded in [0017] of special open 2002-258051 bulletin.

As described in special open 2001-083328 bulletin and special open 2002-022950 bulletin, parallel transmitance is smaller to the dependence of wavelength.Optical property when setting polarizing film to cross Nicols state can in the range described in special open 2001-091736 bulletin [0007], parallel transmitance with the relationship of orthogonal transmitance can be special open 2002-174728 bulletin [0006] described in range.

In addition, as described in special open 2002-221618 bulletin, when the wavelength of light is between 420~700nm, the standard deviation of the parallel transmitance of every 10nm is 3 hereinafter, and the minimum value of (the parallel transmitance/orthogonal transmitance) of between a length of 420~700nm of light wave when every 10nm is 300 or more.

The parallel transmitance and orthogonal transmitance in wavelength 440nm of polarizing film, parallel transmitance and orthogonal transmitance when wavelength 550nm, parallel transmitance and orthogonal transmitance in wavelength 610nm are also preferably range described in special open 2002-258042 bulletin [0012] and special open 2002-258043 bulletin [0012].

(2) color

The brightness index L* and chromaticity index a* and b* that the color of polarizing film of the invention is preferably used as in the L*a*b* color specification system of CIE equalization sense space are evaluated.

The definition of L*, a*, b* are documented in such as Tokyo motor university press office periodical, color optics.

The preferred a* range of individual polarizing film is -2.5~0.2, more preferably -2.0~0.The range of the preferred b* of individual polarizing film is 1.5~5, more preferably 2~4.5 or less.The preferred range of the parallel a* through light of 2 polarizing films is -4.0~0, more preferably -3.5~-0.5.The preferred range of the parallel b* through light of 2 polarizing films is 2.0~8, more preferably 2.5~7.The preferred range of the orthogonal a* through light of 2 polarizing films is -0.5~1.0, more preferably 0~2.The preferred range of the orthogonal b* through light of 2 polarizing films is -2.0~2, more preferably -1.5~0.5.

Chromaticity coordinates (x, the y) evaluation calculated from aforementioned X, Y, Z, such as the parallel coloration (x through light of 2 polarizing films can be used in color_p, y_p) and the orthogonal coloration (x through light_c, y_c) [0017] of special open 2002-214436 bulletin, No. 2002-169024 each bulletin in [0007] of special open 2001-166136 bulletin and special open [0005]-[0008] described in range, in the relationship of color (tone) and the absorbance preferably range described in [0005]-[0006] of special open 2001-311827 bulletin.

(3) field angle property

When setting polarizing film to the light of cross Nicols state and incident wavelength 550nm, the situation of incident vertical light and direction from 45 degree of opposite polarizing axis with 40 degree of relative normal of angle it is incident in the case of, transmitance is than being preferably range described in special open 2001-166135 bulletin and special open 2001-166137 bulletin with xy colour difference.In addition, as described in Japanese Laid-Open Patent Publication 10-068817 bulletin, the light transmittance (T of the vertical direction of the polarization sheet laminate of cross Nicols configuration₀) and 60 ° of normal slope of the direction from laminated body light transmittance (T₆₀) ratio (T₆₀/T₀) it is preferably 10000 or less；As described in special open 2002-139625 bulletin, when being incident on natural light on polarizing film under 80 degree of any angle from normal to the elevation angle, in its wave-length coverage through 520nm~640nm of spectrum, the transmitance difference through light within wavelength domain 20nm is preferably 6% or less；As described in Japanese Laid-Open Patent Publication 08-248201 bulletin, the luminance difference through light on film on the position of arbitrary deviation 1cm is preferably within 30%.

(4) durability

(4-1) humidity resistance

After being placed 500 hours under 60 DEG C, the atmosphere of 95% relative humidity, before and after light transmittance and the absolute value of degree of polarization change rate be preferably 3% or less.The change rate of light transmittance be particularly preferably 2% hereinafter, and based on the absolute value of the change rate of degree of polarization, preferably 1.0% or less.In addition, the degree of polarization after placing 500 hours under 80 DEG C, 90% relative humidity is also preferably 95% or more, and singleton transmittance is preferably 38% or more as described in Japanese Laid-Open Patent Publication 07-077608 bulletin.

(4-2) dry strength

After being placed 500 hours under 80 DEG C of drying atmosphere, before and after light transmittance and the absolute value of degree of polarization change rate be preferably also 3% or less.Particularly, the change rate of light transmittance be particularly preferably 2% hereinafter, and based on the absolute value of the change rate of degree of polarization, preferably 1.0% hereinafter, further preferably 0.1% or less.

(4-3) other durabilities

In addition, the shrinking percentage after placing 2 hours at 80 DEG C is preferably 0.5% or less as described in Japanese Laid-Open Patent Publication 06-167611 bulletin；After the polarization sheet laminate that cross Nicols are arranged on the two sides of glass plate is placed 750 hours in 69 DEG C of atmosphere, x value and y value are preferably range described in Japanese Laid-Open Patent Publication 10-068818 bulletin；80 DEG C, place processing 200 hours in the atmosphere of 90% relative humidity after, the 105cm of Raman spectroscopy^-1And 157cm^-1The variation of spectral intensity ratio be preferably range documented by Japanese Laid-Open Patent Publication 08-094834 bulletin and Japanese Laid-Open Patent Publication 09-197127 bulletin.

