CN104540891A - Cellulose acylate film, polarizing plate using same, and liquid crystal display device - Google Patents

Abstract

A cellulose acylate film which contains cellulose acylate and at least one compound represented by general formula (I); a polarizing plate which uses the cellulose acylate film; and a liquid crystal display device. In general formula (I), each of R1, R3 and R5 represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an alkenyl group having 2-20 carbon atoms or an aromatic group having 6-20 carbon atoms, provided that one of the R1, R3 and R5 groups is an aralkyl group or a cycloalkyl group and the total number of ring structures present in the R1, R3 and R5 groups is 3 or more.

Description

Cellulose acylate film, the Polarizer using it and liquid crystal indicator

Technical field

The present invention relates to a kind of cellulose acylate film, use its Polarizer and liquid crystal indicator.

Background technology

Cellulose acylate film as the optical component of liquid crystal indicator, the supporter of such as optical compensation films, the protective membrane etc. of Polarizer, and for various liquid crystal indicator.

Liquid crystal indicator except if televisor (Television, TV) purposes etc. is generally beyond the use of indoor, such as, also increases in the chance of outdoor application centered by mancarried device etc.Therefore, need to develop a kind of ratio before more can the liquid crystal indicator of use under withstanding high temperatures high humidity.But, if at hot and humid lower use liquid crystal indicator, then produce the inequality caused by polaroid (polarizer) shrinks or polarizing properties decline, there is this problem of display performance deterioration thus.And then requirement liquid crystal indicator also being stood in more and more various purposes to harsh working conditions uprises, require the weather resistance than level higher before year by year.

Record in patent documentation 1 utilize containing acid ionization constant in specific solvent be 2 ~ 7 organic acid resin molding (comprising cellulose acylate film), the weather resistance of polaroid under hot and humid can be improved.In addition, also disclose in patent documentation 2 and have a kind of cellulose acylate film containing barbituric acid (barbituric acid) derivative known as organic acid, but not about the record of the weather resistance of polaroid.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2011-118135 publication

Patent documentation 2: Japanese Patent Laid-Open 2011-126968 publication

Summary of the invention

The problem that invention will solve

Research according to people such as the present inventor: when the weather resistance of polaroid under hot and humid will be improved further, must solve by adding the disadvantage that produces of various additive in the lump, the problem that such as, film caused by light painted or the improvement of adhesion when being provided with hard coat (hardcoat layer), the lower degradation of metal protection newly produce.

Problem of the present invention is to provide a kind of cellulose acylate film, use its Polarizer and liquid crystal indicator; above-mentioned cellulose acylate film can improve optical characteristics and the weather resistance of Polarizer; the adhesion particularly suppressing the painted of the film caused by light or improve when being provided with hard coat etc., and can further improve the performance of liquid crystal indicator.

The technique means of dealing with problems

The above-mentioned problem of solution that the present inventor etc. the are artificial and relation of various additive and various performance is studied.Its result, if find to add in cellulose acylate film that there is the barbituric acid derivatives of specific structure, then can suppress caused by rayed through time painted.Also comprise substituting group and be combined in interior result of carrying out studying further, the known ring structure with barbituric acid alternatively base is important, and is repeatedly studied further.According to the result of these researchs, the people such as the present inventor find the protective membrane by the cellulose acylate film comprising the barbituric acid with specific structure being used as polaroid, and can promote the weather resistance of Polarizer further.

In addition, the barbituric acid derivatives of above-mentioned ad hoc structure shows corrodibility hardly, and also excellent for the solvability of the solvent used during masking, and be vaporized also few, therefore above-mentioned cellulose acylate film also possesses advantage at its manufacture view.

That is, above-mentioned problem is reached by following means.

<1> cellulose acylate film, it comprises acylated cellulose and at least a kind of compound represented by following general formula (I).

[changing 1]

[in general formula (I), R ¹, R ³and R ⁵separately represent hydrogen atom, carbon number be 1 ~ 20 alkyl, carbon number be 3 ~ 20 cycloalkyl, carbon number be 2 ~ 20 thiazolinyl or carbon number be 6 ~ 20 aromatic series base.Abovementioned alkyl, cycloalkyl, thiazolinyl and aromatic series base can have substituting group.Wherein, R ¹, R ³and R ⁵in any one be aralkyl or cycloalkyl, and R ¹, R ³and R ⁵in existing ring structure add up to more than 3]

The cellulose acylate film of <2> according to <1>, wherein in general formula (I), R ⁵for aralkyl or cycloalkyl.

The cellulose acylate film of <3> according to <1> or <2>, wherein in general formula (I), R ¹, R ³and R ⁵there is the ring structure of more than 1 respectively.

The cellulose acylate film of <4> according to any one of <1> to <3>, wherein in general formula (I), R ¹, R ³and R ⁵there is the aromatic ring structure of more than 1 respectively.

The cellulose acylate film of <5> according to any one of <1> to <4>, wherein in general formula (I), R ¹, R ³and R ⁵institute has ring structure and is aromatic ring structure.

The cellulose acylate film of <6> according to any one of <1> to <5>, wherein total acyl substitution (A) of acylated cellulose meets following formula.

1.5≤A≤3.0

The cellulose acylate film of <7> according to any one of <1> to <6>; wherein the acyl group of acylated cellulose is ethanoyl, and total degree of substitution with acetyl group (B) meets following formula.

2.0<B<3.0

The cellulose acylate film of <8> according to <7>, wherein total degree of substitution with acetyl group (B) be more than 2.5, less than 2.97.

The cellulose acylate film of <9> according to any one of <1> to <8>, it comprises at least a kind of polycondensation ester cpds.

The cellulose acylate film of <10> according to <9>, wherein polycondensation ester cpds makes at least a kind of dicarboxylic acid represented by following general formula (a), carries out polycondensation with at least a kind of glycol represented by following general formula (b) and the compound that obtains.

[changing 2]

[in general formula (a), X represents the carbon number of divalence to be the fatty group of 2 ~ 18 or the carbon number of divalence is the aromatic series base of 6 ~ 18.In general formula (b), Z represents that the carbon number of divalence is the fatty group of 2 ~ 8]

The cellulose acylate film of <11> according to <9> or <10>, wherein the number average molecular weight of polycondensation ester cpds is 500 ~ 2000.

The cellulose acylate film of <12> according to any one of <9> to <11>, wherein the end of polycondensation ester cpds is through end-blocking.

The cellulose acylate film of <13> according to any one of <1> to <12>, it comprises the carbohydrate compound that monose or at least a kind comprise 2 ~ 10 monosaccharide units.

The cellulose acylate film of <14> according to <13>, wherein carbohydrate compound has alkyl, aryl or acyl group alternatively base.

<15> Polarizer, it at least comprises cellulose acylate film according to any one of above-mentioned <1> to <14> and polaroid.

<16> liquid crystal indicator, it at least comprises Polarizer according to above-mentioned <15> and liquid crystal cells.

In this manual, numerical range represented by " ~ " is used to refer to comprise numerical value described before and after it as the scope of lower value and higher limit.

In addition, in this manual, as long as in advance without special instruction, then as " base " illustrated by each base for comprising the form be unsubstituted and the implication with substituent form simultaneously.Such as, " alkyl " refers to have substituent alkyl.In addition, in this manual, " fatty group " is the fatty group of straight chain, branch or ring-type, can be representative examples of saturated aliphatic base, also can be unsaturated aliphatic base (can not become aromatic nucleus).

In this manual, when simultaneously or when specifying multiple substituting group or concatenating group (hereinafter referred to as substituting group etc.) alternatively, each substituting group etc. mutually can be identical, also can be different.

The effect of invention

Cellulose acylate film of the present invention can suppress further caused by rayed through time painted.In addition, if be used as the protective membrane of the polaroid in Polarizer, then the weather resistance of Polarizer can be promoted further.

Its result; a kind of cellulose acylate film can be provided, use its Polarizer and liquid crystal indicator; above-mentioned cellulose acylate film can improve optical characteristics and the weather resistance of Polarizer; the adhesion particularly suppressing the painted of the film caused by light or improve when being provided with hard coat etc., and can further improve the performance of liquid crystal indicator.

It is graphic that suitable reference is enclosed, and make above-mentioned and other feature of the present invention and advantage become clearer and more definite according to following record.

Accompanying drawing explanation

Fig. 1 is the sketch chart representing the in-built example schematically showing liquid crystal indicator.

Fig. 2 represents to use altogether curtain coating mould, and by the sketch chart of example when curtain coating makes 3 layers of cellulose acylate film constructed salivate altogether simultaneously.

Embodiment

Below, the present invention is described in detail to enumerate example.

" cellulose acylate film "

Cellulose acylate film of the present invention contains acylated cellulose and at least a kind of compound represented by following general formula (I).

Cellulose acylate film of the present invention can show the effect of the deterioration suppressing Polarizer, is suitable for being used as protective membrane.

The compound > of < represented by general formula (I)

The compound used in the present invention is the compound represented by following general formula (I).

[changing 3]

In general formula (I), R ¹, R ³and R ⁵separately represent hydrogen atom, carbon number be 1 ~ 20 alkyl, carbon number be 3 ~ 20 cycloalkyl, carbon number be 2 ~ 20 thiazolinyl or carbon number be 6 ~ 20 aromatic series base.This alkyl, cycloalkyl, thiazolinyl and aromatic series base can have substituting group.Wherein, R ¹, R ³and R ⁵in any one be aralkyl or cycloalkyl, and R ¹, R ³and R ⁵in existing ring structure add up to more than 3.

Above-mentioned R ¹, R ³and R ⁵in the carbon number of alkyl be preferably 1 ~ 10, be more preferably 1 ~ 5, and then be more preferably 1 ~ 3, be particularly preferably methyl or ethyl.Wherein, replacing the alkyl having aryl, namely when aralkyl, the carbon number of aralkyl is preferably 7 ~ 20, is more preferably 7 ~ 12, and then is more preferably 7 ~ 10.

Above-mentioned R ¹, R ³and R ⁵in the carbon number of cycloalkyl be preferably 3 ~ 10, be more preferably 4 ~ 8, and then be more preferably 5 or 6.As the concrete example of cycloalkyl, include, for example cyclopropyl, cyclopentyl, cyclohexyl, be particularly preferably cyclohexyl.

Above-mentioned R ¹, R ³and R ⁵in the carbon number of thiazolinyl be preferably 2 ~ 10, be more preferably 2 ~ 5.Include, for example vinyl, allyl group.

Above-mentioned R ¹, R ³and R ⁵in aromatic series base can be aromatic hydrocarbyl, also can be aromatic heterocycle, but be preferably aromatic hydrocarbyl.The carbon number of aromatic series base is preferably 6 ~ 16, is more preferably 6 ~ 12.

As the aromatic hydrocarbyl in aromatic series base, be preferably phenyl, naphthyl, be more preferably phenyl.

R ¹, R ³and R ⁵above-mentioned each base can have substituting group.

As this substituting group, there is no particular restriction, can enumerate: (be preferably carbon number is 1 ~ 10 to alkyl, such as methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-carboxymethyl etc.), (be preferably carbon number is 2 ~ 20 to thiazolinyl, such as vinyl, allyl group, oleyl (oleyl) etc.), (be preferably carbon number is 2 ~ 20 to alkynyl, such as ethynyl, diacetylene base (butadiynyl), phenylene-ethynylene etc.), (be preferably carbon number is 3 ~ 20 to cycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl etc.), (be preferably carbon number is 6 ~ 26 to aryl, such as phenyl, 1-naphthyl, 4-p-methoxy-phenyl, 2-chloro-phenyl-, 3-aminomethyl phenyl etc.), (be preferably carbon number is the heterocyclic radical of 0 ~ 20 to heterocyclic radical, and ring forms heteroatoms and is preferably Sauerstoffatom, nitrogen-atoms, sulphur atom, 5 rings or 6 rings can be utilized on phenyl ring or heterocycle to carry out contracting ring, and this ring can be saturated rings, unsaturated ring, aromatic nucleus, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl-, 2-thiazolyl, 2-oxazolyl etc.), (be preferably carbon number is 1 ~ 20 to alkoxyl group, such as methoxyl group, oxyethyl group, isopropoxy, benzyloxy etc.), (be preferably carbon number is 6 ~ 26 to aryloxy, such as phenoxy group, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), (be preferably carbon number is 1 ~ 20 to alkylthio, such as methylthio group, ethylmercapto group, isopropyisulfanyl, benzylthio-etc.), (be preferably carbon number is 6 ~ 26 to arylthio, such as thiophenyl, 1-naphthalene sulfenyl, 3-methylphenyl-sulfanyl, 4-Methoxv-phenylsulfanvl etc.), (be preferably the alkylsulfonyl of alkyl or aryl, carbon number is preferably 1 ~ 20 to alkylsulfonyl, such as methyl sulphonyl, ethylsulfonyl, benzenesulfonyl, tosyl group etc.), acyl group (comprises alkyl-carbonyl, alkenyl carbonyl, aryl carbonyl, heterocyclecarbonyl, carbon number is preferably less than 20, such as ethanoyl, pivaloyl (pivaloyl), acryl, methacryloyl, benzoyl, nicotinoyl (nicotinoyl) etc.), (be preferably carbon number is 2 ~ 20 to alkoxy carbonyl, such as ethoxy carbonyl, 2-ethyl hexyl oxy carbonyl etc.), (be preferably carbon number is 7 ~ 20 to aryloxycarbonyl, such as phenyloxycarbonyl, naphthoxycarbonyl etc.), amino (comprises amino, alkylamino, arylamino, heterocyclic amino group, being preferably carbon number is 0 ~ 20, such as amino, N, N-dimethylamino, N, N-diethylin, N-ethylamino, anilino, 1-pyrrolidyl, piperidyl, morpholinyl etc.), (be preferably the sulfoamido of alkyl or aryl, carbon number is preferably 0 ~ 20 to sulfoamido, such as N, N-dimethyl sulfonamide, N-phenyl-sulfamide etc.), (be preferably the sulfamyl of alkyl or aryl, carbon number is preferably 0 ~ 20 to sulfamyl, such as N, N-DimethylsuIfamoyl, N-phenyl sulfamoyl base etc.), (be preferably carbon number is 1 ~ 20 to acyloxy, such as acetoxyl group, benzoyloxy etc.), (be preferably the carbamyl of alkyl or aryl, carbon number is preferably 1 ~ 20 to carbamyl, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl etc.), (be preferably carbon number is 1 ~ 20 to acyl amino, such as acetylamino, Acryloyl amino, benzoyl-amido, niacinamide etc.), cyano group, hydroxyl, sulfydryl or halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.).

Above-mentioned substituting group can and then be replaced by above-mentioned substituting group.Include, for example the alkyl etc. replaced just like the perfluoroalkyl as trifluoromethyl, aralkyl, acyl group.

Moreover, these substituting groups not only R ¹, R ³, R ⁵each base substituting group that can have, and be applied to the substituting group in compound described in present specification.

Herein, R ¹, R ³and R ⁵each base above-mentioned substituting group that can have among, be preferably alkyl, aryl, alkoxyl group, alkylthio, alkyl sulphonyl, halogen atom, acyl group, be more preferably alkyl, aryl, alkoxyl group, acyl group, and then be more preferably alkyl, alkoxyl group.

In compound represented by general formula (I), R ¹, R ³and R ⁵any one be aralkyl or cycloalkyl, be preferably any one be aralkyl.

Wherein, R is preferably ⁵for the compound of aralkyl or cycloalkyl.

R ⁵preferably can replace the alkyl or cycloalkyl having aryl, acyl group; be more preferably alkyl (the i.e. aralkyl replacing and have aryl; hereinafter referred to as aralkyl), replace and have the alkyl of acyl group (be preferably to replace and have the alkyl of acyl group and aryl) or cycloalkyl; and then be more preferably aralkyl or cycloalkyl, be particularly preferably aralkyl.

Below, R is further illustrated ⁵in above-mentioned preferred alkyl, cycloalkyl.

As the alkyl be unsubstituted in alkyl, include, for example: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, n-hexyl, 2-ethylhexyl, n-octyl.

Alternatively there are alkyl and the aralkyl of aryl, include, for example: benzyl, styroyl (phenethyl), 3-phenyl propyl.

Replacing has the acyl group in the alkyl of acyl group to be preferably alkyl-carbonyl, naphthene base carbonyl, aryl carbonyl, wherein, preferably has the naphthene base carbonyl of ring structure, aryl carbonyl, is particularly preferably aryl carbonyl.

As abovementioned alkyl carbonyl; include, for example ethanoyl, propionyl, butyryl radicals, pivaloyl; as naphthene base carbonyl; include, for example cyclopropyl carbonyl, cyclopentylcarbonyl, cyclohexyl-carbonyl; as aryl carbonyl, include, for example benzoyl, toluyl, naphthoyl (naphthoyl).

Replacing has the alkyl of acyl group to include, for example 2-methylaminosulfonylethyl, 3-acyl propyl, 2-acyl propyl, is preferably 2-methylaminosulfonylethyl.

In the present invention, wherein replace and have the alkyl of acyl group to be preferably the alkyl replacing and have acyl group and aryl, the aryl in this situation is preferably phenyl.

Alternatively there is the alkyl of acyl group and aryl, include, for example 1-phenyl-2-benzoylethyl, 1-tolyl-2-benzoylethyl.

Cycloalkyl, aralkyl can enumerate R ¹, R ³and R ⁵in illustrated base.

If enumerate the preferred compound in the compound represented by general formula (I), then as follows.