(5) degree of orientation

The degree of orientation of PVA obtains good polarizing properties compared with Gao Zeneng, is preferably 0.2~1.0 as the order parameter value calculated by the methods of polarisation Raman scattering and polarisation FT-IR.In addition, the difference of the orientation coefficient (0.75 or more) of the orientation coefficient and dye molecule of the macromolecule segment of the full non-crystalline areas of the polarizer is more preferably at least 0.15 as described in tekiaki 59-133509 bulletin；As described in Japanese Laid-Open Patent Publication 04-204907 bulletin, the orientation coefficient of the non-crystalline areas of the polarizer is preferably 0.65~0.85；As order parameter value, I₃ ^-And I₅ ^-The degree of orientation of such high price iodide ion is preferably 0.8~1.0.

(6) other properties

As described in special open 2002-006133 bulletin, when heating 30 minutes at 80 DEG C, per unit width is preferably 4.0N/cm or less absorbing the convergent force of axis direction；As described in special open 2002-236213 bulletin, polarizing film is placed under 70 DEG C of heating condition 120 it is small in the case of, polarizing film is absorbing the size changing rate on size changing rate and polarisation axis direction in axis direction all preferably within ± 0.6%；As described in special open 2002-090546 bulletin, the moisture rate of polarizing film is also preferably 3 weight % or less.In addition, as described in special open 2000-249832 bulletin, the average boldness based on middle line, the surface roughness on the direction vertical with tensile axis is preferably 0.04 μm or less；As described in Japanese Laid-Open Patent Publication 10-268294 bulletin, preferably make the refractive index n through axis direction₀Greater than 1.6；The relationship of the thickness of the thickness and protective film of polarizing film is preferably range documented by [0004] of Japanese Laid-Open Patent Publication 10-111411 bulletin.

<liquid crystal display device>

Liquid crystal display device of the invention is illustrated below.

Fig. 2 is the schematic diagram for indicating the example of liquid crystal display device of the invention.In Fig. 2, liquid crystal display device 10 includes: to descend with liquid crystal layer 7 and on it the liquid crystal cells of electrode base board 8 on the downside of the liquid crystal cells side electrode substrate 5 and liquid crystal cells that are arranged, in the upside polarizing film 1 and lower-side polarizing plate 12 of the setting of the two sides of liquid crystal cells.Colour filter can also be set between liquid crystal cells and each polarizing film.When using above-mentioned liquid crystal display device 10 as infiltration type in use, can overleaf be arranged using cold cathode and thermic cathode fluorimetric pipe or light emitting diode, electroluminescent cell, electroluminescent cell as the backlight of light source.

Upside polarizing film 1 and lower-side polarizing plate 12 are respectively provided with the structure being laminated in the way of clamping the polarizer with two panels protective film.Liquid crystal display device 10 of the invention is preferably from the outside of device (far from liquid crystal cells side), laminating transparent protective film, the polarizer, acylated cellulose film of the invention in order.As liquid crystal display device 10, including direct image viewing type, image projecting type and light modulation type.It the use of three terminals of such as TFT and MIM or the active matrix liquid crystal display apparatus of two terminal semiconductor elements is effective in the present invention.Certainly be referred to as timesharing driving is also effective by the passive matrix liquid crystal display device of representative of STN mode.

(VA mode)

The preferred VA mode of the liquid crystal cells of liquid crystal display device of the invention.

Dielectric anisotropy is negative between upper and lower base plate in VA mode, can be by the liquid crystal of Δ n=0.0813, Δ ε=- 4.6 or so by friction orientation, and production indicates the indicator of the differently- oriented directivity of liquid crystal molecule, about 89 ° of so-called inclination angle.The thickness d of the liquid crystal layer 7 of Fig. 1 is set to 3.5 μm.Brightness when white displays can wherein be changed according to thickness d and the size of the product Δ nd of refractive anisotrop Δ n.Therefore the thickness for being used to obtain the liquid crystal layer of maximum brightness is set as in the range of 0.2 μm~0.5 μm.

Absorption axiss 2 of the upside polarizing film 1 of the liquid crystal cells and absorption axiss 13 of lower-side polarizing plate 12 are substantially vertical is laminated.The inside of the respective alignment films of lateral electrode substrate 5 and liquid crystal cells downside electrode base board 8 forms transparent electrode (not shown) on liquid crystal cell, and under the non-driven state for not applying driving voltage to electrode, liquid crystal molecule in liquid crystal layer 7 is orientated relative to real estate is substantially vertical, and as a result the polarization state by the light of liquid crystal display panel is almost unchanged.That is, realizing ideal black display in non-driven state in liquid crystal display device.On the contrary, at any driving condition, liquid crystal molecule is tilted to the direction for being parallel to real estate, polarization state is changed by the inclined liquid crystal molecule by the light of liquid crystal display panel.In other words, in liquid crystal display device, white displays are obtained in driving condition.In addition in Fig. 2, symbol 6 and 9 is tropism control direction.

Wherein due to applying electric field between upper and lower base plate, so the liquid crystal material being negative such as liquid crystal molecule along respond, dielectric anisotropy vertical with direction of an electric field can be used.In addition when by electrode setting, on one substrate, edge is parallel to when being laterally applied to electric field of real estate, has the material of positive dielectric anisotropy using liquid crystal material.

In addition in the liquid crystal display device of VA mode, the chiral agent being usually added into the liquid crystal display device of TN mode is rarely employed because the deterioration of dynamic response feature is made, but also for reducing, orientation is bad and is added sometimes.