R ¹, R ³and R ⁵any one be the compound of aralkyl

Moreover among aralkyl, being preferably replacement on alkyl has 1 or 2 aryl persons (when replacement has 2 aryl, being preferably replaced in same carbon atom).And then, alkyl replaces and has aryl and acyl group (preferably aroyl) person also preferred.

R ¹, R ³and R ⁵any one be base containing cycloalkyl, the base be preferably containing cycloalkyl is the compound of cycloalkyl

At above-mentioned " R ¹, R ³and R ⁵in existing ring structure add up to more than 3 " time ring structure in, except R ¹, R ³or R ⁵substituent basic framework itself adopt beyond the situation of ring structure, also comprise as illustrating, R ¹, R ³or R ⁵contained substituting group has the form of ring structure.

As above-mentioned ring structure, be preferably cyclic saturated hydrocarbon structure or aromatic ring structure (aromatic hydrocarbon structures or heteroaromatic structure).In addition, this ring structure also can be contracting ring structure.

When above-mentioned ring structure is cyclic saturated hydrocarbon structure, this cyclic saturated hydrocarbon structure optimization is that the cycloalkyl being 3 ~ 20 as carbon number exists.More specifically, be more preferably as cyclopropyl, cyclopentyl or cyclohexyl and exist, being particularly preferably and existing as cyclohexyl.

In addition, when above-mentioned ring structure is aromatic ring structure, be preferably aromatic hydrocarbon structures.The aryl that it is 6 ~ 20 that this aromatic hydrocarbon structures is preferably as carbon number exists.More specifically, be more preferably as phenyl, naphthyl and existing, be particularly preferably and exist as phenyl.

With regard to the viewpoint of steady dissolution during masking, the compound represented by general formula (I) is more preferably R ¹, R ³and R ⁵for carbon number be 1 ~ 20 alkyl, carbon number be 2 ~ 20 thiazolinyl or carbon number be the aryl of 6 ~ 20.In addition, R is more preferably ¹, R ³and R ⁵there is the ring structure of more than 1 respectively, and then be more preferably there is 1 ring structure respectively.

Compound represented by general formula (I) of the present invention is more preferably the compound represented by following general formula (I-a).

[changing 4]

In general formula (I-a), L ¹, L ³and L ⁵separately represent that singly-bound or carbon number are the concatenating group of the divalence of more than 1.L ¹, L ³and L ⁵be more preferably singly-bound or carbon number is the alkylidene group of 1 ~ 6, and then be more preferably singly-bound, methylene radical or ethylidene, be particularly preferably singly-bound or methylene radical.If consider steady dissolution, be then preferably L ¹, L ³and L ⁵in at least one for carbon number be the alkylidene group of 1 ~ 6, be preferably methylene radical or ethylidene.

By L ¹, L ³and L ⁵the concatenating group of represented divalence can have substituting group, and this substituting group can enumerate above-mentioned R ¹, R ³and R ⁵each base substituting group that can have.

In general formula (I-a), Ar ¹, Ar ³and Ar ⁵separately represent that carbon number is the aryl of 6 ~ 20, is preferably phenyl, naphthyl, is more preferably phenyl.Ar ¹, Ar ³and Ar ⁵can have substituting group, this substituting group can enumerate above-mentioned R ¹, R ³and R ⁵each base substituting group that can have.As this kind of substituting group, its implication and R ¹, R ³and R ⁵for the substituting group that can carry out during aromatic series base replacing is identical, preferred scope is also identical.

Work as Ar ¹, Ar ³and Ar ⁵when not having substituting group or have substituting group, this substituting group does not preferably have ring structure.

The molecular weight of the compound represented by general formula (I) and general formula (I-a) is preferably 250 ~ 1200, is more preferably 300 ~ 800, is particularly preferably 350 ~ 600.

By molecular weight being set to this kind of preferred scope, excellence in being vaporized in film of suppressing compound of the present invention, can obtain the film that the transparency is high.

Below, represent the concrete example of the compound represented by general formula (I) of the present invention, but the present invention is not limited to these concrete examples.

[changing 5]

[changing 6]

[changing 7]

[changing 8]

[changing 9]

Known compound represented by general formula (I) of the present invention can utilize the synthesis method making urea derivatives and malonate derivative carry out the barbituric acid of condensation to synthesize.Nitrogen-atoms has 2 substituent barbituric acids by N, N ' bis-substituted type urea and malonyl chloride heat, or carry out heating obtaining after the activator such as propanedioic acid and diacetyl oxide is combined, such as preferably can use " JACS (Journal of the American Chemical Society) " (the 61st volume, 1015 pages (nineteen thirty-nine)), " pharmaceutical chemistry magazine (Journal of Medicinal Chemistry) " (the 54th volume, 2409 pages (2011)), " Tet Lett (Tetrahedron Letters) " (the 40th volume, 8029 pages (1999)), method described in International Publication No. 2007/150011 handbook etc.

In addition, the propanedioic acid for condensation can be and is unsubstituted, and also to can be to have substituent, is equivalent to R if use to have ⁵substituent propanedioic acid, then can synthesize the compound represented by general formula (I) of the present invention by constructing barbituric acid.In addition, the propanedioic acid be unsubstituted if make and urea derivatives carry out condensation, then can obtain 5 barbituric acids be unsubstituted, and therefore by modifying it, also can synthesize the compound represented by general formula (I) of the present invention.

As the method for the modification of 5, can use with the nucleophilic substitution reaction of halogenated alkyl etc. or as Michael addition (MichaelAddition) react as addition reaction.In addition, also preferably can use and carry out dehydrating condensation with aldehydes or ketones and generate alkylidene compound or arylidene (arylidene) compound, the method for thereafter double bond being reduced.Such as in " Tet Lett " (the 44th volume, 2203 pages (2003)), record the method for reducing utilizing zinc, in " Tet Lett " (the 42nd volume, 4103 pages (calendar year 2001)) or " JACS " (the 119th volume, 12849 pages (1997)), record the method for reducing utilizing contact reduction, record in " Tet Lett " (the 28th volume, 4173 pages (1987)) and utilize NaBH ₄method of reducing.These methods are the synthetic method situation or 5 that can be preferably used for 5 having aralkyl with the situation of cycloalkyl.

Moreover the synthesis method of the compound represented by general formula (I) used in the present invention is not limited to aforesaid method.

The content of compound in cellulose acylate film represented by general formula (I) is not particularly limited; relative to acylated cellulose 100 mass parts; be preferably 0.1 mass parts ~ 20 mass parts, be more preferably 0.2 mass parts ~ 15 mass parts, be particularly preferably 0.3 mass parts ~ 10 mass parts.

By the addition of the compound represented by general formula (I) is set to above-mentioned scope, and effectively can reduce Water Vapour Permeability, in addition, the generation of mist degree (haze) can be suppressed.

< acylated cellulose >

In the present invention, acylated cellulose is used as the principal constituent of film.Herein, in this manual, so-called " principal constituent ", is be called " principal constituent " by this composition in the form of a kind at the composition becoming raw material, is in form of more than two kinds, is called " principal constituent " by composition the highest for mass fraction at the composition becoming raw material.Only can use a kind of acylated cellulose, also can use two or more.About the acyl substituent of acylated cellulose, such as, can be the acylated cellulose only comprising ethanoyl, also can use the acylated cellulose with multiple different acyl substituents, also can be the mixture of different acylated celluloses.

As the Mierocrystalline cellulose of the raw material of the acylated cellulose used in the present invention, there are velveteen or wood pulp (deciduous tree paper pulp, softwood tree paper pulp) etc., the acylated cellulose obtained from any raw cellulose can be used, according to circumstances also can be used in combination.Detailed record for these raw celluloses such as can use " plastic material lecture (17) cellulose-based resin ", and (ball is damp, space field is outstanding, Nikkan Kogyo Shimbun's (distribution in 1970)), or Mierocrystalline cellulose described in No. 2001-1745, institute of invention Technical Publication Technical Publication No. (7 pages ~ 8 pages).

In the present invention, the acyl group of acylated cellulose can be only a kind or also can use acyl group of more than two kinds.The acylated cellulose used in the present invention preferably has the acyl group alternatively base that carbon number is 2 ~ 4.When using acyl group of more than two kinds, being preferably wherein one is ethanoyl, is the acyl group of 2 ~ 4 as carbon number used in addition, is preferably propionyl or butyryl radicals.Can usually manufacture the preferred solution of solvability by these acylated cellobioses, especially in chlorine-free organic solvent, good solution can be made.And then, the solution that viscosity is low, filterableness is good can be made.

First, record in detail acylated cellulose of the present invention can be preferably used for.

Forming cellulosic bond has the glucose of β-Isosorbide-5-Nitrae (gluoose) unit to have free hydroxyl on 2,3 and 6.Acylated cellulose utilizes acyl group by the polymkeric substance (polymer) of part or all acylations in addition of these hydroxyls.

Acyl substitution represents the degree of the acylations of the cellulosic hydroxyl be positioned on 2,3 and 6; when the hydroxyl of 2,3 of all glucose units and 6 is all through acylations; total acyl substitution is 3; such as when in all glucose units; only 6 all when acylations, total acyl substitution is 1.Similarly, when in all hydroxyls at all glucose, in each glucose unit, any one of 6 or 2 is all when acylations, and total acyl substitution is also 1.

That is, all hydroxyls in glucose molecule are all set to 3 to represent the degree of acylations through the situation of acylations.

About the details of the measuring method of acyl substitution; can according to Asklsl etc., in " carbohydrate research (Carbohydr.Res.) " (273,83-91 (1995)), in described method or ASTM-D817-96, the method for defined measures.

Total acyl substitution (A) of the acylated cellulose used in the present invention is preferably more than 1.5, less than 3 (1.5≤A≤3.0); be more preferably 2.0 ~ 2.97; and then be more preferably more than 2.5, less than 2.97, be particularly preferably 2.70 ~ 2.95.

In addition; in the rhodia only using ethanoyl as the acyl group of acylated cellulose; total degree of substitution with acetyl group (B) is preferably more than 2.0, less than 3 (2.0≤B≤3.0); be more preferably 2.0 ~ 2.97; and then be more preferably more than 2.5, less than 2.97, wherein, be preferably more than 2.55, less than 2.97; be particularly preferably 2.60 ~ 2.96, most preferably be 2.70 ~ 2.95.

Moreover the compound represented by general formula (I) of the present invention, for total degree of substitution with acetyl group (B) acylated cellulose more than 2.50, shows effect especially effectively.

Carbon number as the acylated cellulose used in the present invention is the acyl group of more than 2, can be aliphatic acyl group, also can be aromatic acyl group, is not particularly limited.These acyl groups are such as cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester, aromatic carbonyl ester or aromatic alkyl carbonyl ester (aromatic alkyl carbonyl ester), and these acyl groups also can have substituting group.Above-mentioned carbon number be more than 2 acyl group be preferably ethanoyl, propionyl, butyryl radicals, pentanoyl, oenanthyl, caproyl, capryloyl, decanoyl, lauroyl, tridecanoyl, myristoyl, palmitoyl, stearoyl, isobutyryl, tertiary butyryl radicals, cyclohexane carbo, oleoyl (oleoyl), benzoyl, naphthyl carbonyl or cinnamoyl (cinnamoyl).Among these; be more preferably ethanoyl, propionyl, butyryl radicals, lauroyl, stearoyl, tertiary butyryl radicals, oleoyl, benzoyl, naphthyl carbonyl or cinnamoyl; and then the carbonatoms be more preferably as ethanoyl, propionyl or butyryl radicals is the acyl group of 2 ~ 4; and then be more preferably ethanoyl (that is, acylated cellulose is the situation of rhodia).

In cellulosic acylations process; when using acid anhydrides or acyl chlorides as acylating agent, the organic solvent as reaction solvent preferably can use organic acid solvent or halogen solvent (such as acetic acid or methylene dichloride (methylene chloride)).

As catalyzer, when acylating agent is acid anhydrides, preferably can use the protic catalyzer as sulfuric acid, when acylating agent is acyl chlorides (such as CH ₃cH ₂cOCl), time, basic cpd can be used.

The industrial preparative method of the most general cellulosic mixed aliphatic ester is following method: the mixed organic acid composition utilizing the acid anhydrides containing the lipid acid corresponding to the acyl group such as ethanoyl (such as corresponding to acetic acid, the propionic acid corresponding to propionyl, the valeric acid etc. corresponding to pentanoyl of ethanoyl) or this lipid acid, by Mierocrystalline cellulose in addition acylations.

Acylated cellulose such as synthesizes by method described in Japanese Patent Laid-Open 10-45804 publication.

With regard to the viewpoint of Water Vapour Permeability; cellulose acylate film of the present invention is preferably in total solids composition; acylated cellulose containing 5 quality % ~ 99 quality %; be more preferably the acylated cellulose containing 20 quality % ~ 99 quality %, be particularly preferably the acylated cellulose containing 50 quality % ~ 95 quality %.

Other additives of < >

In cellulose acylate film of the present invention, also can add and postpone the additive such as adjusting agent (postpone visualization reagent and postpone depressant), fluidizer (the polynary ester, phthalic ester, phosphoric acid ester etc. of polycondensation ester cpds (polymkeric substance), polyvalent alcohol), UV light absorber, antioxidant, matting agent.

Such as, moreover in present specification, when wanting tagged compound group, as phosphoric acid ester based compound, sometimes add " being " to record, in these cases, its implication is identical with phosphate compound.

(delay depressant)

Polymer at least a kind of postponing that depressant is preferably selected from phosphoric acid polyester polymers, styrene polymer, acrylate copolymer and these multipolymer, is more preferably at least a kind of being selected from acrylate copolymer and styrene polymer and has negative intrinsic birefringent polymkeric substance.

In addition, the lower molecular weight of non-phosphate compound also can be preferably used as to postpone depressant.

Lower molecular weight as non-phosphate compound postpones depressant and is not particularly limited, and specifically, is preferably compound described in the paragraph 0066 ~ paragraph 0085 of Japanese Patent Laid-Open 2007-272177 publication.

With regard to realizing the viewpoint of suitable Nz factor (factor), postpone depressant and be more preferably Rth depressant.As Rth depressant, the low molecular compound etc. represented by general formula (3) ~ general formula (7) described in acrylate copolymer and styrene polymer, Japanese Patent Laid-Open 2007-272177 publication can be enumerated.

Relative to acylated cellulose 100 mass parts, the content of the delay depressant in cellulose acylate film is preferably 0.01 mass parts ~ 30 mass parts, is more preferably 0.1 mass parts ~ 20 mass parts, is particularly preferably 0.1 mass parts ~ 10 mass parts.By relative to acylated cellulose 100 mass parts, the addition postponing depressant is set to below 30 mass parts, and the consistency with acylated cellulose can be promoted, and the transparency of cellulose acylate film can be improved.When using delay depressant of more than two kinds, being preferably its total amount is in above-mentioned scope.

(delay visualization reagent)

In order to make length of delay manifest, cellulose acylate film of the present invention is preferably and postpones visualization reagent containing at least a kind.

As delay visualization reagent, there is no particular restriction, can enumerate comprise rod-shaped compound or discoid compound or demonstrate the compound postponing manifesting property in above-mentioned non-phosphate compound.As rod-shaped compound or discoid compound, the compound with at least 2 aromatic rings preferably can be used as to postpone visualization reagent.

In cellulose acylate film, relative to component of polymer 100 mass parts containing acylated cellulose, the content comprising the delay visualization reagent of rod-shaped compound is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 0.5 mass parts ~ 20 mass parts.In addition, in cellulose acylate film, relative to acylated cellulose 100 mass parts, the content postponing discoid compound contained in visualization reagent is preferably less than 3 mass parts, is more preferably less than 2 mass parts, is particularly preferably less than 1 mass parts.

In delay (Rth delay) the manifesting property of film thickness direction, discoid compound is better than rod-shaped compound, therefore can be preferably used for the situation needing king-sized Rth to postpone.Also can and with delay visualization reagent of more than two kinds.

Postpone visualization reagent and preferably in the wavelength region may of 250nm ~ 400nm, there is maximum absorption, and preferably in visibility region, not there is absorption in fact.

The details postponing visualization reagent is on the books in 49 pages of Technical Publication 2001-1745.

(fluidizer (hydrophobizers))

Cellulose acylate film of the present invention be preferably containing be selected from polyvalent alcohol polybasic esterification compound (after; also referred to as polyol ester fluidizer), polycondensation ester cpds (after; also referred to as polycondensation ester fluidizer) and carbohydrate compound (after, also referred to as carbohydrate derivative fluidizer) in the compound of at least one as fluidizer (hydrophobizers).

The second-order transition temperature (Tg) that fluidizer does not preferably acidylate cellulose membrane as far as possible declines and the water ratio person that can reduce in cellulose acylate film.By using this kind of fluidizer, and the additive in hot and humid lower cellulose acylate film can be suppressed to spread towards layer of polarizer, and the deterioration of polaroid performance can be improved.

Below the fluidizer used in the present invention is described in detail.

(polyol ester fluidizer)

In the present invention, the polyvalent alcohol as the synthesis material of polyol ester fluidizer is represented by following general formula (c).

General formula (c)

Rα-(OH)m

In general formula (c), R α represents the organic radical of m valency, and m represents the positive integer of more than 2.

Among compound represented by above-mentioned general formula (c), be preferably ribitol (adonitol), arabitol (arabitol), ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1, 2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, dibutylene glycol, 1, 2, 4-trihydroxybutane, 1, 5-pentanediol, 1, 6-hexylene glycol, hexanetriol, melampyrum (galactitol), N.F,USP MANNITOL (mannitol), 3-methylpentane-1, 3, 5-triol, tetramethyl ethylene ketone (pinacol), Sorbitol Powder, TriMethylolPropane(TMP), trimethylolethane, or Xylitol is as raw material, be more preferably triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, Sorbitol Powder, TriMethylolPropane(TMP), or Xylitol.

It is the polyvalent alcohol of more than 5 that polyol ester fluidizer is preferably from carbon number, to be preferably carbon number be 5 ~ 20 polyvalent alcohol and the polyol ester synthesized by monocarboxylic acid.

For the monocarboxylic acid of the synthesis of polyol ester fluidizer, there is no particular restriction, can enumerate known aliphatics monocarboxylic acid, alicyclic monocarboxylic acid, aromatic series monocarboxylic acid etc.If use alicyclic monocarboxylic acid or aromatic series monocarboxylic acid, then preferred with regard to promoting the viewpoint of water vapour permeability, retention.

Monocarboxylic acid can enumerate following compound, but the present invention is not limited to these compounds.

It is the straight chain of 1 ~ 32 or the lipid acid of branch that aliphatics monocarboxylic acid is preferably carbon number.Carbon number is more preferably 1 ~ 20, is particularly preferably 1 ~ 10.If containing acetic acid, then to increase with the consistency of derivatived cellulose, therefore preferably, by acetic acid and other monocarboxylic acids used in combination also preferred.

Above-mentioned aliphatics monocarboxylic acid is preferably selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undeeanoic acid, lauric acid, tridecylic acid, tetradecanoic acid, pentadecanoic acid, palmitinic acid, margaric acid, stearic acid, nonadecanoic acid, eicosanoic acid, behenic acid (behenic acid), tetracosanoic acid (lignoceric acid), cerinic acid (ceroticacid), carboceric acid (heptacosanoic acid), octacosanoic acid (montanic acid), myricyl acid (melissic acid), and at least a kind of saturated fatty acid in lacceroic acid (lacceric acid), or be selected from undecylenic acid, oleic acid, Sorbic Acid, linolenic acid (linoleic acid), linolenic acid (linolenic acid), and at least a kind of unsaturated fatty acids in arachic acid (arachidonic acid).

Above-mentioned alicyclic monocarboxylic acid is preferably selected from least a kind in Cyclopentane carboxylic acid, hexahydrobenzoic acid, cyclooctanecarboxylic acid and these derivative.

Above-mentioned aromatic series monocarboxylic acid is preferably selected from phenylformic acid, alkyl is directed into the person of forming in benzoic phenyl ring by toluic acid (toluic acid) etc., biphenyl carboxylic acids, naphthalene monocarboxylic acid, naphthane carboxylic acid etc. have the aromatic series monocarboxylic acid of the phenyl ring of more than 2, and in these derivative at least a kind.Wherein, phenylformic acid is preferably.

There is no particular restriction for the molecular weight of above-mentioned polyol ester fluidizer, but be preferably 300 ~ 3000, is more preferably 350 ~ 1500.By being set to this kind of molecular weight, suppressing excellent in the volatilization in film, water vapour permeability can made, become good with the consistency of derivatived cellulose.

Carboxylic acid for the synthesis of polyol ester fluidizer can be only a kind, also can mix two or more.In addition, the hydroxyl in polyvalent alcohol all can carry out esterification, and a part also can be made to maintain the state of hydroxyl and remaining.

Below, represent the concrete example of polyol ester fluidizer, but the present invention is not limited to these concrete examples.

[changing 10]

[changing 11]

[changing 12]

[changing 13]

(polycondensation ester fluidizer)

It is also preferred that cellulose acylate film of the present invention contains polycondensation ester fluidizer.By containing polycondensation ester fluidizer, and the cellulose ester membrane of humidity stability, Polarizer excellent in te pins of durability can be obtained

Polycondensation ester fluidizer makes at least a kind of dicarboxylic acid represented by following general formula (a), carries out polycondensation with at least a kind of glycol represented by following general formula (b) and obtain.

[changing 14]

In general formula (a), general formula (b), X represents the carbon number of divalence to be the fatty group of 2 ~ 18 or the carbon number of divalence is the aromatic series base of 6 ~ 18, and Z represents that the carbon number of divalence is the fatty group of 2 ~ 8.

Herein, the carbon number of the divalence in X be 2 ~ 18 fatty group can be representative examples of saturated aliphatic base, also can be unsaturated aliphatic base, and can be the chain of divalence or the fatty group (such as cycloalkylidene etc.) of ring-type any one.In addition, when it is the fatty group of the chain of divalence, can be straight-chain, also can be branch-like.The carbon number of the fatty group of divalence is more preferably 2 ~ 12, and then is more preferably 2 ~ 6.Wherein, the carbon number of divalence be 2 ~ 18 fatty group be preferably the representative examples of saturated aliphatic base of the chain of divalence, be more preferably the alkylidene group of chain, and then be more preferably the alkylidene group of straight-chain.It is the fatty group of the chain of 2 ~ 18 as carbon number, include, for example: ethylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene radical, decamethylene, ten dimethylenes, propylidene, 2-methyl trimethylene, 2,2-dimethyltrimethylene, cyclopentylidene, cyclohexylidene etc.

The carbon number of the divalence in X be 6 ~ 18 aromatic series base can be the aromatic hydrocarbyl of divalence, also can be the aromatic heterocycle of divalence.As the aromatic series base of divalence, carbon number is preferably 6 ~ 15, is more preferably 6 ~ 12.Aromatic nucleus in the aromatic hydrocarbyl of divalence is preferably phenyl ring, naphthalene nucleus, anthracene nucleus, cyclohexyl biphenyl or terphenyl ring, is more preferably phenyl ring, naphthalene nucleus or cyclohexyl biphenyl.Heteroaromatic in the aromatic heterocycle of divalence is preferably containing at least 1 in Sauerstoffatom, nitrogen-atoms or sulphur atom as ring atom.This heteroaromatic is preferably furan nucleus, pyrrole ring, thiphene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine skeleton, thiazoline ring, Thiadiazole, oxazoline ring, oxazole ring, oxadiazole rings, quinoline ring, isoquinoline 99.9 ring, phthalazines ring, naphthyridines ring, quinoxaline ring, quinazoline ring, cinnolines ring (cinnoline ring), to talk endlessly pyridine ring, acridine ring, phenanthroline ring (phenanthroline ring), azophenlyene ring, tetrazole ring, benzoglyoxaline ring, benzoxazole ring, benzothiazole ring, benzotriazole ring or purine ring (tetrazaindene ring), be more preferably pyridine ring, triazine ring or quinoline ring.

Z represents that the carbon number of divalence is the fatty group of 2 ~ 8.The carbon number of divalence be 2 ~ 8 fatty group can be representative examples of saturated aliphatic base, also can be unsaturated aliphatic base, and can be the chain of divalence or the fatty group (such as cycloalkylidene etc.) of ring-type any one.In addition, when it is the fatty group of the chain of divalence, can be the straight-chain of divalence, also can be branch-like.The carbon number of the fatty group of divalence is more preferably 2 ~ 6, and then is more preferably 2 ~ 4.Wherein, the carbon number of divalence be 2 ~ 8 fatty group be preferably the representative examples of saturated aliphatic base of the chain of divalence, be more preferably the alkylidene group of chain, and then be more preferably the alkylidene group of straight-chain.Carbon number is that the alkylidene group of the chain of 5 ~ 10 such as include, for example ethylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene radical, decamethylene, propylidene, 2-methyl trimethylene, 2,2-dimethyltrimethylene etc.

Moreover, as the cycloalkylidene of divalence, cyclopentylidene, cyclohexylidene can be enumerated.

Aliphatic diol represented by general formula (b) is more preferably and is selected from ethylene glycol, 1, at least a kind in 2-propylene glycol and 1,3-PD, with regard to preventing the viewpoint of the crystallization of polycondensation ester fluidizer, be particularly preferably at least a kind that is selected from ethylene glycol and 1,2-PD.

In the aliphatic diol residue of polycondensation ester fluidizer, be preferably the glycol residue containing 10mol% ~ 100mol%, be more preferably the glycol residue containing 20mol% ~ 100mol%.

Polycondensation ester fluidizer is preferably at least a kind of dicarboxylic acid (also referred to as aromatic dicarboxylic acid) from the X aromatic series base that is above-mentioned divalence, at least a kind of compound obtained with the Z glycol (also referred to as aliphatic diol) that is above-mentioned fatty group.The average carbon number of the aliphatic diol used is preferably 2.5 ~ 8.0.In addition, also preferred from the mixture of at least one aromatic dicarboxylic acid and the X at least one dicarboxylic acid (also referred to as aliphatic dicarboxylic acid) that is the fatty group of above-mentioned divalence, the polycondensation ester fluidizer that obtains with at least one average carbon number aliphatic diol that is 2.5 ~ 8.0.

In the explanation of polycondensation ester fluidizer, the calculating of the average carbon number of dicarboxylic acid or dicarboxylic acid residue is following value: the total of the carbon number that the whole dicarboxylic acid residue in the whole dicarboxylic acid used or polycondensation ester fluidizer have is divided by the value of the mole number gained of the dicarboxylic acid residue in the mole number of used dicarboxylic acid or polycondensation ester fluidizer.Such as, when in whole dicarboxylic acid residue, when comprising hexanodioic acid residue and each 50mol% of phthalic acid residue respectively, the average carbon number of dicarboxylic acid residue becomes 7.0.The average carbon number of glycol or diol residue calculates similarly.Such as when comprising glycol residue 50mol% and 1,2-PD residue 50mol%, the average carbon number of diol residue becomes 2.5.

The number average molecular weight of polycondensation ester fluidizer is preferably 500 ~ 2000, is more preferably 600 ~ 1500, and then is more preferably 700 ~ 1200.If the number average molecular weight of polycondensation ester is more than 600, then volatility step-down, under hot conditions during extension by cellulose ester membrane to be vaporized the suppression that caused film fault or step pollute excellent.

In addition, if number average molecular weight is less than 2000, then uprise with the consistency of cellulose ester, the suppression of oozing out during masking and when heating extends is excellent.

The number average molecular weight of polycondensation ester fluidizer is undertaken measuring, evaluating by gel permeation chromatography.In addition, when the polyester polyol of end not end-blocking, the amount (hereinafter also referred to as hydroxyl value) also by the hydroxyl of unit mass calculates.In the present invention, hydroxyl value after polyester polyol is in addition acetylating, can measure the amount (mg) of the superfluous potassium hydroxide needed for acetic acid of neutralization and obtains.

When the mixture of aromatic dicarboxylic acid and aliphatic dicarboxylic acid is used as dicarboxylic acid component, the average carbon number of dicarboxylic acid component is preferably 5.5 ~ 10.0, is more preferably 5.6 ~ 8.

By average carbon number is set to more than 5.5, and the more excellent Polarizer of weather resistance can be obtained.In addition, by average carbon number is set to less than 10, more excellent with the consistency of cellulose ester, the suppression of oozing out in the film-forming process of cellulose ester membrane is excellent.

In the polycondensation ester using aromatic dicarboxylic acid to obtain, containing aromatic dicarboxylic acid residue.

In the dicarboxylic acid residue of the polycondensation ester fluidizer used in the present invention, the ratio of aromatic dicarboxylic acid residue is preferably more than 40mol%, is more preferably 40mol% ~ 95mol%.

By the ratio of the aromatic dicarboxylic acid residue in dicarboxylic acid residue is set to more than 40mol%, and can obtains and demonstrate sufficient optically anisotropic cellulose ester membrane, and the Polarizer of excellent in te pins of durability can be obtained.In addition, by the ratio of the aromatic dicarboxylic acid residue in dicarboxylic acid residue is set to below 95mol%, with the excellent compatibility of cellulose ester, the suppression of oozing out when the masking of cellulose ester membrane and when heating extends is also excellent.

Dicarboxylic acid residue is the part-structure of polycondensation ester, such as, from dicarboxylic acid HOC (=O)-X-CO ₂the dicarboxylic acid residue that H is formed be-C (=O)-X-C (=O)-.

The aromatic dicarboxylic acid that can be used for the synthesis of polycondensation ester fluidizer is preferably selected from phthalic acid, terephthalic acid, m-phthalic acid, 1,5-naphthalic acid, Isosorbide-5-Nitrae-naphthalic acid, 1,8-naphthalic acid, 2, at least a kind in 8-naphthalic acid and NDA.Wherein, be more preferably at least a kind that is selected from phthalic acid, terephthalic acid and NDA, and then be more preferably at least a kind that is selected from phthalic acid and terephthalic acid, and then be more preferably terephthalic acid.

Can in the synthesis of plain agent, use terephthalic acid as aromatic dicarboxylic acid at polycondensation ester, more excellent with the consistency of cellulose ester thus, can be made into the cellulose ester membrane that the suppression of oozing out when the masking of cellulose ester membrane and when heating extends is also excellent.In addition, a kind of aromatic dicarboxylic acid can be used, also can use two or more.When use 2 kinds of aromatic dicarboxylic acids, be preferably and use phthalic acid and terephthalic acid.

In addition, by also with phthalic acid and these 2 kinds of aromatic dicarboxylic acids of terephthalic acid, the polycondensation ester under normal temperature can be made plain agent can to soften and become preferred with regard to easy viewpoint with regard to operation.

The content of the terephthalic acid residue in the dicarboxylic acid residue of polycondensation ester fluidizer is preferably 40mol% ~ 100mol%.

By terephthalic acid residue's ratio is set to more than 40mol%, and can obtains and demonstrate sufficient optically anisotropic cellulose ester membrane.

In the polycondensation ester using aliphatic dicarboxylic acid to obtain, containing aliphatic dicarboxylic acid residue.

Aliphatic dicarboxylic acid for the synthesis of polycondensation ester fluidizer is preferably selected from least a kind in oxalic acid, propanedioic acid, succinic acid, maleic acid, FUMARIC ACID TECH GRADE, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid and Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid.

The average carbon number of aliphatic dicarboxylic acid residue is preferably 5.5 ~ 10.0, is more preferably 5.5 ~ 8.0, and then is more preferably 5.5 ~ 7.0.If the average carbon number of aliphatic dicarboxylic acid residue is less than 10.0; then can reduce the weight loss on heating of compound; and the generation of condition of surface fault can be prevented, the caused step of the oozing out when producing cause of this condition of surface fault can be thought dry by acylated cellulose net is polluted.In addition, if the average carbon number of aliphatic dicarboxylic acid residue is more than 5.5, then excellent compatibility, the precipitation of polycondensation ester is difficult to produce and preferably.

Specifically, the aliphatic dicarboxylic acid residue in polycondensation ester fluidizer is preferably containing succinic acid residue.In addition, when containing aliphatic dicarboxylic acid residue of more than two kinds in polycondensation ester fluidizer, this aliphatic dicarboxylic acid residue is preferably containing succinic acid residue and hexanodioic acid residue.

Containing diol residue in polycondensation ester fluidizer.

Be-O-Z-O-by the diol residue formed with the diol compound (HO-Z-OH) represented by general formula (b).

Polycondensation ester fluidizer be preferably containing average carbon number be 2.5 ~ 7.0 aliphatic diol residue, be more preferably containing average carbon number be 2.5 ~ 4.0 aliphatic diol residue.

If the average carbon number of aliphatic diol residue is less than 7.0; then improve with the consistency of cellulose ester, be difficult to generation and ooze out, in addition; the weight loss on heating of compound is difficult to increase, and be difficult to produce can think reason be acylated cellulose net dry time the condition of surface fault polluted of step.In addition, if the average carbon number of aliphatic diol residue is more than 2.5, then easily synthesize.

The end of polycondensation ester fluidizer can not end-blocking and directly (that is, polymkeric substance chain length end is-OH or-CO as glycol or carboxylic acid ₂h) ,-OH end and monocarboxylic acid also can and then be made to carry out reacting or making-CO ₂h end and monohydroxy-alcohol carry out reaction to carry out so-called end-capped.Moreover by carrying out end-blocking to the end of polycondensation ester fluidizer, state is at normal temperatures difficult to become solid shape, operation becomes good.In addition, the cellulose ester membrane of humidity stability, Polarizer excellent in te pins of durability can be obtained.

Monocarboxylic acid for end-blocking is preferably selected from least a kind in acetic acid, propionic acid, butyric acid and phenylformic acid.As the monohydroxy-alcohol for end-blocking, be preferably selected from least a kind in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and isopropylcarbinol, most preferably be methyl alcohol.If the monocarboxylic carbon number for the end of polycondensation ester is less than 7, then the weight loss on heating of compound diminishes, and the suppression of the generation of condition of surface fault is excellent.

Enumerate the concrete example J-1 ~ concrete example J-41 of polycondensation ester fluidizer in following table 1, but the present invention is not limited to these concrete examples.

[table 1]

Herein, in abbreviation in table 1 above, PA represents phthalic acid, and TPA represents terephthalic acid, and AA represents hexanodioic acid, and SA represents succinic acid, and 2,6-NPA represents NDA.

The synthesis of polycondensation ester fluidizer is easily synthesized by any one following method: by the polyesterification reaction of glycol and dicarboxylic acid that utilizes ordinary method or the acyl chlorides of the heat fusing condensation method of transesterification reaction or these acid and the interfacial condensation method of glycols.In addition, be documented in polycondensation Zhi village well filial piety one (human editor) " its theoretical and application of fluidizer " (good fortune study limited-liability company, the 1st edition distribution of first edition on March 1st, 1973), also can use these compounds.