VA mode is characterized in high-speed response and high contrast.But problem when being in terms of front contrast it is high, and contrast is low when in terms of tilted direction.Liquid crystal molecule is orientated perpendicular to real estate when black display.If be observed from the front, since liquid crystal molecule is almost without birefringent, so transmitance is low, high contrast is obtained.But liquid crystal molecule generation is birefringent when from oblique.In addition the angle of the crossing of polarizing film absorption axiss is 90 ° orthogonal when front is seen up and down, and from oblique see when is greater than 90 °.In view of the two reasons, light leakage, contrast decline are generated on oblique direction.It is provided with optical compensating sheet in order to solve this problem.

In addition liquid crystal molecule is inclined in white displays, and in the opposite direction with inclined direction, liquid crystal molecule is birefringent of different sizes when from oblique, generates difference in brightness and tone.In order to solve this problem, it forms the structure for the referred to as multizone that a pixel separation of liquid crystal display device is multiple regions.

[multizone]

For example, liquid crystal molecule is tilted in different multiple regions in a pixel by applying electric field and equalizes field angle characteristic in VA mode.When subregion is orientated in a pixel, gap, or setting protrusion can be set on the electrode, change direction of an electric field or electric field density is made to keep deflection.To obtain the field angle of Omnibearing even, the best increase number of partitions, and more than four subregions or octant when, can get substantially uniform field angle.Especially octant when polarizing film absorption axiss can be set as to arbitrary angle, it is advantageous to.

Furthermore in the zone boundary of subregion orientation, liquid crystal molecule has lower response.Therefore the reason of this becomes in general black display to keep black display, and brightness declines.Therefore chiral agent can be added into liquid crystal material to reduce borderline region.

[embodiment]

The present invention is more specifically described below by embodiment is enumerated.Material shown in embodiment below, usage amount, ratio, process content, processing sequence etc. are without departing from spirit of the invention, so that it may suitably be changed.Therefore, the scope of the present invention is not limited to specific example as shown below.

[reference example 1]

(production of low latency film A-1)

<modulation of cellulose acetate solution>

By in following composition investment mixing channels, stirring dissolves each ingredient, to modulate cellulose acetate solution A.

Cellulose acylate solutions A composition

100.0 mass parts of cellulose ethanoate of degree of acetylation 2.94, average degree of polymerization 310

Postpone 12.0 mass parts of depressant A-12

Methylene chloride (the 1st solvent) 402.0 mass parts

Methanol (the 2nd solvent) 60.0 mass parts

<modulation of Mat agent solution>

Following compositions is put into disperser, stirring dissolves each ingredient, to modulate Mat agent solution.

Mat agent solution composition

The silicon dioxide granule of average particle size 20nm

(AEROSIL R972, Japan's ア エ ロ ニ Le (strain) system)

2.0 mass parts

Methylene chloride (the 1st solvent) 75.0 mass parts

Methanol (the 2nd solvent) 12.7 mass parts

10.3 mass parts of cellulose acylate solutions A

<modulation of ultraviolet absorbent solution>

By in following composition investment mixing channels, stirring dissolves each ingredient, to modulate ultraviolet absorbent solution.

Ultraviolet absorbent solution composition

2.0 mass parts of ultraviolet absorbing agent UV-1

2.0 mass parts of ultraviolet absorbing agent UV-19

Methylene chloride (the 1st solvent) 58.4 mass parts

Methanol (the 2nd solvent) 8.7 mass parts

12.8 mass parts of cellulose acylate solutions A

Ultraviolet absorbing agent UV-101

[chemical formula 113]

Ultraviolet absorbing agent UV-103

[chemical formula 114]

Ultraviolet absorbing agent UV-104

[chemical formula 115]

It will mix after above-mentioned cellulose acylate solutions A94.6 mass parts, 1.3 mass parts of Mat agent solution, the filtering of 4.1 mass parts of ultraviolet absorbent solution, be cast using band casting machine according to the width of 1500mm.When residual solvent levels are 40 mass % from conveyer belt stripping film, film is kept with tenter clip gap under conditions of 100 DEG C and cross directional stretch is carried out with 8% stretching ratio, be dried until residual solvent levels are (dry 1) 5 mass %.In addition it is kept for 30 seconds at 100 DEG C in the state of the width after film stretches.Film is decontroled by tenter clip gap, after the width direction of film respectively cuts away 5% from both ends, again after making it spend 30 minutes dry sections by 140 DEG C under width direction is free (not keeping) state (dry 2), film roll is taken as roll.The residual solvent amount of obtained acylated cellulose film is 0.1 mass %, and film thickness is 80 μm.

(production of acylated cellulose film 102~105)

Other than the type and additive amount of the type of acylated cellulose and additive are changed according to the content of table 1, acylated cellulose film 102~105 is made in the same manner as described above.Wherein, the additive A -12 in table and D-5 be respectively equivalent to it is above-mentioned shown in postpone depressant exemplary compounds A-12 and D-5.