In the present invention, as polycondensation ester fluidizer, compound described in each publication of No. 05-155809, Japanese Patent Laid-Open, No. 05-155810, Japanese Patent Laid-Open, No. 5-197073, Japanese Patent Laid-Open, No. 2006-259494, Japanese Patent Laid-Open, No. 07-330670, Japanese Patent Laid-Open, No. 2006-342227, Japanese Patent Laid-Open, No. 2007-003679, Japanese Patent Laid-Open etc. also can be utilized.

(carbohydrate derivative fluidizer)

Cellulose acylate film of the present invention is preferably and then contains carbohydrate derivative fluidizer.By containing carbohydrate derivative fluidizer, and the cellulose ester membrane of humidity stability, Polarizer excellent in te pins of durability can be obtained.

As carbohydrate derivative fluidizer, be preferably the derivative of monose or the carbohydrate containing 2 ~ 10 monosaccharide units.

Preferably form part or all of the base (such as hydroxyl, carboxyl, amino, sulfydryl etc.) that the monose of carbohydrate derivative fluidizer or polysaccharide replaced by the carrying out that substituting group replaces in molecule.As the substituting group that carbohydrate derivative fluidizer can have, can enumerate alkyl, aryl, acyl group etc., details is by aftermentioned.In addition, can enumerate replaced by alcohol and the ether structure formed, hydroxyl formed by acyl substituted ester structure, replaced by amino and the amide structure formed or imide structure etc.

Monose or the carbohydrate containing 2 ~ 10 monosaccharide units are preferably red algae sugar, threose, ribose, pectinose, wood sugar, lyxose, allose, altrose, glucose, fructose, seminose, gulose, idose, semi-lactosi, talose, trehalose, isotrehalose, neotrehalose, Trehalosamine (trehalosamine), kojibiose, Nigerose (nigerose), maltose, maltose alcohol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactose amine, Saccharum lactis, milk ketose, melibiose, primeverose, rutinose, scillarabiose, sucrose, Sucralose, turanose, vicianose (vicianose), procellose, chacotriose (chacotriose), gentianose, Isomaltotriose, isopanose (isopanose), trisaccharide maltose, mannotriose, melizitose, Pernod sugar, planteose (planteose), raffinose, solatriose (solatriose), umbelliferose, lycotetraose, maltotetrose, stachyose, maltopentaose, verbascose, MALTOHAXAOASE, alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, Xylitol, or Sorbitol Powder.

Be preferably ribose, pectinose, wood sugar, lyxose, glucose, fructose, seminose, semi-lactosi, trehalose, maltose, cellobiose, lactose, sucrose, Sucralose, alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, Xylitol, Sorbitol Powder, be more preferably pectinose, wood sugar, glucose, fructose, seminose, semi-lactosi, maltose, cellobiose, sucrose, beta-cyclodextrin, or γ-cyclodextrin, be particularly preferably wood sugar, glucose, fructose, seminose, semi-lactosi, maltose, cellobiose, sucrose, Xylitol, or Sorbitol Powder.

In addition, the substituting group that carbohydrate derivative fluidizer has is preferably alkyl, and (being preferably carbon number is 1 ~ 22, being more preferably carbon number is 1 ~ 12, be particularly preferably the alkyl that carbon number is 1 ~ 8, such as methyl, ethyl, propyl group, hydroxyethyl, hydroxypropyl, 2-cyano ethyl, benzyl etc.), (be preferably carbon number is 6 ~ 24 to aryl, being more preferably carbon number is 6 ~ 18, be particularly preferably the aryl that carbon number is 6 ~ 12, such as phenyl, naphthyl), acyl group (comprises alkyl-carbonyl, aryl carbonyl, heterocyclecarbonyl, being preferably carbon number is 1 ~ 22, being more preferably carbon number is 2 ~ 12, be particularly preferably the acyl group that carbon number is 2 ~ 8, such as ethanoyl, propionyl, butyryl radicals, pentanoyl, caproyl, capryloyl, benzoyl, toluyl, phthaloyl, naphthoyl etc.).In addition, the preferred structure formed as being replaced by amino, can enumerate: (be preferably carbon number is 1 ~ 22 to amide structure, being more preferably carbon number is 2 ~ 12, be particularly preferably the acid amides that carbon number is 2 ~ 8, such as methane amide, ethanamide etc.) or imide structure (be preferably carbon number be 4 ~ 22, being more preferably carbon number is 4 ~ 12, be particularly preferably the imide that carbon number is 4 ~ 8, such as succinimide, phthalic imidine etc.).

The substituting group that carbohydrate derivative fluidizer has is more preferably at least a kind that is selected from alkyl, aryl and acyl group, and then is more preferably acyl group.

As the preference of carbohydrate derivative fluidizer, following example can be enumerated, but the present invention is not limited to these examples.

Be selected from least a kind in following compound: xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, semi-lactosi pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, Xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, seminose five propionic ester, semi-lactosi five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, Xylitol five propionic ester, Sorbitol Powder six propionic ester, wood sugar four butyric ester, Glucose Pentabutyrate, fructose five butyric ester, seminose five butyric ester, semi-lactosi five butyric ester, maltose eight butyric ester, cellobiose eight butyric ester, sucrose eight butyric ester, Xylitol five butyric ester, Sorbitol Powder six butyric ester, wood sugar four benzoic ether, glucose pentaphene manthanoate, fructose pentaphene manthanoate, seminose pentaphene manthanoate, semi-lactosi pentaphene manthanoate, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, Xylitol pentaphene manthanoate, and Sorbitol Powder six benzoic ether.

Be more preferably at least a kind that is selected from following compound: xylose tetraacetate, alpha-glucose pentaacetate, fructose pentaacetate, Mannose pentaacetate, semi-lactosi pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, Xylitol pentaacetate, sorbitol hexaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, seminose five propionic ester, semi-lactosi five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, Xylitol five propionic ester, Sorbitol Powder six propionic ester, wood sugar four benzoic ether, glucose pentaphene manthanoate, fructose pentaphene manthanoate, seminose pentaphene manthanoate, semi-lactosi pentaphene manthanoate, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, Xylitol pentaphene manthanoate, and Sorbitol Powder six benzoic ether.

And then be more preferably at least a kind that is selected from following compound: maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, wood sugar four propionic ester, glucose pentapropiopanoate, fructose five propionic ester, seminose five propionic ester, semi-lactosi five propionic ester, maltose eight propionic ester, cellobiose eight propionic ester, sucrose octapropanoate, wood sugar four benzoic ether, glucose pentaphene manthanoate, fructose pentaphene manthanoate, seminose pentaphene manthanoate, semi-lactosi pentaphene manthanoate, maltose eight benzoic ether, cellobiose eight benzoic ether, sucrose eight benzoic ether, Xylitol pentaphene manthanoate, and Sorbitol Powder six benzoic ether.

Carbohydrate derivative fluidizer preferably has pyranose structure or furanose structure.

As the carbohydrate derivative fluidizer used in the present invention, compound shown below is also preferred.But, in the present invention, be not limited to these compounds.

Moreover in following structural formula, R separately represents arbitrary substituting group, and multiple R can be identical, also can be different.

Utilize 2 kinds of acylating agents by the acylations person of forming in addition of the hydroxyl (R is hydrogen atom) in 1 molecule in following table 2 ~ table 5; the R imported by these 2 kinds of acylating agents is represented as " substituting group 1 "; represented as " substituting group 2 " by another R, substitution value represents the number in the whole hydroxyls in 1 molecule.

[changing 15]

[table 2]

[changing 16]

[table 3]

[changing 17]

[table 4]

[changing 18]

[table 5]

Carbohydrate derivative fluidizer is as commercially available product, such as can obtain Tokyo and change into the commercially available product that company manufactures, Ai Erdixi (Aldrich) company manufactures, in addition, easily synthesize by carrying out known esterification (such as, described in Japanese Patent Laid-Open 8-245678 publication method) to commercially available carbohydrate.

Relative to acylated cellulose 100 mass parts, the content of the fluidizer in cellulose acylate film of the present invention is preferably 1 mass parts ~ 20 mass parts.By relative to acylated cellulose 100 mass parts, the content of fluidizer is set to more than 1 mass parts, and easily obtains polaroid weather resistance improved effect; in addition; by relative to acylated cellulose 100 mass parts, the content of fluidizer is set to below 20 mass parts, also can suppresses to ooze out.Relative to acylated cellulose 100 mass parts, the preferred content of the fluidizer in cellulose acylate film is 2 mass parts ~ 15 mass parts, is particularly preferably 5 mass parts ~ 15 mass parts.

Moreover these fluidizers also can add two or more.When adding two or more, concrete example and the preferred scope of addition are also same as described above.

(degradation inhibitor)

In cellulose acylate film, also can add degradation inhibitor (such as antioxidant, peroxide decomposer, free radical inhibitors, metal passivator, sour trapping agent, amine).In addition, UV light absorber is also a kind of degradation inhibitor.These degradation inhibitors etc. are No. 60-235852, Japanese Patent Laid-Open No. Sho, No. 3-199201, Japanese Patent Laid-Open, No. 5-1907073, Japanese Patent Laid-Open, No. 5-194789, Japanese Patent Laid-Open, No. 5-271471, Japanese Patent Laid-Open, No. 6-107854, Japanese Patent Laid-Open, No. 6-118233, Japanese Patent Laid-Open, No. 6-148430, Japanese Patent Laid-Open, No. 7-11056, Japanese Patent Laid-Open, No. 7-11055, Japanese Patent Laid-Open, No. 7-11056, Japanese Patent Laid-Open, No. 8-29619, Japanese Patent Laid-Open, No. 8-239509, Japanese Patent Laid-Open, on the books in each publication of No. 2000-204173, Japanese Patent Laid-Open.

In addition, commercially available stablizer described in 21 pages ~ 69 pages of " polymeric additive handbook " (CMC publication) all can preferably use.

(antioxidant)

Cellulose acylate film of the present invention is preferably containing antioxidant.

As antioxidant, include, for example: 2,6-bis--tert-butyl-4-methyl-Phenol, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 1,1 '-bis-(4-hydroxyphenyl) hexanaphthene, 2, phenol system or the Resorcinol system antioxidants such as 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,5-bis--Tert. Butyl Hydroquinones, tetramethylolmethane-four [3-(3,5-, bis--tertiary butyl-4-hydroxyphenyl) propionic ester].

Use three (4-methoxyl groups-3,5-phenylbenzene) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (2,4-bis--tert-butyl-phenyl) phosphorous acid ester, two (2,6-bis--tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4-bis--tert-butyl-phenyl) phosphorous antioxidant such as pentaerythritol diphosphites, or N, the oxyamine system antioxidants such as N-bis--octadecyl oxyamine, N, N-dibenzylhydroxylamine are also preferred.About oxyamine based compound, compound described in the paragraph 0005 ~ paragraph 0020 of Japanese Patent Laid-Open 8-62767 publication, paragraph 0022 ~ paragraph 0026 also preferably can be used.

In addition, the reductones represented by following general formula (A) or general formula described later (B) is also preferred as the antioxidant used in the present invention.

[changing 19]

In general formula (A), R ^a1and R ^a2separately represent hydroxyl, amino, acyl amino, alkyl sulfonyl-amino, arlysulfonylamino, alkoxycarbonyl amino, sulfydryl or alkylthio.X comprises carbon atom and Sauerstoffatom and/or nitrogen-atoms, and represents and-C (=O)-C (R ^a1)=C (R ^a2)-together forms the non-metallic atom group of 5 ring ~ 6 rings.

R ^a1and R ^a2be preferably hydroxyl, amino, alkyl sulfonyl-amino or arlysulfonylamino, be more preferably hydroxyl or amino, and then be more preferably hydroxyl.

X preferably has at least 1-O-key, and by-C (R ^a3) (R ^a4)-,-C (R ^a5-C)=, (=O)-, the one kind or two or more combination of-N (Ra)-and-N=forms.Herein, R ^a3~ R ^a5and Ra is preferably separately for hydrogen atom, carbon number are 1 ~ 10 have substituent alkyl, can have aryl, hydroxyl or carboxyl that substituent carbon number is 6 ~ 15.

Above-mentioned 5 ring ~ 6 rings formed via X include, for example cyclopentenone ring (2-cyclopentene-1-one ring; The compound formed becomes reductinic acid), furanone ring [2 (5H)-furanone ring], dihydro pyrone ring [3,4-dihydro-2H-pyrans-4-ketone ring (2,3-dihydro-4H-pyrone ring), 3,6-dihydro-2H-pyran-2-one ring, 3,6-dihydro-2H-pyrans-6-ketone ring (5,6-dihydro-2-pyrone ring)], 3,4-dihydro-2H-pyrone ring, be preferably cyclopentenone ring, furanone ring, dihydro pyrone ring, be more preferably furanone ring, dihydro pyrone ring, be particularly preferably furanone ring.

These rings also can carry out contracting ring, as the ring that this carries out contracting ring, can be saturated rings, unsaturated ring any one.

Among reductones represented by above-mentioned general formula (A), be preferably the compound represented by following general formula (A1), wherein, be preferably the compound represented by following general formula (A2).

[changing 20]

In general formula (A1), R ^a1represent hydrogen atom, alkyl, aryl or heterocyclic radical, these bases also can have substituting group.

R ^a1preferably can have substituent alkyl, be more preferably-CH (OR ^a1) CH ₂oR ^a2, in the case, become the compound represented by above-mentioned general formula (A2).

In general formula (A2), R ^a2and R ^a3separately represent hydrogen atom, alkyl, acyl group or alkoxy carbonyl, R ^a2with R ^a3can bond and form ring mutually, as formed ring, be preferably 1,3-dioxolanes ring (1,3-dioxolane ring), this ring and then can have substituting group.The compound with dioxolanes ring is by utilizing the acetalation of the reaction of xitix and ketone or aldehydes or ketalizationly synthesizing, and the ketone of raw material or aldehydes can use with no particular limitation.

One of particularly preferred substituent combination is R ^a2for acyl group and R ^a3for the compound of hydrogen atom, as acyl group, can be any one of aliphatic acyl radical and aromatic acyl, when aliphatic acyl radical, being preferably carbon number is 2 ~ 30, and being more preferably carbon number is 4 ~ 24, and then to be more preferably carbon number be 8 ~ 18.When aromatic acyl, being preferably carbon number is 7 ~ 24, and being more preferably carbon number is 7 ~ 22, and then to be more preferably carbon number be 7 ~ 18.As preferred acyl group, can enumerate: butyryl radicals, caproyl, 2-ethyl hexyl acyl group, decanoyl, lauroyl, myristoyl, palmitoyl, stearyl-, palm enoyl-, macene acyl group, oleoyl, benzoyl, 4-methyl benzoyl and 2-methyl benzoyl.

Compound represented by following general formula (B) is also together preferred with the compound represented by above-mentioned general formula (A).

[changing 21]

In general formula (B), R ^b1and R ^b2separately represent hydrogen atom, alkyl, thiazolinyl, cycloalkyl, aryl, acyl group, carboxyl, amino, alkoxyl group, alkoxy carbonyl or heterocyclic radical, R ^b3and R ^b4separately represent hydroxyl, amino, acyl amino, alkyl sulfonyl-amino, arlysulfonylamino, alkoxycarbonyl amino or sulfydryl.

R ^b1and R ^b2in alkyl to be preferably carbon number be 1 ~ 10.This alkyl is preferably methyl, ethyl, the tertiary butyl.

R ^b1and R ^b2in alkyl to be preferably carbon number be 1 ~ 10.

R ^b1and R ^b2in thiazolinyl to be preferably carbon number be 2 ~ 10.This thiazolinyl is preferably vinyl, allyl group, is preferably vinyl.

R ^b1and R ^b2in cycloalkyl to be preferably carbon number be 3 ~ 10.This cycloalkyl is preferably cyclopropyl, cyclopentyl, cyclohexyl.

These alkyl, thiazolinyl, cycloalkyl can have substituting group, and this substituting group is preferably selected from least a kind in hydroxyl, carboxyl and sulfo group.

Moreover, when thiazolinyl is vinyl, replaces and have the vinyl of carboxyl also preferred.

R ^b1and R ^b2in aryl to be preferably carbon number be 6 ~ 12.Aryl can have substituting group, and this substituting group is preferably selected from least a kind in alkyl, hydroxyl, carboxyl, sulfo group, halogen atom, nitro and cyano group.

R ^b1and R ^b2in acyl group be preferably formyl radical, ethanoyl, isobutyryl or benzoyl.

R ^b1and R ^b2in amino comprise amino, alkylamino, arylamino, be preferably amino, methylamino-, dimethylamino, ethylamino, diethylin, dipropyl amino, anilino, N-methyl-N-anilino.

R ^b1and R ^b2in alkoxyl group to be preferably carbon number be 1 ~ 10.This alkoxyl group is preferably methoxy or ethoxy.

R ^b1and R ^b2in alkoxy carbonyl be preferably methoxycarbonyl.

R ^b1and R ^b2in heterocyclic radical be preferably ring form heteroatoms be Sauerstoffatom, sulphur atom or nitrogen-atoms, and be preferably ring structure be 5 rings or 6 rings.This heterocyclic radical can be aromatic heterocycle, also can be saturated heterocyclyl, in addition, also can carry out contracting ring.

Heterocycle in heterocyclic radical is preferably pyridine ring, pyrimidine ring, pyrrole ring, furans cyclic group, thiphene ring, pyrazole ring, piperidine ring, piperazine ring or morpholine ring.

R ^b1and R ^b2be more preferably carbon number be 1 ~ 6 alkyl or carbon number be the aryl of 6 ~ 12.

R ^b3and R ^b4in amino comprise amino, alkylamino, arylamino, be preferably amino or as methylamino-, ethylamino, n-butyl amine base, hydroxyethylamino alkylamino.

R ^b3and R ^b4in acyl amino be preferably acetylamino or benzoyl-amido.

R ^b3and R ^b4in alkyl sulfonyl-amino be preferably Methylsulfonylamino.

R ^b3and R ^b4in arlysulfonylamino to be preferably BENZENESUFONYLAMINO or p-toluenesulfonyl amino.

R ^b3and R ^b4in alkoxycarbonyl amino be preferably methyloxycarbonylamino.

R ^b3and R ^b4be more preferably hydroxyl, amino, alkyl sulfonyl-amino or arlysulfonylamino.

The antioxidant used in the present invention is more preferably reductones, as concrete example, compound illustrated in the paragraph 0022 ~ paragraph 0031 of compound illustrated in the paragraph 0012 ~ paragraph 0020 of compound illustrated in the paragraph 0014 ~ paragraph 0034 of Japanese Patent Laid-Open 6-27599 publication, Japanese Patent Laid-Open 6-110163 publication, Japanese Patent Laid-Open 8-114899 publication can be enumerated.

Wherein, the myristinate of L-AA, cetylate, stearate is particularly preferably.

As long as the time point be added into by above-mentioned antioxidant in cellulose acylate film adds at the time point be filmed, be then not particularly limited.Such as, can adding at the generated time point of acylated cellulose, also can mix with acylated cellulose when preparing dope (dope).

Relative to acylated cellulose 100 mass parts, the content of the antioxidant in cellulose acylate film is preferably 0.0001 mass parts ~ 5.0 mass parts.By being set in above-mentioned scope by the content of antioxidant, and sufficient antioxidant effect and polaroid weather resistance can be obtained.Relative to acylated cellulose 100 mass parts, the content of the antioxidant in cellulose acylate film is more preferably 0.001 mass parts ~ 1.0 mass parts, and then is more preferably 0.01 mass parts ~ 0.5 mass parts.

(free radical scavenger)

Cellulose acylate film of the present invention is preferably containing free radical scavenger.By containing free radical scavenger, the decomposition of the compound represented by above-mentioned general formula (I) is inhibited, and can obtain the better weather resistance of polaroid.

As free radical scavenger used in the present invention, be preferably the compound (hindered amine as light stabilizer (Hindered Amine Light Stabilizer, HALS)) represented by following general formula (H).

[changing 22]

In general formula (H), R ^h1and R ^h2separately represent hydrogen atom or substituting group, R ^h01~ R ^h04separately represent alkyl.

R ^h1in substituting group be not particularly limited, but be preferably alkyl or utilize nitrogen-atoms or Sauerstoffatom and piperidine ring to carry out the substituting group of bond.The substituting group utilizing nitrogen-atoms or Sauerstoffatom and piperidine ring to carry out bond is preferably amino, acyl amino, hydroxyl, alkoxyl group, aryloxy or acyloxy.These bases also can have substituting group.

R ^h1in substituting group be preferably alkyl, aryl or there is the amino of heterocyclic radical, be more preferably hydroxyl, alkoxyl group or acyloxy.

R ^h2in substituting group be not particularly limited, be preferably alkyl (being preferably carbonatoms is 1 ~ 20, and being more preferably carbonatoms is 1 ~ 12, and then to be more preferably carbonatoms be 1 ~ 8, wherein, methyl, ethyl, sec.-propyl, the tertiary butyl, n-octyl, 2-ethylhexyl, positive decyl, positive hexadecyl), (be preferably carbonatoms is 2 ~ 20 to thiazolinyl, and being more preferably carbonatoms is 2 ~ 12, and then to be more preferably carbonatoms be 2 ~ 8, and then is more preferably vinyl, allyl group, crotyl or 3-pentenyl), (be preferably carbonatoms is 2 ~ 20 to alkynyl, and being more preferably carbonatoms is 2 ~ 12, and then to be more preferably carbonatoms be 2 ~ 8, and then is more preferably propargyl, or 3-pentynyl), (be preferably carbon number is 3 ~ 20 to cycloalkyl, and being more preferably carbon number is 3 ~ 12, and then to be more preferably carbon number be 3 ~ 8, cyclopropyl, cyclopentyl or cyclohexyl), (be preferably carbon number is 6 ~ 30 to aryl, and being more preferably carbon number is 6 ~ 20, and then to be more preferably carbon number be 6 ~ 12, and then is more preferably phenyl, xenyl or naphthyl), amino (comprises amino, alkylamino, arylamino, being preferably carbonatoms is 0 ~ 20, and being more preferably carbonatoms is 0 ~ 10, and then to be more preferably carbonatoms be 0 ~ 6, and then is more preferably amino, methylamino-, dimethylamino, diethylin, anilino, N-methyl-N-anilino or dibenzyl amido), (be preferably carbonatoms is 1 ~ 20 to alkoxyl group, and being more preferably carbonatoms is 1 ~ 12, and then to be more preferably carbonatoms be 1 ~ 8, and then is more preferably methoxyl group, oxyethyl group, butoxy), (cycloalkyl ring in cycloalkyloxy is preferably 3 ring ~ 8 rings to cycloalkyloxy, and being preferably carbon number is 3 ~ 20, and cycloalkyloxy is preferably ring propoxy-, cyclopentyloxy, cyclohexyloxy), acyl group (comprises alkyl-carbonyl, aryl carbonyl, being preferably carbon number is 2 ~ 20, and being more preferably carbon number is 2 ~ 16, and then to be more preferably carbon number be 2 ~ 8, and then is more preferably ethanoyl, propionyl, 2-ethyl hexyl acyl group or benzoyl), hydroxyl or oxyradical (-O).

R ^h01~ R ^h04being preferably carbon number is the alkyl of 1 ~ 6, is more preferably ethyl or methyl, and then is more preferably R ⁰¹~ R ⁰⁴be methyl.

Compound represented by above-mentioned general formula (H) is preferably selected from least a kind: 4-hydroxyl-2,2,6,6-tetramethyl piperidine in following compound, 1-allyl group-4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-benzyl-4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-(the 4-tertiary butyl-crotyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 1-ethyl-4-bigcatkin willow acyloxy-2,2,6,6-tetramethyl piperidine, 4-methacryloxy-1,2,2,6,6-pentamethvl, 1,2,2,6,6-pentamethvl-4-base-β (3,5-, bis--tertiary butyl-4-hydroxyphenyl)-propionic ester, 1-benzyl-2,2,6,6-tetramethyl piperidine-4-base maleate (maleinate), two (2,2,6,6-tetramethyl piperidine-4-base) adipic acid ester, two (2,2,6,6-tetramethyl piperidine-4-base) sebate, two (1,2,3,6-tetramethyl--2,6-diethyl-piperidin-4-yl) sebate, two (1-allyl group-2,2,6,6-tetramethyl--piperidin-4-yl) phthalic ester, 1-ethanoyl-4-acetoxyl group-2,2,6,6-tetramethyl piperidine, trimellitic acid (trimellitic acid)-three (2,2,6,6-tetramethyl piperidine-4-base) ester, 1-acryl-4-benzyloxy-2,2,6,6-tetramethyl piperidine,

Dibutyl propanedioic acid-bis-(1, 2, 2, 6, 6-pentamethyl--piperidin-4-yl) ester, dibenzyl propanedioic acid-bis-(1, 2, 3, 6-tetramethyl--2, 6-diethyl-piperidin-4-yl) ester, dimethyl-bis-(2, 2, 6, 6-tetramethyl piperidine-4-base oxygen base)-silane, three (1-propyl group-2, 2, 6, 6-tetramethyl piperidine-4-base)-phosphorous acid ester, three (1-propyl group-2, 2, 6, 6-tetramethyl piperidine-4-base)-phosphoric acid ester, N, N '-bis-(2, 2, 6, 6-tetramethyl piperidine-4-base)-hexa-methylene-1, 6-diamines, four (2, 2, 6, 6-tetramethyl piperidine-4-base)-1, 2, 3, 4-butane tetracarboxylic acid esters, four (1, 2, 2, 6, 6-pentamethvl-4-base)-1, 2, 3, 4-butane tetracarboxylic acid esters, N, N '-bis--(2, 2, 6, 6-tetramethyl piperidine-4-base)-hexa-methylene-1, 6-diethylamide, 1-ethanoyl-4-(N-cyclohexyl ethanamide)-2, 2, 6, 6-tetramethyl--piperidines, 4-benzyl amino-2, 2, 6, 6-tetramethyl piperidine, N, N '-bis--(2, 2, 6, 6-tetramethyl piperidine-4-base)-N, N '-dibutyl-adipamide, N, N '-bis-(2, 2, 6, 6-tetramethyl piperidine-4-base)-N, N '-dicyclohexyl-(2-hydroxyl) trimethylene diamine, N, N '-bis--(2, 2, 6, 6-tetramethyl piperidine-4-base)-terephthaldehyde base-diamines, 4-two (2-hydroxyethyl) amino-1, 2, 2, 6, 6-pentamethvl, 4-Methacrylamide-1, 2, 2, 6, 6-pentamethvl and alpha-cyano-Beta-methyl-β-[N-(2, 2, 6, 6-tetramethyl piperidine-4-base)]-amino-acrylonitrile acid methyl esters.

Be more preferably N, N ', N ", N " '-four-[4, 6-pair-[butyl-(N-methyl-2, 2, 6, 6-tetramethyl piperidine-4-base) amino]-triazine-2-base]-4, 7-diaza decane-1, 10-diamines, dibutylamine and 1, 3, 5-triazine N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl)-1, 6-hexamethylene-diamine and N-(2, 2, 6, 6-tetramethyl--4-piperidyl) polycondensate (BASF (BASF) company manufacture intelligence Ma Suobu (CHIMASSORB) 2020FDL) of butylamine, dibutylamine and 1, 3, 5-triazine and N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) polycondensate of butylamine, poly-[{ (1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-base } { (2, 2, 6, 6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2, 2, 6, 6-tetramethyl--4-piperidyl) imino-}] (BASF AG manufactures intelligence Ma Suobu (CHIMASSORB) 944FDL), 1, 6-hexanediamine-N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl) and morpholine-2, 4, 6-tri-chloro-1, 3, the polycondensate of 5-triazine, poly-[(6-morpholinyl-guanamine, 4-bis-base) [(2, 2, 6, 6,-tetramethyl--4-piperidyl) imino-]-hexa-methylene [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] etc. via triazine skeleton, bond has the HMW HA LS of multiple piperidine ring,

Or dimethyl succinate and 4-hydroxyl-2,2,6 can be used aptly, the polycondensate, 1 of 6-tetramethyl--1-piperidine ethanol, 2,3,4-BTCA and 1,2,2,6,6-pentamethyl--4-piperidine alcohols and two (the 2-hydroxyl-1 of 3,9-, 1-dimethyl ethyl)-2,4,8, via ester bond, bond has the HMW HA LS of piperidine ring to 10-tetra-oxaspiro [5,5] undecanoic mixed ester compounds etc., but the present invention is not limited to these change platform things.

Among these, from dibutylamine and 1,3,5-triazine and N, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl) polycondensate, poly-[{ (1,1 of butylamine, 3,3-tetramethyl butyl) amino-1,3,5-triazine-2,4-bis-base } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imino-} and dimethyl succinate and 4-hydroxyl-2,2,6, select in the polycondensate of 6-tetramethyl--1-piperidine ethanol, number average molecular weight (Mn) is preferably 2,000 ~ 5,000.

Free radical scavenger is the compound (trade(brand)name represented by following structure (H α), Su meter Lai Ze (Sunlizer) HA-622, Suo Te (SORT) limited-liability company manufactures) and compound represented by following structure (H β) also suitable.

[changing 23]

Moreover the m in said structure (H α) is 2 ~ 30.

The compound of said structure (H α) or structure (H β) can obtain trade(brand)name intelligence Ma Suobu (CHIMASSORB) 2020FDL (CAS-No.192268-64-7) that the BASF AG (former Ciba (CibaSpecialty Chemicals) limited-liability company) of having gone on the market manufactures, intelligence Ma Suobu (CHIMASSORB) 944FDL (CAS-No.71878-19-8) and ground slave refined (TINUVIN) 770DF (CAS-No.52829-07-9), trade(brand)name West Asia rope cloth (Cyasorb) UV-3346 (CAS-No.82541-48-7) that sun chemistry (Sun Chemical) limited-liability company manufactures, West Asia rope cloth (Cyasorb) UV-3529 (CAS-No.193098-40-7).

In addition, the compound represented by following general formula (H1), and can particularly preferably for cellulose acylate film of the present invention because alkalescence is low, for side effect this reason little of polarizing properties.

[changing 24]

In general formula (H1), Z ^h1represent alkyl, cycloalkyl or aryl, Y ^h1represent hydrogen atom or substituting group.R ^h01~ R ^h04implication and the R of above-mentioned general formula (H) ^h01~ R ^h04identical, preferred form is also identical.

Z ^h1preferably can have substituent alkyl or cycloalkyl, be more preferably the alkyl be unsubstituted with branched structure, the alkyl or cycloalkyl with aryl alternatively base, and then be more preferably cycloalkyl.Moreover, Z ^h1the substituting group had is not particularly limited.

Z ^h1in the carbon number of alkyl be preferably 1 ~ 20, be more preferably 1 ~ 14.Z ^h1in the carbon number of cycloalkyl be preferably 3 ~ 20, be more preferably 3 ~ 14.In addition, Z ^h1in the carbon number of aryl be preferably 6 ~ 20, be more preferably 6 ~ 14.

Y ^h1be preferably substituting group.Y ^h1in substituting group be not particularly limited, but preferably utilize nitrogen-atoms or Sauerstoffatom and piperidine ring to carry out the substituting group of bond, in addition, be more preferably and can have substituent amino, hydroxyl, (carbon number is preferably 1 ~ 20 to alkoxyl group, be more preferably 1 ~ 14), (carbon number is preferably 6 ~ 20 to aryloxy, be more preferably 6 ~ 12), or acyloxy (carbon number is preferably 2 ~ 20, be more preferably 2 ~ 14), and then be more preferably the alkyl that carbon number is 1 ~ 10, carbon number is the aryl of 6 ~ 12 or has the amino of heterocyclic radical alternatively base, hydroxyl, carbon number is the alkoxyl group of 1 ~ 10, or carbon number is the acyloxy of 2 ~ 10.

Compound represented by general formula (H1) especially has feature in following: the nitrogen (N) of piperidine ring with by Z ^h1the represented substituent alkyl or aryl that has carries out ehter bond knot.In present specification, will containing being somebody's turn to do " N-O-Z ^h1" the compound with piperidine scaffolds represented by above-mentioned general formula (H1) of structure be called " NOZ ^h1type ".

In addition, the only hydrogen compound be directly binding on the nitrogen (N) of piperidine ring is called " NH type ", the compound that only methyl is directly binding on nitrogen (N) is called " NCH ₃type ".NH type and NCH ₃the alkalescence of type compares NOZ ^h1type is strong.In the present invention, the NOZ by using alkalescence weak ^h1the compound of type, and can more effectively to suppress cellulose acylate film of the present invention to be assembled in Polarizer and hot and humid lower long-time use time polaroid performance degradation.

By the NOZ represented by general formula (H1) ^h1as long as the compound of type has the piperidine scaffolds person of regulation, then and indefinite, but the compound be preferably represented by following general formula (H1-1) or general formula (H1-2).

[changing 25]

In general formula (H1-1), general formula (H1-2), R ^h01~ R ^h04implication and above-mentioned general formula (H) in R ^h01~ R ^h04identical, preferred scope is also identical.Z ^h2expression can have substituent alkyl or aryl.R ^h11and R ^h12separately represent alkyl, aryl, acyl group or heterocyclic radical.R ^h13represent hydrogen atom, alkyl, acyl group or aryl.

Z ^h2preferred scope and the Z of above-mentioned general formula (H1) ^h1identical.

R ^h11be more preferably hydrogen atom or alkyl, be particularly preferably hydrogen atom or carbon number is the alkyl of 1 ~ 6, and then be particularly preferably propyl group or butyl.

R ^h12be more preferably alkyl or heterocyclic radical, be particularly preferably carbon number be 1 ~ 6 alkyl or ring element number be 1 ~ 2 containing the heterocyclic radical of nitrogen-atoms, be particularly preferably triazine.

R ^h13be preferably hydrogen atom, carbon number be 1 ~ 12 alkyl or carbon number be the acyl group of 1 ~ 12, be particularly preferably the acyl group that carbon number is 1 ~ 12.

Above-mentioned R ^h11~ R ^h13in above-mentioned each base also can be replaced by substituting group.As this kind of substituting group, such as, can have self-drifting (H1) and eliminate Y ^h1substituting group.

Change platform thing represented by above-mentioned general formula (H1-1) or general formula (H1-2) is preferably the change platform thing represented by following general formula (H1-a) ~ general formula (H1-c).

[changing 26]

In general formula (H1-a) ~ general formula (H1-c), Z ^h1and Z ^h2same as described above, preferred scope is also identical.R ^h01~ R ^h04implication and above-mentioned general formula (H) in R ^h01~ R ^h04identical, preferred scope is also identical.

In general formula (H1-c), R ^h05~ R ^h06separately represent alkyl, R ^haand R ^hbseparately represent hydrogen atom, alkyl, aryl or heterocyclic radical, W ^h1represent substituting group.

Below represent the preference of the change platform thing represented by above-mentioned general formula (H), but the present invention is not limited to these preferences.