[table 1]

Acylated cellulose film	The degree of acetylation of acylated cellulose	Additive 1		Additive 2		Wavelength dispersion adjusts 1		Wavelength dispersion adjusts 2
										Type	Additive amount(a)	Type	Additive amount(a)	Type	Additive amount(a)	Type	Additive amount(a)
		101	2.94	A-12	12	-	-	UV-101	1.6									UV-19	1.6
102	2.95									D-5	12	-	-	UV-101	1.2	-	-
		103	2.91	D-5	16	-	-	UV-19	5.1									-	-
104	2.95									D-5	9	-	-	UV-101	3.2	-	-
		105	2.86	Triphenyl phosphate	8	Phosphoric acid Biphenyl Ester	4	UV-103	1.2									UV-104	0.4

(measurement of optical characteristics)

It uses " WR KOBRA " (prince's measurement instrument (strain)) in the environment of 25 DEG C of 60% relative humidity, measures Re and Rth of the acylated cellulose film 101~105 at 446nm, 548nm, 628nm respectively.As a result it is shown in table 2.

[table 2]

Acylated cellulose film	Re(nm)			Rth(nm)
							446nm	548nm	628nm	446nm	548nm	628nm
	101	-1	0	0	-15	-9							-5
102							-1	0	1	-5	1	4
	103	1	0	0	0	3							5
104							0	0	0	9	14	17
	105	-2	0	1	27	36							42

[reference example 2]

<production of optical compensating film A>

105 μm of thickness of isotropism norbornene film is laterally uniaxially stretched 180% with stenter at 175 DEG C, obtains the stretching norbornene film with a thickness of 63 μm.

It will be by 2,2 '-bis- (3,4- dicarboxyphenyi) hexafluoropropane (6FDA) and 2, the polyimides of 2 '-bis- (trifluoromethyl) -4, the weight average molecular weight (Mw) 120,000 of 4 '-benzidines (PFMBTFMB) synthesis is dissolved in the polyimide solution that 15 weight % are modulated in cyclohexanone.By the solution coated on above-mentioned stretching norbornene film.Then it is heat-treated 10 minutes at 100 DEG C, forms 5.5 μm of thickness of fully transparent and smooth Kapton on above-mentioned stretching norbornene film, then be uniaxially stretched 4% at 180 DEG C, obtain optical compensating film A.

[reference example 3]

<production of optical compensating film B>

With the following method make the structure 1 of Fig. 1 used in optical compensating film B (laminated body of phase difference film and biaxial films).

[modulation of cellulose acylate solutions]

Following compositions is put into mixing channel, stirring dissolves each ingredient, to modulate cellulose acylate solutions.

(compositions of cellulose acylate solutions)

100.0 mass parts of acylated cellulose (CA-1)

Degree of acetylation 1.75, benzoylation degree 0.65

6 substitution ratios 0.90 of benzoyl

Plasticizer: triphenyl phosphate (wavelength of maximum absorption is shorter than the wavelength of 280nm)

6.0 mass parts

Plasticizer: phosphoric acid Biphenyl Ester (wavelength of maximum absorption is shorter than the wavelength of 280nm)

3.0 mass parts

Methylene chloride (the 1st solvent) 402.0 mass parts

Methanol (the 2nd solvent) 60.0 mass parts

[modulation of Mat agent solution]

Following compositions is put into disperser, stirring dissolves each ingredient, to modulate Mat agent solution.

(Mat agent solution composition)

2.0 mass parts of silicon dioxide granule of average particle size 20nm

" AEROSIL R972 " Japan's ア エ ロ ニ Le (strain) system

Methylene chloride (the 1st solvent) 75.0 mass parts

Methanol (the 2nd solvent) 12.7 mass parts

10.3 mass parts of cellulose acylate solutions

[modulation that delay shows agent solution]

Following compositions is put into mixing channel, the side Bian Jiare is stirred, and dissolves each ingredient, so that modulating delay shows agent solution.

(composition that delay shows agent solution)

Postpone visualization reagent (41) (wavelength of maximum absorption is shorter than the wavelength of 250nm)

20.0 mass parts

Methylene chloride (the 1st solvent) 58.4 mass parts

Methanol (the 2nd solvent) 8.7 mass parts

12.8 mass parts of cellulose acylate solutions

Above-mentioned 94.3 mass parts of cellulose acylate solutions, 1.3 mass parts of Mat agent solution and delay are shown after 4.4 mass parts of agent solution filter respectively and mixed, is cast using band casting machine.It will be that the thin slice that 35 mass % are obtained removes conveyer belt with residual solvent levels, after carrying out stretching ratio of the cross directional stretch until 55% using stenter under conditions of 120 DEG C with the tensile speed of 40%/minute, kept for 30 seconds under 48% stretching ratio in 120 DEG C.Then, clip and drying 30 minutes at 120 DEG C are removed, to manufacture stretching acylated cellulose film.The ready-made residual solvent amount for stretching acylated cellulose film is 0.1 mass %, and film thickness is 92 μm.

(saponification process for stretching acylated cellulose film)

5.2mL/m is applied on the stretching acylated cellulose film (CAF1) of production²The liquid of following compositions, it is 10 seconds dry at 60 DEG C.For film surface with water displacement wash 10 seconds, being blown into 25 DEG C of air kept film surface dry.

(composition of saponification liquor)

818 mass parts of isopropanol

167 mass parts of water

187 mass parts of propylene glycol

Japanese エ マ Le ニ ヨ Application (strain) makes " EMALEX " 10 mass parts

67 mass parts of potassium hydroxide

(formation of orientation film layer)

24ml/m is applied on a face of the stretching acylated cellulose film (CAF1) of saponification process by the wire rod coating, dip coated device (wire bar coater) of #14²Following compositions coating liquid.Under 60 DEG C of warm wind after drying 60 seconds, then drying 150 seconds under 90 DEG C of warm wind.

Then, friction treatment is carried out to the alignment films that the draw direction (substantially uniform with slow phase axis) of the stretching acylated cellulose film (CAF1) in saponification process and 90 ° of side are upwardly formed.

Oriented film coating liquid composition

Following 20 mass parts of modified polyvinylalcohol

360 mass parts of water

120 mass parts of methanol

1.0 mass parts of glutaraldehyde (crosslinking agent)

Modified polyvinylalcohol

[chemical formula 116]

(production of optical anisotropic layer)

15.4ml/m is coated in alignment films using 4# wire rod coating, dip coated device²Following compositions coating fluid.It is adhered on metal frame, is heated 2 minutes in 100 DEG C of thermostat, be orientated liquid crystal compounds.Then, it is irradiated 1 minute using the high-pressure mercury-vapor lamp UV of 90 DEG C, 120W/cm, polymerize liquid crystal compounds.Later, it places and is cooled to room temperature.

Optical anisotropic layer coating liquid composition

Rod-shaped liquid crystalline compound I-6 (wavelength of maximum absorption is the wavelength for being longer than 280nm)

100 mass parts

(1) 0.7 parts by weight of polymer containing bridging property base

Fluorine system polymer

(big Japanese ink (strain) ガ Off ア Star Network F-780-F processed) 0.5 mass parts

Photoepolymerizationinitiater initiater (Irgacure 907, Ciba Geigy corporation) 2.9 mass parts

Sensitizer (mono- DETX of カ ヤ キ ユ ア, Japanese chemical drug (strain) are made) 1.0 mass parts

253 mass parts of methyl ethyl ketone

Production optical compensating film B as described above.

[reference example 4]

With the following method make the structure 2 of Fig. 1 used in optical compensating film C (laminated body of A piece and C piece) and low latency film laminated body.

<production of C piece>

(saponification process of acylated cellulose film)

2 minutes in the sodium hydrate aqueous solution that commercially available acylated cellulose film (Fuji タ Star Network TD80UL) is immersed in 2.3mol/L at 55 DEG C.Washed in the washing bath of room temperature, at 30 DEG C using 0.05mol/L sulfuric acid carry out in and.It is washed in the washing bath of room temperature, then is dried under 100 DEG C of warm wind again.

(formation of orientation film layer)

24ml/m is applied on a face of the stretching acylated cellulose film of saponification process by the wire rod coating, dip coated device (wire bar coater) of #14²Following compositions coating liquid.Under 60 DEG C of warm wind after drying 60 seconds, then drying 150 seconds under 90 DEG C of warm wind.

Then, friction treatment is carried out to the film that the draw direction (substantially uniform with slow phase axis) of the stretching acylated cellulose film in saponification process and 90 ° of side are upwardly formed.

Oriented film coating liquid composition

Following 20 mass parts of modified polyvinylalcohol

360 mass parts of water

120 mass parts of methanol

1.0 mass parts of glutaraldehyde (crosslinking agent)

Modified polyvinylalcohol

[chemical formula 117]

(production of optical anisotropic layer)

15.4ml/m is coated in alignment films using 4# wire rod coating, dip coated device²Following compositions coating fluid.It is adhered on metal frame, is heated 2 minutes in 135 DEG C of thermostat, be orientated liquid crystal compounds.Then, it is irradiated 1 minute using the high-pressure mercury-vapor lamp UV of 90 DEG C, 120W/cm, polymerize liquid crystal compounds.Later, it places and is cooled to room temperature.

Optical anisotropic layer coating liquid composition

100 mass parts of discotic liquid crystalline compound (D)

Ethylene-oxide-modified trimethylolpropane trimethacrylate

" V#360 " { Osaka organic chemistry (strain) system } 9.1 mass parts

1.1 parts by weight of average slope angle controlling agent (E)

0.2 mass parts of fluorine system polymer (F)

Photoepolymerizationinitiater initiater (Irgacure 907, Ciba Geigy corporation) 3.3 mass parts

Sensitizer (mono- DETX of カ ヤ キ ユ ア, Japanese chemical drug (strain) are made) 1.1 mass parts

253 mass parts of methyl ethyl ketone

Discotic liquid crystalline compound (D)

[chemical formula 118]

Average slope angle controlling agent (E)

[chemical formula 119]

Fluorine system polymer (F)

[chemical formula 120]

<production of the laminated body of A piece and C piece>

Only optical anisotropic layer is removed from the C piece of above-mentioned production, using adhesive, it is fitted in it and is formed on the polycarbonate film (trade name: mono- ス WR of ピ ユ ア エ (Supreme Being people's (strain) system)) (A piece) that the copolymer of the high molecular monomeric unit of different wavelength dispersion characteristics forms by containing.

<saponification process of low latency acylated cellulose film>

The acylated cellulose film 101 made by reference example 1 is impregnated 3 minutes at 55 DEG C in the sodium hydrate aqueous solution of 2.3mol/L.Washed in the washing bath of room temperature, at 30 DEG C using 0.05mol/L sulfuric acid carry out in and.It is washed in the washing bath of room temperature, then is dried under 100 DEG C of warm wind again.In this way, carrying out saponification process (hereinafter referred to as protective film E) to 101 surface of acylated cellulose film.