[changing 27]

[changing 28]

Above-claimed cpd HA-11 (goods name " refined (TINUVIN) 152 of slave ", Ciba limited-liability company manufactures, and compound H A-12 (goods name " good fortune LeAnn Rimes tower Catalina Ponor (FLAMESTAB NOR) 116FF " CAS-No.191743-75-6), Ciba limited-liability company manufactures, CAS-No.191680-81-6) easily can obtain from market.

In addition, following compound H A-13 (goods name " refined (TINUVIN) 123 of slave ", Ciba limited-liability company manufactures, CAS-No.129757-67-1) also preferably can be used as free radical scavenger.

[changing 29]

Moreover the compound represented by above-mentioned general formula (H) can as above obtain with commercial system, also can use by synthesizing manufactured person.There is no particular restriction for the synthetic method of the compound represented by above-mentioned general formula (H), synthesizes by the method in common organic synthesis.In addition, as process for purification, can be suitable for using distillation, recrystallize, redeposition, utilize the method for filtering medium sorbent material.And then, what usually sell can the cheap compound obtained be not only the compound represented by above-mentioned general formula (H), sometimes be also mixture, in the present invention, as long as play function as free radical scavenger, no matter then manufacture method, composition, fusing point, acid number etc., all can be used.

The molecular weight of the compound represented by above-mentioned general formula (H) is also unrestricted, but with regard to suppressing the viewpoint of the volatilization in cellulose acylate film, being preferably as molecular weight described as follows is polymer to a certain extent.By being adjusted to the molecular weight of appropriateness, with the excellent compatibility of acylated cellulose, the film that the transparency is high can be obtained.

Therefore, the molecular weight of the compound represented by above-mentioned general formula (H) is preferably 300 ~ 100000, is more preferably 500 ~ 50000, is particularly preferably 700 ~ 30000.

By by above-mentioned general formula (H) as long as represented by compound be added into time point in cellulose acylate film and add at the time point be filmed, be then not particularly limited.Such as, can adding at the generated time point of acylated cellulose, also can mix with acylated cellulose when preparing dope.

Relative to acylated cellulose 100 mass parts, the content of the compound represented by above-mentioned general formula (H) in cellulose acylate film is preferably 0.0001 mass parts ~ 5.0 mass parts.By being set in above-mentioned scope by the content of the compound represented by above-mentioned general formula (H) in cellulose acylate film, and sufficient antioxidant effect and polaroid wear properties can be obtained.Relative to acylated cellulose 100 mass parts, the content of the compound represented by above-mentioned general formula (H) in cellulose acylate film is more preferably 0.001 mass parts ~ 1.0 mass parts, and then is more preferably 0.01 mass parts ~ 0.5 mass parts.

(UV light absorber)

In the present invention, with regard to preventing the viewpoint of the deterioration of Polarizer or liquid crystal etc., also can add UV light absorber in cellulose acylate solutions.With regard to the ultraviolet receptivity of below wavelength 370nm with regard to the excellent and viewpoint that liquid-crystal display is good, UV light absorber preferably can use the UV light absorber that the absorption of the visible ray of more than wavelength 400nm is few.The UV light absorber used in the present invention is preferably selected from least a kind in hindered phenol compound, hydroxybenzophenone compound, benzotriazole cpd, salicylate compounds, benzophenone cpd, cyanoacrylate compounds and nickel complexing salt compound.

There is no particular restriction for hindered phenol compound, but be preferably selected from 2,6-, bis--t-butyl-p-cresol, tetramethylolmethane-four [3-(3,5-, bis--tertiary butyl-4-hydroxyphenyl) propionic ester], N, N '-hexa-methylene two (3,5-bis--tertiary butyl-4-hydroxy-phenylpropyl aldehyde), 1,3,5-trimethylammonium-2,4, at least a kind in 6-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl) benzene and three-(3,5-, bis--tertiary butyl-4-hydroxy benzyl)-isocyanuric acid esters.

There is no particular restriction for benzotriazole cpd, but be preferably selected from 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2, 2-methylene-bis [4-(1, 1, 3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol], (2, 4-pair-(just pungent sulfenyl)-6-(4-hydroxyl-3, 5-bis--tertiary-butyl anilino)-1, 3, 5-triazine, triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], N, N '-hexa-methylene two (3, 5-bis--tertiary butyl-4-hydroxy-phenylpropyl aldehyde), 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-bis--tertiary butyl-4-hydroxy benzyl) benzene, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-pentyl phenyl)-5-chlorobenzotriazole, 2, 6-bis--t-butyl-p-cresol, and tetramethylolmethane-four [3-(3, 5-bis--tertiary butyl-4-hydroxyphenyl) propionic ester] at least a kind.

In quality criteria, the content of the anti UV agent in cellulose acylate film is preferably 1ppm ~ 1.0%, is more preferably 10ppm ~ 1000ppm.

(other degradation inhibitors)

As the degradation inhibitor of acylated cellulose, peroxide decomposer, free radical inhibitors, metal passivator and known additive also can be used as.As these stablizers, include, for example compound described in the paragraph 0074 ~ paragraph 0081 of Japanese Patent Laid-Open 2006-251746 publication, paragraph 0082 ~ paragraph 0117.

In addition, amine is also known as degradation inhibitor, include, for example compound described in the paragraph 0009 ~ paragraph 0080 of Japanese Patent Laid-Open 5-194789 publication, or the fatty amine such as three-n-octyl amine, tri-iso-octylamine, tris-(2-ethylhexyl)amine, N, N-dimethyl dodecyl amine.

In addition, also preferably can use the polynary amine of the amino with more than 2, as polyamine, preferably there is one-level amino or the amino person of secondary of more than 2.As the compound of amino with more than 2, can enumerate: nitrogen-containing heterocycle compound (there is the compound of pyrazoles pyridine ring, piperazine ring etc.), the polyamine based compound (polyamine of chain or ring-type, such as Diethylenetriamine, tetraethylene-pentamine, N, N '-bis-(amino-ethyl)-1,3-propanediamine, N, N, N ', N ", N "-five (2-hydroxypropyl) Diethylenetriamine, draw amine (cyclam) as the compound of basic framework containing ring) etc.

As the concrete example of this polynary amino, can enumerate: Diethylenetriamine, three second tetramines, tetraethylene-pentamine, five second hexamines, dipropanetriamine, 3 third tetramines, amino ethyl ethanolamine, polymine (polyethyleneimine), PAH, polyvinylamine, N ', N '-four (2-hydroxyethyl) quadrol, N, N, N ', N '-four (2-hydroxypropyl) quadrol, N, N, N ', N ", N "-five (2-hydroxypropyl) Diethylenetriamine etc.In addition, in commercially available product, include, for example Ai Pomin (Epomin) SP-006, Ai Pomin (Epomin) SP-012, Ai Pomin (Epomin) SP-018 etc. that Japanese catalyzer (share) company manufactures.

(matting agent)

With regard to film slipperiness and the stable viewpoint manufactured, also can add matting agent in cellulose acylate film of the present invention.Matting agent can be the matting agent of mineral compound, also can be the matting agent of organic compound.

The matting agent of mineral compound is preferably selected from mineral compound (the such as silicon-dioxide containing silicon, baked calcium silicate, calcium silicate hydrate, pure aluminium silicate, Magnesium Silicate q-agent etc.), titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium white, strontium oxide, weisspiessglanz, stannic oxide, tin-antiomony oxide, calcium carbonate, talcum, clay, at least a kind in calcined kaolin and calcium phosphate, be more preferably at least a kind in the mineral compound and zirconium white be selected from containing silicon, with regard to reducing the viewpoint of the turbidity of cellulose acylate film further, be particularly preferably use silicon-dioxide.

The micropartical of silicon-dioxide such as can use has Ai Luoxier (Aerosil) R972, Ai Luoxier (Aerosil) R974, Ai Luoxier (Aerosil) R812, Ai Luoxier (Aerosil) 200, Ai Luoxier (Aerosil) 300, Ai Luoxier (Aerosil) R202, the commercially available product of the trade(brand)name of Ai Luoxier (Aerosil) OX50, Ai Luoxier (Aerosil) TT600 (above Japanese Ai Luoxier (Aerosil) (share) manufactures) etc.Zirconic micropartical such as can use with the trade(brand)name institute sellers of Ai Luoxier (Aerosil) R976 and Ai Luoxier (Aerosil) R811 (above Japanese Ai Luoxier (share) manufactures) etc.

There is no particular restriction for the matting agent of organic compound, is preferably selected from least a kind of polymkeric substance in silicone resin, fluoro-resin and acrylic resin, wherein, is preferably silicone resin.Among silicone resin, be particularly preferably and there is three-dimensional reticulated structure person, such as, can use the commercially available product of the trade(brand)name with Tuo Sipaer (Tospearl) 103, Tuo Sipaer (Tospearl) 105, Tuo Sipaer (Tospearl) 108, Tuo Sipaer (Tospearl) 120, Tuo Sipaer (Tospearl) 145, Tuo Sipaer (Tospearl) 3120 and Tuo Sipaer (Tospearl) 240 (above Toshiba silicone (Toshiba Silicone) (share) manufacture) etc.

As long as the time point be added into by these matting agents in cellulose acylate film adds at the time point be filmed, be then not particularly limited.Such as, the stage of acylated cellulose and solvent additive can be contained, also additive can be added after utilizing acylated cellulose and solvent to make mixing solutions.

And then, also can be about to make dope carry out curtain coating before add mixing, this mixing is preferably and onlinely arranges spiral mixingly to carry out.Specifically, the static mixer used as on-line mixing device is preferably.In addition, as on-line mixing device, such as, be preferably the mixing tank as static mixer SWJ (in eastern beautiful silent oscillation pipe mixing tank HI mixing tank (HI-Mixer)) (eastern beautiful engineering (Toray Engineering) manufacture).

Moreover, about online interpolation, in order to eliminate the cohesion etc. of density unevenness, particle, method described in Japanese Patent Laid-Open 2003-053752 publication can be used.And then, few and also there is not the peeling of interlayer and slipperiness is good, the transparency is excellent phase retardation film in order to make bleeding of additive, also can use method described in Japanese Patent Laid-Open 2003-014933 publication.

The content of the matting agent in cellulose acylate film is particularly preferably 0.05 quality % ~ 1.0 quality %.By being set to this kind of value, the mist degree of cellulose acylate film can not become large, when being actually used in liquid crystal indicator, contributes to suppressing the unfavorable condition such as the decline of contrast gradient and the generation of bright spot.In addition, above-mentioned creak sound, scuff resistance can be realized.With regard to these viewpoints, the content of the matting agent in cellulose acylate film is particularly preferably 0.05 quality % ~ 1.0 quality %.

(peeling off promotor)

Cellulose acylate film of the present invention also can add known stripping promotor.

Peel off promotor and be preferably organic acid, polycarboxylic acid derivative, interfacial agent or sequestrant.Such as preferably can use compound etc. described in the paragraph 0030 ~ paragraph 0056 of compound described in the paragraph 0077 ~ paragraph 0086 of compound described in the paragraph 0048 ~ paragraph 0081 of Japanese Patent Laid-Open 2006-45497 publication, Japanese Patent Laid-Open 2002-322294 publication, Japanese Patent Laid-Open 2012-72348 publication.

As organic acid, compound described in the paragraph 0079 ~ paragraph 0082 of Japanese Patent Laid-Open 2002-322294 publication can be enumerated, include, for example: citric acid, oxalic acid, hexanodioic acid, succinic acid, oxysuccinic acid, tartrate etc.

And then, as organic acid, amino acids is also preferred, include, for example: l-asparagine acid, aspartic acid, VITAMIN B4, L-Ala, Beta-alanine, arginine, L-iLeu, glycine, glutamine acid, L-glutamic acid, Serine, tyrosine, tryptophane, Threonine, nor-leucine, α-amino-isovaleric acid, phenylalanine (phenylalanine), methionine(Met), Methionin, L-LEU (leucine) etc.

Organic acid also can be used as free acid, can enumerate the salt of an alkali metal salt, alkaline earth salt, heavy metal containing transition metal.Among the metal of each salt, basic metal can exemplary lithium, potassium, sodium etc., and alkaline-earth metal can illustrate calcium, magnesium, barium, strontium etc.Heavy metal containing transition metal can illustrate aluminium, zinc, tin, nickel, iron, lead, copper, silver etc.In addition, carbon number is that the salt of the amine being substituted, being unsubstituted of less than 5 is also preferred, as the amine of this salt, such as, can illustrate: ammonium, methylamine, ethamine, propylamine, butylamine, dimethylamine, Trimethylamine 99, triethylamine, oxyethylamine, two (hydroxyethyl) amine, triethanolamine etc.Preferred metal is the sodium in basic metal, the calcium in alkaline-earth metal, magnesium.These basic metal, alkaline-earth metal can be used alone respectively or are used in combination of two or more, also can also with basic metal and alkaline-earth metal.

As polycarboxylic acid derivative, be preferably ester cpds and amide compound.

Carboxylic acid composition is polycarboxylic acid, and this carboxylic acid can be aliphatics or any one carboxylic acid aromatic, but is preferably aliphatic carboxylic acid.Aliphatic carboxylic acid can be saturated, unsaturated, is preferably the aliphatic carboxylic acid of straight-chain, branched or ring-type, also can has substituting group.This substituting group can be enumerated: alkyl, thiazolinyl, aryl, hydroxyl, amino, alkoxyl group, alkene oxygen base, acyloxy, acyl amino.

Aromatic carboxylic acid can be enumerated: phthalic acid, terephthalic acid, m-phthalic acid, 1,3,5-benzene tricarboxylic acid etc., aliphatic carboxylic acid can enumerate oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, as having substituent aliphatic carboxylic acid, oxysuccinic acid, citric acid, tartrate can be enumerated.

In multi-carboxylate, the alkyl [such as methyl, ethyl, sec.-propyl, the tertiary butyl, 2-the ethylhexyl ,-CH that be preferably substituted as the base on the Sauerstoffatom of-C (=the O)-O-being binding on ester functional group of alcohol composition, are unsubstituted ₂cH ₂o-(CH ₂cH ₂) _n-C ₂h ₅deng], thiazolinyl (such as vinyl, allyl group, 2-methyl-2-propenyl, crotyl, oleyl etc.), total carbon number of this alcohol composition (being binding on the base on Sauerstoffatom) is preferably 1 ~ 200, be more preferably 1 ~ 100, and then be more preferably 1 ~ 50.The substituting group that this alkyl and thiazolinyl can have is preferably alkoxyl group, alkene oxygen base, hydroxyl, acyloxy, is more preferably alkoxyl group.This alkoxyl group or alkene oxygen base are preferably containing (gathering) oxyalkylene person, especially, should be preferably poly-(oxygen ethylidene) base, (gathering) oxygen propylidene, (gathering) oxygen butylidene by (gathering) oxyalkylene.

In addition, the alcohol of the raw material in alcohol composition can be monohydroxy-alcohol, also can be polyvalent alcohol, and polyvalent alcohol include, for example ethylene glycol, propylene glycol, glycerine, tetramethylolmethane, and these hydroxylic moiety (-OH) becomes poly (oxyalkylene) oxygen base person [such as-(OCH ₂cH ₂) _n-OH ,-(OC ₃h ₆) _n-OH] also preferred.

In polycarboxylic acid acid amides, the amine compound of amine component can be any one of primary amine or secondary amine, is not particularly limited.The substituting group be replaced on the nitrogen-atoms of-C (=the O)-N < of amide functional base is preferably alkyl [such as methyl, ethyl, sec.-propyl, the tertiary butyl, 2-ethylhexyl ,-CH ₂cH ₂o-(CH ₂cH ₂) _n-C ₂h ₅deng], thiazolinyl (such as vinyl, allyl group, 2-methyl-2-propenyl, crotyl etc.), be preferably 1 ~ 200 as total carbon number of the amine compound of this amine component, be more preferably 1 ~ 100, and then be more preferably 1 ~ 50.The substituting group that this alkyl and thiazolinyl can have is preferably alkoxyl group, alkene oxygen base, hydroxyl, acyloxy, amino, acyl amino, is more preferably alkoxyl group.This alkoxyl group or alkene oxygen base are preferably containing (gathering) oxyalkylene person, especially, should be preferably poly-(oxygen ethylidene) base, (gathering) oxygen propylidene, (gathering) oxygen butylidene by (gathering) oxyalkylene.In addition, this kind of polyoxyalkylene moieties structure is also preferred containing the polyoxy alkylidene through branch via glycerine.

In addition, the amine compound of the raw material in amine component can be monoamine, also can be polyamine.

Among polycarboxylic acid derivative, be particularly preferably and there is unreacted and the organic acid list glyceride of the carboxyl that can dissociate, as its commercially available product, include, for example: reason grinds Po Aimu (Poem) K-37V (glycerine citric acid oleic acid ester) of VITAMIN (Riken Vitamin) (share) company manufacture, rank, Shanxi (Step) SS (glycerol stearate/palmitinic acid succinate) etc. of KAO. Corp. SA's manufacture.

As above-mentioned interfacial agent, compound described in the paragraph 0127 ~ paragraph 0128 of compound described in the paragraph 0050 ~ paragraph 0051 of Japanese Patent Laid-Open 2006-45497 publication, Japanese Patent Laid-Open 2002-322294 publication preferably can be used.As the interfacial agent of nonionic system, specifically, can enumerate: Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyol fat acid moieties ester, polyoxyethylene polyol fatty acid moieties ester, polyoxyethylene fatty acid ester, polyglycerol fatty acid ester, fatty diglycollic amide, trolamine fatty acid part ester, polyetheramine.In addition, as commercially available product, can enumerate: Na Yimin (NYMEEN) L-202, Si Tahaomu (STAFOAM) DO, Si Tahaomu (STAFOAM) DL (day oil) etc.