<production of optical compensating film C>

It is applied on the acylated cellulose film 101 of saponification process by polyvinyl alcohol resin (Network ラ レ PVA217, the degree of polymerization 1700; saponification degree 88%) bonding agent that is mixed to form according to the ratio for being 7: 3 with weight ratio meter of 5 mass % aqueous solutions and 25 mass % aqueous solution of water-soluble polymer (Japanese catalyst WS700) containing oxazoline group, and it is bonded with the polycarbonate film side of the laminated body of the A piece+C piece of above-mentioned production.

[reference example 5]

<production of optical compensating film D>

The poly-vinyl alcohol solution of 1 weight % is applied on the acylated cellulose film 101 of saponification process; it is dry at 90 DEG C to form thick about 0.01 μm of film; after carrying out friction treatment formation alignment films to its surface; cholesteric crystal liquid of the coating containing liquid crystal compounds (G), chiral agent (H) and polymerization initiator; it is heat-treated 1 minute at 90 DEG C and is carried out ultraviolet-crosslinkable, to form the phase difference film liquid crystal compounds (G) for being 185nm with a thickness of 2.5 μm, Re 0nm, Rth

[chemical formula 121]

Chiral agent (H)

[chemical formula 122]

<production of optical compensating film E>

(modulation of polymer solution)

It will be as 6- (2,4- the Dimethoxyphenyl) -6- azepine-five rings (9.2.1.1 of orbornene-based monomer (Im) indicated with following structural formula (A)^3,9.0^2,10.0^4,8) 14-12- alkene-5,7- diketone 7.90g (21.6 mMs), the 8- methyl-8- methoxycarbonyl Fourth Ring (4.4.0.1 indicated with following structural formula (C) as orbornene-based monomer (IIm)^2,5.1^7,10) -3- dodecylene 5.01g (21.6 mMs), the 1- hexene 0.27g as molecular weight regulator and the toluene 51.5g as solvent be fitted into nitrogen displacement reaction vessel, it is heated to 80 DEG C.Toluene solution (0.6 mole/L) 0.13mL of the triethyl aluminum as polymerization catalyst and toluene solution (0.025 mole/L) 0.34mL of carbinol-modified tungsten hexachloride are added into the reaction system, it is reacted 4 hours at 80 DEG C, thus to obtain the polymer solution containing norbornene polymer obtained therefrom through ring opening polymerization.

[chemical formula 123]

Structural formula (A)

[chemical formula 124]

Structural formula (C)

(modulation of ring-opening polymerisation resin)

Obtained polymer solution is added in autoclave, toluene 300g is added.Then, RuHCl (CO) (P (C for the amount for being 2500ppm relative to the additional amount of monomer is added into the system₆H₅)₃〕₃As hydrogenation catalyst, hydrogenation is carried out under conditions of Hydrogen Vapor Pressure is 9~10MPa, reaction temperature is 160~165 DEG C, reaction condition is 4 hours.After reaction, obtained reaction solution is injected in a large amount of methanol, makes its precipitating, to obtain the norbornene polymer obtained therefrom through ring opening polymerization of hydrogenation.The norbornene polymer obtained therefrom through ring opening polymerization is defined as " resin (P1) ".

(production of oriented film)

Resin obtained above (P1) is dissolved in toluene according to 30% concentration, use one タ mono- of metal industry INVEX ラ ボ U on well, it is applied in the PET film (eastern レ (strain) system, mono- U94 of Le ミ ラ) for 100 μm of surface-treated thickness for carrying out hydrophiling (easily combining) with acrylic compounds, so that the film thickness after drying is 350 μm, after it is carried out primary drying at 50 DEG C, redrying is carried out at 100 DEG C.The resin film of removing PET film is defined as (P1-F).

The film is heated to 228 DEG C in stenter, after being stretched as 1.7 times with 300%/minute of tensile speed, the state is kept under 221 DEG C of atmosphere gas about 1 minute, then cools to room temperature taking-up, to obtain optical compensating film (E).

[reference example 6]

<production of biaxial films F>

188 μm of thickness of ARTON films (JSR corporation) are stretched as 130% at 175 DEG C in a manner of longitudinal stretching, 135% is stretched as in a manner of cross directional stretch, to obtain 120 μm of thickness of film.The film shows the optical characteristics of Re=50nm, Rth=250nm.

The optical characteristics of the optical compensating film A~C and biaxial films D that are made as described above in the environment of 25 DEG C of 60% relative humidity using U Block ラ WR measurement.As a result it is shown in Table 3.

[table 3]

Sample	Re(nm)					Rth(nm)
											446nm	548nm	628nn	446nm/548nm	628nm/548nm	446nm	548nm	628nm	446nm/548nm	628nm/548nm
	Optical compensating layer A	47	52	56	0.90	1.08	256	250	240	1.02											0.96
Optical compensating layer B											38	63	80	0.60	1.27	252	230	220	1.10	0.96
	Optical compensating layer C	87	110	124	0.79	1.13	255	245	239	1.04											0.98
Optical compensating layer D											1	1	1	1.00	1.00	178	164	158	1.09	0.95
	Optical compensating layer E	100	135	146	0.74	1.08	53	70	76	0.76											1.09
Biaxial films F											51	50	50	1.02	1.00	252	250	249	1.01	1.00

[reference example 7]

The production of polarizing film

(basic treatment of acylated cellulose film)

The surface to acylated cellulose film 102~105 and the acylated cellulose surface of optical compensating film B and optical compensating film C and optical compensating film D carry out saponification process identically as reference example 4.

[reference example 8]

(surface treatment of optical compensating film A, E and biaxial films F)

In 12W points/m on the surface of the norbornene film side of optical compensating film A²Under conditions of by springtime motor (strain) corona discharge processed assign hydrophily.

In addition, identical processing can also be carried out even for the surface of optical compensating film E and biaxial films F, hydrophily is assigned.

[reference example 9]

<production of polarizing film 101>

(saponification process of polarizer protection film)

Commercially available acylated cellulose film (Fujiphoto system, Fuji タ Star Network TD80) is impregnated 1 minute at 55 DEG C in the sodium hydrate aqueous solution of 1.5mol/L.Washed in the washing bath of room temperature, at 30 DEG C using 0.05mol/L sulfuric acid carry out in and.It is washed in the washing bath of room temperature, then is dried under 100 DEG C of warm wind again.(hereinafter referred to as protective film G).

(production of the polarizer)

After the degree of polymerization is 1700, is swollen in 30 degree of tepidarium with a thickness of 39 μm of polyvinyl alcohol films, about 4 times are stretched as in 30 DEG C of the dye bath that the aqueous solution by iodine and potassium iodide forms.Then, it is stretched in 50 DEG C of the crosslinking bath that joined boric acid and potassium iodide, so that total stretching ratio is 5.5 times, and is crosslinked.It is impregnated in 35 DEG C progress color (tone) adjustment in liquor kalii iodide 10 seconds.Pass through washing, dry, the polarizer of 18 μm of thickness of acquisition again.The regain of the polarizer is 14%.In addition (Δ n) is 0.0482 to the birefringence under wavelength 900nm, transmitance 43%, degree of polarization 99.9%.

In addition, birefringence is found out by finding out phase difference value (Δ nd) using parallel Nicolle rotary process with the wavelength light of 900nm divided by thickness d (nm).

Transmitance is measured using spectrophotometer (color technical research institute system, DOT-3 in village), is 2 degree of visuals field (illuminant-C) with JIS Z8701, is carried out the Y value of visibility correction.

Transmitance (H90) when degree of polarization is the transmitance (H0) and orthogonal superposition when being overlapped two identical polarizers for parallel mode according to polarizing axis, measures according to the measurement method of above-mentioned transmitance and is found out by following formula.In addition, the transmitance (H0) and orthogonal transmitance (H90) of polarised light are the Y values of correction visibility.

Degree of polarization (%)=√ { (H0-H90)/(H0+H90) } × 100

(modulation of bonding agent)

Make polyester based urethane's (three field Jing Wu chemical company systems, タ ケ ラ Star Network XW-74-C154) 10 parts and isocyanates crosslinking agent (three field Jing Wu chemical company systems, mono- ト WD-725 of タ ケ ネ) for 1 partial dissolution in water, solid component is adjusted to 20% solution by modulation.It is used as bonding agent.

(production of polarizing film 101)

After applying above-mentioned adhesive solution on two faces of the above-mentioned polarizer; the protective film G of low latency film 101 and above-mentioned production that saponification process is crossed is bonded in the way of clamping the polarizer; it is dried 72 hours in 40 DEG C of baking oven, makes polarizing film 101.

[reference example 8]

(production of polarizing film 102~105)

Polarizing film 102~105 can also be made respectively identically as polarizing film 101 even for acylated cellulose film 102~105.

[reference example 9]

(production of polaroid A, E and F)

Above-mentioned adhesive solution is also coated with even for the optical compensating film A, optical compensating film E and biaxial films F being surface-treated in reference example 6; then the protective film G of above-mentioned production is bonded in the way of clamping the polarizer; it is dried 72 hours in 40 DEG C of baking oven, makes polaroid A and D.In addition, for polaroid A according to be bonded with the aspectant mode of the polarizer assign the hydrophilic norbornene film of optical compensating film A.

(production of polarizing film B and polarizing film C and polarizing film D)

It is also coated with above-mentioned adhesive solution even for optical compensating film B, the protective film F of above-mentioned production is then bonded in the way of clamping the polarizer, is dried 72 hours in 40 DEG C of baking oven, polarizing film B and polarizing film C is made.In addition, being bonded acylated cellulose film according to the aspectant mode of the polarizer.In addition, also making polarizing film C and polarizing film D respectively in the same manner even for optical compensating film C and optical compensating film D.

[embodiment 1]

(production of liquid crystal display device (a))

On the upside polarizing film of the liquid crystal display device (Fig. 3) of embodiment 7; it is the mode of liquid crystal cell side by the polarizing film (101) made by reference example 7 acylated cellulose film 101 (low latency film, protective film E) according to the invention; on lower-side polarizing plate; it is the mode of liquid crystal cell side by polarizing film (A) polyimide layer according to the invention made by reference example 9; by adhesive, one is respectively bonded in observer side and backlight side.Transmission axis according to the polarizing film of observer side is up and down direction, and the transmission axis of the polarizing film of backlight side is the mode of left and right directions, is configured to cross Nicols.Liquid crystal display device (a) has been made in this way.

In addition, liquid crystal display device (a)~(j) of the invention by the content production that upside polarizing film, lower-side polarizing plate are changed into table 4.

[embodiment 2]

(variation of color field angle)

To the liquid crystal display device 1-10 made by embodiment 1 in 60 ° of polar angle, changed with the color at 80 ° of 0 ° of measuring appliance (ELDIM corporation Ezcontrast) measurement azimuth and azimuth, absolute value delta x, the Δ y changed so as to find out color on xy chromatic diagram.