Above-mentioned sequestrant is can the compound of coordination (chelating) on the polyvalent metal ions such as the alkaline-earth metal ions such as metal ion or calcium ion such as iron ion, can use as any one of the various sequestrants that are representative with aminopolycanboxylic acid, aminopolyphosphonic acid, alkyl phosphonic acid, phosphono-carboxylic acids.As sequestrant, compound described in each publication of No. 6-8956, Japanese Patent Laid-fair, No. 11-190892, Japanese Patent Laid-Open, No. 2000-18038, Japanese Patent Laid-Open, No. 2010-158640, Japanese Patent Laid-Open, No. 2006-328203, Japanese Patent Laid-Open, No. 2005-68246, Japanese Patent Laid-Open, No. 2006-306969, Japanese Patent Laid-Open can be used.

Specifically, can enumerate: ethylenediamine tetraacetic acid (EDTA), hydroxyethylethylene diamine tri-acetic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid(NTA) (nitrilotriacetic acid), teiethylene tetramine-hexacetic acid, CDTA, hydroxyethyliminodiacetic acid, ethyleneglycolbis(2-aminoethylether)tetraacetic acid, 1, 3-diaminopropanetetraacetic acid, phosphonic acids, 1-hydroxy ethylene-1, 1-di 2 ethylhexyl phosphonic acid, nitrilo-N, N, N-trimethylene phosphonic, quadrol-N, N, N, N-tetramethylene phosphonic acid, quadrol-two (ortho-hydroxyphenyl acetic acid), DL-Alanine-N, N-oxalic acid, aspartic acid-N, N-oxalic acid, L-glutamic acid-N, N-oxalic acid, Serine-N, N-oxalic acid, polyacrylic acid, isopentene-acid/maleic acid copolymers, vinylformic acid-acid/maleic acid copolymers, acrylic acid-methacrylic acid multipolymer, silicic acid, gluconic acid, hydroxybenzyl iminodiethanoic acid, iminodiethanoic acid etc.In addition, use oil-soluble sequestrant also preferred.As commercially available product, can use: Te Kulang (Techrun) DO (length is rapids changes into (Nagase chemteX) limited-liability company), lucky this moral (Chelest) MZ-2, this moral lucky (Chelest) MZ-8 (lucky this moral (Chelest) limited-liability company).

The formation of < cellulose acylate film and physical property >

(the layer structure of film)

Cellulose acylate film of the present invention can be individual layer, also can be the duplexer of more than 2 layers.

When cellulose acylate film of the present invention is the duplexer of more than 2 layers, be more preferably 2 layers of structure or 3 layers of structure, be preferably 3 layers of structure.3 layers of structure preferably comprise core (core) layer (hereinafter also referred to as basic unit) of 1 layer and clamp this core layer and epidermis (skin) layer (being called epidermis A layer and epidermis B layer) (the epidermis B layer/core layer/epidermis A layer) of mutual subtend.

Moreover, also epidermis A layer and epidermis B layer are generically and collectively referred to as epidermal area (or top layer).

In cellulose acylate film of the present invention; the acyl substitution of the acylated cellulose in each layer can be consistent; also multiple acylated cellulose can be made to mix be present in a layer, but with regard to the viewpoint adjusting optical characteristics, the acyl substitution being preferably the acylated cellulose in each layer is all fixed.In addition, when cellulose acylate film of the present invention is 3 layers of structure, with regard to the viewpoint of manufacturing cost, be preferably acylated cellulose contained in the upper layer on two sides and use the acylated cellulose that acyl substitution is identical.

(Young's modulus)

The scope of the Young's modulus of cellulose acylate film of the present invention is not particularly limited, but with regard to the viewpoint manufacturing adaptability and operability, is preferably 1.0GPa ~ 5.0GPa, is more preferably 2.0GPa ~ 4.5GPa.By being added in acylated cellulose by the compound represented by general formula (I) of the present invention, and making film hydrophobization, having the effect promoting Young's modulus thus.That is, the interpolation of the compound represented by general formula (I) of the present invention is also favourable with regard to the viewpoint of Young's modulus.

(photoelastic coefficient)

The absolute value of the photoelastic coefficient of cellulose acylate film of the present invention is preferably 8.0 × 10 ^-12m ²/ below N, is more preferably 6 × 10 ^-12m ²/ below N, and then be more preferably 5 × 10 ^-12m ²/ below N.By making the photoelastic coefficient of resin molding diminish, when being assembled in liquid crystal indicator as polarization board protective film by this resin molding, hot and humid lower generation can be suppressed uneven.As long as in advance without special instruction, then photoelastic coefficient is set to and is undertaken measuring and the person of calculating by following method.

The lower value of modulus of photoelasticity is not particularly limited, but actual be 0.1 × 10 ^-12m ²/ more than N.

(calculation method of modulus of photoelasticity)

Film is cut into 3.5cm × 12cm, utilize ellipsometer (M150 [trade(brand)name], Japan's light splitting (share)) measure Re under the various loads of zero load, 250g, 500g, 1000g, 1500g, carry out calculating by the obliquity of the straight line changed according to the Re corresponding to stress and measure photoelastic coefficient.

(water ratio)

The water ratio of cellulose acylate film is evaluated by the equilibrium moisture content measured under fixing humiture.Equilibrium moisture content is placed after 24 hours under above-mentioned humiture, utilize Ka Erfei snow dust (Karl Fischer ' s method) to measure the amount of moisture reaching the sample of balance, and make amount of moisture (g) divided by sample mass (g) person of calculating.

Cellulose acylate film of the present invention 25 DEG C, water ratio under relative humidity 80% is preferably below 5 quality %, be more preferably below 4 quality %, and then be more preferably less than 3 quality %.Diminished by the water ratio acidylating cellulose membrane, when being assembled in liquid crystal indicator as polarization board protective film by cellulose acylate film, the suppression of the black display quality badness of the liquid crystal indicator under hot and humid is excellent.The lower value of water ratio is not particularly limited, but actual be more than 0.1 quality %.

(Water Vapour Permeability)

The Water Vapour Permeability of cellulose acylate film is evaluated by such as under type: according to Water Vapour Permeability test (agar diffusion method (cupmethod)) of JIS Z0208; in the environment of temperature 40 DEG C, relative humidity 90%RH; measure the quality by the water vapour of sample in 24 hours, and be converted into Area of Sample 1m ²value.

The Water Vapour Permeability of cellulose acylate film of the present invention is preferably 500g/m ²day ~ 2000g/m ²day, is more preferably 900g/m ²day ~ 1300g/m ²day, is particularly preferably 1000g/m ²day ~ 1200g/m ²day.

(mist degree)

The mist degree of cellulose acylate film of the present invention is preferably less than 1%, is more preferably less than 0.7%, is particularly preferably less than 0.5%.By mist degree is set to below above-mentioned higher limit, and the transparency with film becomes higher, be more easily used as this advantage of blooming.The lower value of mist degree is not particularly limited, but actual be more than 0.001%.Mist degree be 25 DEG C, under the environment of relative humidity 60%, use haze meter (HGM-2DP, this Accelerated Life machine (Suga Test Instruments)), according to JIS K7136, the cellulose acylate film of 40mm × 80mm measured.

(thickness)

The average film thickness of cellulose acylate film of the present invention is preferably 10 μm ~ 100 μm, is more preferably 15 μm ~ 80 μm, and then is more preferably 20 μm ~ 70 μm.By being set to more than 20 μm, operability when making netted film promotes and preferably.In addition, by being set to less than 70 μm, and easily tackle humidity change, and easily maintain optical characteristics.

In addition, when the lit-par-lit structure that cellulose acylate film tool of the present invention haves three layers above, the thickness of above-mentioned core layer is preferably 3 μm ~ 70 μm, is more preferably 5 μm ~ 60 μm.When the lit-par-lit structure that film tool of the present invention haves three layers above, the thickness on the top layer (epidermis A layer and epidermis B layer) on film two sides is all more preferably 0.5 μm ~ 20 μm, is particularly preferably 0.5 μm ~ 10 μm, most preferably is 0.5 μm ~ 3 μm.

(film width)

The film width of cellulose acylate film of the present invention is preferably 700mm ~ 3000mm, is more preferably 1000mm ~ 2800mm, is particularly preferably 1300mm ~ 2500mm.

The manufacture method > of < cellulose acylate film

The manufacture method of cellulose acylate film of the present invention is not particularly limited, but manufactures preferably by melting masking method or solution film-forming method.Be more preferably and manufactured by solution film-forming method (solvent casting method).Cellulose acylate film of the present invention manufactures preferably by solvent casting method.About the Production Example of cellulose acylate film utilizing solvent casting method, can with reference to United States Patent (USP) the 2nd, 336, No. 310, United States Patent (USP) the 2nd, 367, No. 603, United States Patent (USP) the 2nd, 492, No. 078, United States Patent (USP) the 2nd, 492, No. 977, United States Patent (USP) the 2nd, 492, No. 978, United States Patent (USP) the 2nd, 607, No. 704, United States Patent (USP) the 2nd, 739, No. 069 and United States Patent (USP) the 2nd, 739, each specification sheets of No. 070, each specification sheets of No. 640731st, English Patent and No. 736892nd, English Patent, and No. 45-4554, Japanese Patent examined patent publication, No. 49-5614, Japanese Patent examined patent publication, No. 60-176834, Japanese Patent Laid-Open No. Sho, each publication of No. 60-203430, Japanese Patent Laid-Open No. Sho and Japanese Patent Laid-Open No. Sho 62-115035 etc.In addition, above-mentioned cellulose acylate film also can be implemented prolonged treatment.About prolonged treatment method and condition, such as can with reference to each publication of No. 62-115035, Japanese Patent Laid-Open No. Sho, No. 4-152125, Japanese Patent Laid-Open, No. 4-284211, Japanese Patent Laid-Open, No. 4-298310, Japanese Patent Laid-Open, No. 11-48271, Japanese Patent Laid-Open etc.

(casting method)

As the casting method of solution, have by the method be extruded into equably in prepared dope self-pressurization mould in metal support, utilize with blade adjustment for the time being in metal support the wing (doctor blade) of the thickness of the dope of curtain coating method, utilize the method etc. of carrying out the reverse roller coating machine regulated with the roller of reverse rotation, but preferably utilize the method for pressurizing mold.Compression molding has clothes hanger type mould or T type matrix etc., can preferably use any one mould.In addition, except method cited herein, also known the various methods that tri acetic acid fiber cellulose solution carries out casting film to be implemented by existing, by considering that the difference of the boiling point of the solvent used etc. sets each condition, and the effect identical with content described in each publication can be obtained.

Curtain coating altogether

In the formation of cellulose acylate film of the present invention; be preferably and use casting method (multilayer is curtain coating simultaneously), the successively stacked casting method such as casting method, coating method altogether; with regard to stable manufacture and reduce production cost viewpoint with regard to, be particularly preferably and use altogether casting method.

When casting method manufactures the cellulose acylate film of more than 2 layers altogether in utilization, first, prepare the cellulose acetate solution (dope) of each layer.Then, dope is extruded from having the curtain coating die head extruding the function of the curtain coating dope of each layer in different slit etc. simultaneously, curtain coating supporter (band or cylinder) make each layer dope carry out curtain coating simultaneously, and in suitable period, self-supporter strips, then carry out drying and film is shaped.Represent with sectional view in Fig. 2 and use casting head 3 altogether, top layer dope 1 and core layer dope 2 these 3 layers are extruded into the state of curtain coating supporter 4 carrying out curtain coating simultaneously.

Successively casting method

In successively casting method, first gravity flow adopts in die head the curtain coating dope extruding the 1st layer, and curtain coating is carried out on curtain coating supporter, then carry out drying or do not carry out drying, the main points of the curtain coating dope curtain coating dope of the 2nd layer being extruded into the 1st layer carrying out curtain coating are adopted in die head with gravity flow, dope is successively made to carry out curtain coating stacked (if be necessary, then to more than the 3rd layer), and in suitable period, self-supporter strips, then carry out drying and film is shaped.

Coating method

Coating method is following method: usually make the film of core layer be configured as film by solution film-forming method, the coating fluid on top layer is coated in preparation, use suitable coating machine, coat on the two sides of film on each one side coating fluid being coated successively film or by coating fluid simultaneously, and carry out drying and be shaped to make the film of lit-par-lit structure.

As the curtain coating supporter (metal support) of cyclically movement used when manufacturing cellulose acylate film, can use and carry out effects on surface by chromium plating and carried out the cylinder of mirror finish or carried out the stainless steel conveyor belt (also referred to as being with) of mirror finish by surface grinding.The pressurizing mold used can arrange more than 1 or 2 above metal support.When arranging more than 2, the dope amount of carrying out curtain coating can be dispensed in each mould.Also dope can be delivered in mould with each ratio from multiple precise quantitative toothed gear pump.Temperature for the dope (resin solution) of curtain coating is preferably-10 DEG C ~ 55 DEG C, is more preferably 25 DEG C ~ 50 DEG C.In the case, all solution temperatures of step can identical or also can different everywhere in step.

In addition, there is no particular restriction for the material of above-mentioned metal support, but be more preferably stainless steel (Stainless Steel, SUS) system (such as SUS316).

(stripping)

In the manufacture of cellulose acylate film of the present invention, preferably comprise the step stripping above-mentioned dope film in above-mentioned metal support.

(prolonged treatment)

In the manufacture method of cellulose acylate film of the present invention, preferably comprise and make manufactured film carry out the step extended.The bearing of trend of cellulose acylate film can be any one of film conveyance direction and the direction orthogonal with conveyance direction (width); but with regard to the viewpoint continuing thereafter the Polarizer complete processing using this film, be preferably the direction (width) orthogonal with film conveyance direction.

The method carrying out in the direction of the width extending is such as on the books in each publication of No. 62-115035, Japanese Patent Laid-Open No. Sho, No. 4-152125, Japanese Patent Laid-Open, No. 4-284211, Japanese Patent Laid-Open, No. 4-298310, Japanese Patent Laid-Open, No. 11-48271, Japanese Patent Laid-Open etc.When the extension of length direction, if such as regulate the speed of carrying roller of film, make the coiling speed of film strip speed faster than film, then film is extended.When the extension of width, one side utilizes tenter machine to keep the width of film one side to transport, and the width of tenter machine is expanded lentamente, and film also can be made thus to extend.Also can, after the drying of film, elongator be used to carry out extending (uniaxial extension preferably using long elongator).

When cellulose acylate film of the present invention is used as the protective membrane of polaroid, in order to suppress from oblique observation Polarizer time light leak, must polaroid be configured to parallel through axle with the slow axis in the face of resin molding of the present invention.The usual width with rolling up film through axle of the polaroid that the volume manufactured continuously is membranaceous is parallel; therefore in order to make the membranaceous polaroid of above-mentioned volume fit continuously with the membranaceous protective membrane comprising cellulose acylate film of volume, in the face of rolling up membranaceous protective membrane, slow axis must be parallel with the width of film.Therefore, preferably extend more in the direction of the width.In addition, prolonged treatmently can to carry out in the way of masking step, also can carry out prolonged treatment to the former film batched after masking.

The extension of width is preferably the extension of 5% ~ 100%, is more preferably the extension carrying out 5% ~ 80%, is particularly preferably the extension carrying out 5% ~ 40%.Moreover what is called does not extend, refer to and extend to 0%.Prolonged treatmently can to carry out in the way of masking step, also can carry out prolonged treatment to the former film batched after masking.In the former case, can extend under the state containing residual solvent amount, can be 0.05% ~ 50% preferably to extend with residual solvent amount=(after remaining volatile component quality/heat treated film quality) × 100%.The extension of 5% ~ 80% is carried out under being particularly preferably the state being 0.05% ~ 5% in residual solvent amount.

(drying)

In the manufacture method of cellulose acylate film of the present invention; with regard to postponing the viewpoint of manifesting property, preferably comprise the step that cellulose acylate film is carried out to dry step and makes dried resin molding of the present invention extend at the temperature of second-order transition temperature (Tg) more than-10 DEG C.

The drying of the dope on metal support relevant to the manufacture of cellulose acylate film of the present invention is usually just like inferior method: from the face side of metal support (cylinder or travelling belt), is namely positioned at the method for the surperficial blowing hot-air of the net in metal support; From the method for the back side blowing hot-air of cylinder or travelling belt; Control the liquid of temperature from the rear-face contact of the opposition side as dope curtain coating face of travelling belt or cylinder, carry out heating and the rear surface liquid heat-transferring method etc. of control surface temperature to cylinder or travelling belt by heat transfer; But be preferably rear surface liquid heat transfer type.As long as the surface temperature of carrying out the metal support before curtain coating for below the boiling point of solvent that uses in dope, then can be any temperature.In order to promote drying and not lose the mobility in metal support, be preferably set to the boiling point of the solvent minimum than the boiling point in used solvent low 1 DEG C ~ temperature of 10 DEG C.Moreover, when stripping when not carrying out drying after cooling cast dope, be not limited to said temperature.

As long as the adjustment of film thickness, to become the mode of desired thickness, regulates solid component concentration, the slit gap of die orifice of mould, the extrusion pressure, metal support speed etc. in mould contained in dope.

Being preferably with the length of cellulose acylate film obtained by the way is that every 1 volume 100m ~ 10000m batches, and is more preferably 500m ~ 7000m, and then is more preferably 1000m ~ 6000m.When batching, be preferably and at least give knurling (knurling) to one end, the width of knurling is preferably 3mm ~ 50mm, is more preferably 5mm ~ 30mm, is highly preferably 0.5 μm ~ 500 μm, is more preferably 1 μm ~ 200 μm.It can be one side pressing, also can be two-sided pressing.