As a result it is shown in table 4.

[table 4]

Liquid crystal display device	Upside polarizing film	Lower-side polarizing plate	Δx	Δy	Remarks
						(a)	101	B	0.18	0.17	The present invention
(b)	102	B	0.21	0.2	The present invention
						(c)	103	B	0.17	0.16	The present invention
(d)	104	B	0.22	0.21	The present invention
						(e)	105	B	0.31	0.30	Comparative example
(f)	101	F	0.33	0.32	Comparative example
						(g)	105	F	0.41	0.39	Comparative example
(h)	101	A	0.25	0.24	The present invention
						(i)	101	C	0.23	0.21	The present invention
(j)	D	E	0.2	0.19	The present invention

As shown in Table 4, liquid crystal display device (e)~(g) of liquid crystal display device (a)~(d), (g), (i) of the invention relative to comparative example, the color variation generated by field angle is small, it is advantageous to.

Claims (11)

1. liquid crystal display device, it is with liquid crystal cells, two polarizing films of the liquid crystal cells two sides are set, and optical compensating film, the protective film that the polarizing film has the polarizer and is arranged on a face at least adjacent to the liquid crystal cell side for the polarizer, the optical compensating film is arranged between the liquid crystal cells and the polarizer, wherein the protective film is also possible to the structure as the optical compensating film, the protective film meets the relationship of following formula (1) and formula (2) in 400-700nm wave-length coverage, and, the optical compensating film meets following formula (3)-formula (8) relationship,

0nm≤Re(λ)≤5nm                         (1)

-20nm≤Rth(λ)≤20nm                     (2)

20nm < Re (548) < 150nm (3)

50nm < Rth (548) < 400nm (4)

0.5 < Re (446)/Re (548) < 1 (5)

1.0 < Re (628)/Re (548) < 2.0 (6)

1.0 < Rth (446)/Rth (548) < 2.0 (7)

0.5 < Rth (628)/Rth (548) < 1.0 (8)

Wherein, Re (λ) and Rth (λ) indicates the Re and Rth under wavelength X.

2. liquid crystal display device according to claim 1, wherein meet the formula (3)-formula (8) relationship optical compensating film with more than two thin polymer films stretched, the thin polymer film of described two above stretchings is laminated according to the mode for keeping mutual draw direction perpendicular.

3. liquid crystal display device according to claim 1, wherein meeting the laminated body that the formula (3)-formula (8) relationship optical compensating film is the overlay on stretching polymer film with liquid crystal compounds.

4. liquid crystal display device, it is with liquid crystal cells, two polarizing films of the liquid crystal cells two sides are set, and at least two optical compensating films being arranged between the polarizing film and liquid crystal cells, the polarizing film is made of the polarizer with two protective films that the polarizer two sides are arranged in, wherein the protective film among the protective film close to liquid crystal cell side is also possible to the structure as the optical compensating film, at least one of the protective film of close liquid crystal cell side meets the relationship of following formula (1) and formula (2) in 400-700nm wave-length coverage among the protective film, and, one of the optical compensating film meets following formula (9)-formula (12) relationship, another of the optical compensating film meets following formula (13)-formula (16) relationship,

0nm≤Re(λ)≤5nm                             (1)

-20nm≤Rth(λ)≤20nm                         (2)

50nm < Re (548) < 200nm (9)

30nm < Rth (548) < 150nm (10)

0.5 < Re (446)/Re (548) < 1 (11)

1.0 < Re (628)/Re (548) < 2.0 (12)

0nm≤Re (548) < 10nm (13)

100nm < Rth (548) < 300nm (14)

1.0 < Rth (446)/Rth (548) < 2.0 (15)

0.5 < Rth (628)/Rth (548) < 1.0 (16).

5. liquid crystal display device according to claim 4 is applied on the acylated cellulose film for meeting the formula (1) and formula (2) and/or formula (17) wherein meeting the formula (13)-formula (16) optical compensating film.

-10nm≤Rth(446)-Rth(629)≤10nm               (17)。

6. the liquid crystal display device recorded in -5 any one according to claim 1, wherein the protective film for meeting the formula (1) and formula (2) relationship meets the relationship of following formula (17),

-10nm≤Rth(446)-Rth(629)≤10nm               (17)。

7. the liquid crystal display device recorded in -5 any one according to claim 1, wherein the protective film for meeting the formula (1) and formula (2) relationship is acylated cellulose film.

8. the liquid crystal display device recorded in -4 any one according to claim 1, wherein the protective film for meeting the formula (1) and formula (2) relationship is the acylated cellulose film for meeting following formula (17) relationship,

-10nm≤Rth(446)-Rth(629)≤10nm             (17)。

9. the liquid crystal display device recorded in -5 any one according to claim 1, wherein the protective film for meeting the formula (1) and formula (2) relationship contains at least one compound indicated by following formula (A),

Formula (A)

In formula (A), R⁴、R⁵And R⁶Respectively indicate substituted or unsubstituted alkyl.

10. the liquid crystal display device recorded in -5 any one according to claim 1, wherein the protective film for meeting the formula (1) and formula (2) relationship contains at least one compound indicated by following formula (B),

Formula (B)

In formula (B), R¹And R²Respectively indicate alkyl or aryl.

11. the liquid crystal display device recorded in -5 any one according to claim 1, wherein liquid crystal cells are VA modes.

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