When being used as the optical compensation films of large picture liquid crystal indicator, such as, preferably film width is set to more than 1470mm to be shaped.In addition, polarization board protective film of the present invention not only comprises and cuts into and can enter the film of the diaphragm form of the size of liquid crystal indicator by direct-assembling, also comprises and is made into strip by continuous seepage, and the film of the form of wound into rolls.The polarization board protective film of the form of the latter carries out keeping, conveyance etc. in this condition, when actual sets loads liquid crystal indicator or when fitting with polaroid etc., cuts into desired size to use.In addition, with the state of strip with comprise after the same polaroid etc. being made into the polyvinyl alcohol film of strip etc. fits, when actual sets loads liquid crystal indicator, cut into desired size to use.As a form of the optical compensation films of wound into rolls, the form that length wound into a roll is the web-like of more than 2500m can be enumerated.

<< Polarizer >>

Polarizer of the present invention at least has polaroid and cellulose acylate film of the present invention.

Polarizer of the present invention preferably has polaroid, and has film of the present invention at the one or both sides of this polaroid.Polaroid has iodine polarizing sheet, the dyestuff system polaroid using dichroic dye or polyenoid system polaroid.Iodine polarizing sheet and dyestuff system polaroid use polyvinyl alcohol mesentery to manufacture usually.When cellulose acylate film of the present invention is used as polarization board protective film, the making method of Polarizer is not particularly limited, and makes by general method.There is following method: alkaline purification is carried out to obtained cellulose acylate film, then utilize fully saponified polyvinyl alcohol water solution to be fitted in by this cellulose acylate film and make polyvinyl alcohol film in iodine solution, carry out flooding the two sides of the polaroid made by extending.Also can implement as in Japanese Patent Laid-Open 6-94915 publication, Japanese Patent Laid-Open 6-118232 publication, described easily then processing replaces alkaline purification.Solid for making protective membrane treated side and polaroid fit include, for example: the polyethenol series such as polyvinyl alcohol, polyvinyl butyral solid, or the ethene system latex etc. such as butyl acrylate.

The applying method of cellulose acylate film of the present invention and polaroid is preferably becoming in fact orthogonal mode through axle and the slow axis of cellulose acylate film of the present invention and fit with polaroid.In liquid crystal indicator of the present invention, the slow axis through axle and cellulose acylate film of the present invention of Polarizer is preferably orthogonal in fact.Herein; what is called is orthogonal in fact; refer to that the direction through axle of the direction of the principal refractive index nx of cellulose acylate film of the present invention and Polarizer is with the angle of intersection of 90 ° ± 10 °, is preferably with the angle of intersection of 90 ° ± 5 °, is more preferably with the angle of intersection of 90 ° ± 1 °.By so adjusting angle when fitting, and the light leak under Polarizer cross-polarized light can be reduced further.The mensuration of slow axis measures by known various method, birefringence meter (examine Bradley (KOBRA) DH, prince measures machine (Oji ScientificInstruments) (share) manufacture) such as can be used to carry out.

Polarizer of the present invention not only comprises and cuts into and can enter the Polarizer of the diaphragm form of the size of liquid crystal indicator by direct-assembling, also comprise and be made into strip by continuous seepage, and the Polarizer of the form of wound into rolls (such as, the long form for more than 2500m or more than 3900m of volume).In order to for large picture liquid crystal indicator, preferably the width of Polarizer is set to more than 1470mm.About the concrete formation of Polarizer of the present invention, there is no particular restriction, can adopt known formation, such as, can adopt formation described in Fig. 6 of Japanese Patent Laid-Open 2008-262161 publication.

< < liquid crystal indicator > >

Liquid crystal indicator of the present invention has liquid crystal cells and Polarizer of the present invention.

Liquid crystal indicator of the present invention is preferably coplanar switching (In-Plane Switching, IPS) pattern, optical compensation curved (Optically Compensated Bend, OCB) pattern or vertical orientated (Vertical Alignment, VA) liquid crystal indicator of pattern, this liquid crystal indicator is the liquid crystal indicator of a pair Polarizer of the both sides having liquid crystal cells and be configured at this liquid crystal cells, and at least one of above-mentioned Polarizer is Polarizer of the present invention.The Inner Constitution of typical liquid crystal indicator is shown in Fig. 1.There is no particular restriction for the concrete formation of liquid crystal indicator of the present invention, can adopt known formation.In addition, formation described in Fig. 2 of Japanese Patent Laid-Open 2008-262161 publication can also preferably be adopted.

[embodiment]

Below, further illustrate the present invention by embodiment, but the present invention can't help this embodiment and restrictively make an explanation.

[synthesis of the compound represented by general formula (I)]

Synthesize the compound represented by general formula (I) of the present invention as follows.

Below represent the synthesis example of representative compound.

Synthesis example 1

Exemplary compounds (A-1) is synthesized by following reaction process.

[changing 30]

1) synthesis of intermediate N-benzyl-N '-phenylurea

Benzyl amine 321g and acetonitrile 2L is added in the glass flask of the 5L with thermometer, reflux cooling pipe and stirrer, utilize water-bath to carry out cooling rear one side to stir, the speed that one side becomes less than 40 DEG C with temperature in reaction solution drips phenylcarbimide 358g.Direct stirring, after 2 hours, carries out suction filtration after adding water 2L, and the crystallization that leaching is separated out, utilize water 1L to clean 3 times.At 80 DEG C, drying under reduced pressure is carried out to obtained crystallization, and obtain intermediate N-benzyl-N '-phenylurea 610g.

The structure of the compound obtained by ¹h-NMR (nuclear magnetic resonance, nucleus magnetic resonance) spectrum confirms.

¹H-NMR(300MHz、DMSO-d6)，δ：8.52(s，1H)，7.45-7.18(m，9H)，6.89(t，1H)，6.59(s，1H)，4.30(d，2H)

2) synthesis of exemplary compounds (A-1)

N-benzyl-N '-phenylurea 5.0g, phenylmalonic acid 8.16g, acetic acid 10mL and diacetyl oxide 15mL is added in the glass flask of the 300ml with thermometer, reflux cooling pipe and stirrer, one side is carried out stirring the mode that temperature within one side becomes 60 DEG C and is heated, and then directly at 60 DEG C, continues stirring 1.5 hours.Thereafter, till being cooled to room temperature, then diisopropyl ether 100mL is added.Utilize ice-water bath to carry out cooling and stir after 1 hour and carry out suction filtration, and the crystallization that leaching is separated out, utilize and carry out drying after the diisopropyl ether of cooling is cleaned, and obtain exemplary compounds (A-1) 4.2g.

The structure of the compound obtained by ¹h-NMR spectrum confirms.

¹H-NMR(300MHz、CDCl ₃)，δ：7.50-7.10(m，15H)，5.13(dd，2H)，4.80(s，1H)

Exemplary compounds (A-3) is such as synthesized by following reaction process.

[changing 31]

Synthesis example 2

(A) synthesis of the exemplary compounds (A-3) in approach 1

Intermediate N-benzyl-N '-phenylurea 5.0g synthesized in synthesis example 1, benzyl malonic acid 6.4g, toluene 10mL and diacetyl oxide 15mL is added in the glass flask of the 300ml with thermometer, reflux cooling pipe and stirrer, one side is carried out stirring the mode that temperature within one side becomes 75 DEG C and is heated, and then directly at 75 DEG C, continues stirring 2 hours.Thereafter be cooled to till 50 DEG C, then add 1mol/dm ³aqueous sodium hydroxide solution 50mL.Discarded organic phase also utilizes ice-water bath to cool aqueous phase, and then one side carries out stirring one side dropping 6M hydrochloric acid 10mL.And then stirring carried out suction filtration after 1 hour at 0 DEG C, and the crystallization that leaching is separated out, after utilizing water to clean, carry out drying, and obtain exemplary compounds (A-3) 7.5g.

The structure of the compound obtained by ¹h-NMR spectrum confirms.

¹H-NMR(300MHz、CDCl ₃)，δ：7.55-7.20(m，9H)，7.13(t，2H)，6.96(d，2H)，6.84(br，2H)，4.96(s，2H)，3.94(t，1H)，3.55(m，2H)

Synthesis example 3

(B) synthesis of the exemplary compounds (A-3) in approach 2

Synthesize exemplary compounds (A-3) as follows.

1) synthesis of intermediate 1-benzyl-3-phenyl barbituric acid

N-benzyl-N '-phenylurea 5.0g, propanedioic acid 2.5g, toluene 20mL and diacetyl oxide 5.6g synthesized in synthesis example 1-1 is added in the glass flask of the 300ml with thermometer, reflux cooling pipe and stirrer, one side is carried out stirring the mode that temperature within one side becomes 80 DEG C and is heated, and then directly at 80 DEG C, continues stirring 3 hours.Thereafter be cooled to till 50 DEG C, then add water 15mL and carry out separatory, and discarded aqueous phase.At room temperature one drip Virahol 5mL in the face of organic layer carries out stirring one side.And then stirring carried out suction filtration after 0.5 hour below 10 DEG C, and the crystallization that leaching is separated out, utilize after the Virahol of cooling cleans, carry out drying, and obtain intermediate 1-benzyl-3-phenyl barbituric acid 4.6g.

The structure of the compound obtained by ¹h-NMR spectrum confirms.

¹H-NMR(300MHz、CDCl ₃)，δ：7.52-7.16(m，10H)，5.10(s，2H)，3.86(s，2H)

2) synthesis of intermediate 1-benzyl-5-benzylidene-3-phenyl barbituric acid

1-benzyl-3-phenyl barbituric acid 4.0g, phenyl aldehyde 1.6g, acetic acid 40mL is added in the glass flask of the 300ml with thermometer, reflux cooling pipe and stirrer, after adding 1 sulfuric acid, one side is carried out stirring the mode that temperature within one side becomes 100 DEG C and is heated, and then directly at 100 DEG C, continues stirring 3 hours.Thereafter be cooled to till 50 DEG C, add Virahol 39mL and water 17mL mixing solutions and stir 1 hour below 10 DEG C after, carry out suction filtration and the leaching crystallization of separating out, after utilizing methyl alcohol to clean, obtain intermediate 1-benzyl-5-benzylidene-3-phenyl barbituric acid 3.9g.

The structure of the compound obtained by ¹h-NMR spectrum confirms.

¹H-NMR(300MHz、CDCl ₃)，δ：8.70(s，1H)，8.10(d，2H)，7.58-7.20(m，15H)，5.20(s，2H)

3) synthesis of exemplary compounds (A-3)

1-benzyl-5-benzylidene-3-phenyl barbituric acid 3.5g, methyl alcohol 8mL is added in the autoclave of 50ml, and add Pd-C (10%) 0.1g, one side carry out stirring one side fill H2 and within the temperature mode that becomes 50 DEG C heat, then directly at 50 DEG C, continue stirring 3 hours.Thereafter leaching Pd-C, and be cooled to till 5 DEG C, and then add water 4mL and stir at 5 DEG C after 1 hour, carry out suction filtration and the leaching crystallization of separating out, after utilizing the mixed solvent of methanol/water=1/1 to clean, carry out drying, and obtain exemplary compounds (A-3) 3.0g.

The structure of the compound obtained by ¹h-NMR spectrum, infrared rays (Infrared, IR) spectrum and mass spectrum (MassSpectrum) confirm.

Moreover, by ¹h-NMR spectrum and confirm that the structure of obtained compound is consistent with the structure of the compound obtained in synthesis example 2.

The compound other than the above used in embodiment synthesizes by method described in method similar to the above or above-mentioned document or according to the method for the method.

Herein, the fusing point of exemplary compounds (A-2) is 139 DEG C, and the fusing point of exemplary compounds (A-4) is 88 DEG C, and the fusing point of exemplary compounds (A-5) is 113 DEG C.

Embodiment 1

Make cellulose acylate film as follows, evaluate painted for the film caused by light as photostabilization.

(preparation of acylated cellulose)

Preparing total degree of substitution with acetyl group (B) is the acylated cellulose of 2.87.This preparation adds sulfuric acid (be 7.8 mass parts relative to Mierocrystalline cellulose 100 mass parts), as catalyzer, be then added to the carboxylic acid of the raw material of acyl substituent and carry out acylation reaction at 40 DEG C.In addition, carry out aging with 40 DEG C after acylations.And then, utilize the low molecular weight compositions of acetone to this acylated cellulose clean and removed.

(preparation of top layer dope)

The preparation of cellulose acylate solutions

Following composition is fed in tempering tank, carries out stirring to make each component dissolves, and prepare cellulose acylate solutions.

Moreover luxuriant the scratching that the first technical chemistry company manufactures sends spy (Monopet) (registered trademark) SB to be the benzoic ether of sucrose, Eastman Chemical manufactures acetic ester and the isobutyrate that SAIB-100 is sucrose.

The preparation of Mat agent solution

Following composition is fed in dispersion machine, carries out stirring to make each component dissolves, and prepare Mat agent solution.

The preparation of ultraviolet absorbent solution

Be fed in tempering tank by following composition, one side is carried out heating one side and is carried out stirring to make each component dissolves, and prepares ultraviolet absorbent solution.

[changing 32]

Filter the online mixing tank of rear use to above-mentioned Mat agent solution 1.3 mass parts and ultraviolet absorbent solution 3.4 mass parts respectively to mix; and then add cellulose acylate solutions 95.3 mass parts; and use online mixing tank to mix, and prepare top layer solution.

(preparation of basic unit's dope)

The preparation of cellulose acylate solutions

Following composition is fed in tempering tank, carries out stirring to make each component dissolves, and prepare basic unit's dope.

(curtain coating)

Use cylinder casting device, from curtain coating mouth makes the top layer dope these 3 layers of basic unit's dope and the both sides thereof of as above preparing while, on the curtain coating supporter (supporter temperature is for-9 DEG C) of stainless steel, carry out curtain coating equably.Strip under the state that residual solvent amount in the dope of each layer is roughly 70 quality %, pin tenter is utilized to fix the two ends of the width of film, under the state that residual solvent amount is 3 quality % ~ 5 quality %, extend 1.28 times (28%) in the direction of the width and carry out drying.Thereafter, transport between the roller of thermal treatment unit, carry out drying further thus, and obtain cellulose acylate film 101 of the present invention.The thickness of the cellulose acylate film 101 obtained is 60 μm, and width is 1480mm.

In above-mentioned cellulose acylate film 101; as the kind of modification compound as described in table 6 described later and addition replace exemplary compounds A-1; in addition, with cellulose acylate film c10 ~ cellulose acylate film c13 that the mode identical with cellulose acylate film 101 manufactures cellulose acylate film 102 ~ cellulose acylate film 118 of the present invention respectively and compare.

In addition, in above-mentioned cellulose acylate film 101, become 40 μm with the thickness of obtained cellulose acylate film, the width mode that becomes 1480mm carries out curtain coating, drying, and obtain cellulose acylate film 131 of the present invention.In this cellulose acylate film 131; as the kind of modification compound replaces exemplary compounds A-1 as described in table 6 described later; in addition, with the cellulose acylate film c21 that the mode identical with cellulose acylate film 131 manufactures cellulose acylate film 132 ~ cellulose acylate film 135 of the present invention respectively and compare.

Same in above-mentioned cellulose acylate film 101, become 25 μm with the thickness of obtained cellulose acylate film, the width mode that becomes 1480mm carries out curtain coating, drying, and obtain cellulose acylate film 141 of the present invention.In this cellulose acylate film 141; as the kind of modification compound replaces exemplary compounds A-1 as described in table 6 described later; in addition, with the cellulose acylate film c22 that the mode identical with cellulose acylate film 141 manufactures cellulose acylate film 142 ~ cellulose acylate film 145 of the present invention respectively and compare.

And then; in above-mentioned cellulose acylate film 101; following polycondensation polymer (A) 12 mass parts of adding as contracting Polyester fluidizer replaces luxuriant scratching to send spy (Monopet) (registered trademark) SB and SAIB-100; in addition, cellulose acylate film 201 of the present invention is obtained in the mode identical with cellulose acylate film 101.In this cellulose acylate film 201; as the kind of modification compound replaces exemplary compounds A-1 as described in table 6 described later; in addition, with cellulose acylate film c30 ~ cellulose acylate film c33 that the mode identical with cellulose acylate film 201 manufactures cellulose acylate film 202 ~ cellulose acylate film 205 of the present invention respectively and compare.

Polycondensation polymer (A): the polyester (end is hydroxyl) (number average molecular weight=1000) comprising hexanodioic acid and ethylene glycol

The painted evaluation of film caused by light is carried out to each cellulose acylate film.

The result of obtained result and embodiment 2, embodiment 3 is together gathered and is shown in table 6 described later.

Moreover, also these cellulose acylate films are called polarization board protective film below.

(evaluation that the film caused by light is painted)

Using super xenon Ageing machine (this adds (Suga) trier (share) manufacture SX75), is 150W/m in radiation illumination ², blackboard temperature is 63 DEG C, relative humidity is under the condition of 50%RH, 120 h light are carried out to each cellulose acylate film made in the above described manner and penetrate.Thereafter, the spectrophotometer UV3150 of Shimadzu Seisakusho Ltd. is used to measure tone b ^*.If tone b ^*value become large at minus side, then the blue degree through light increases, if become large in positive side, then yellow chromaticity increases.

In addition, by the b of each cellulose acylate film before and after above-mentioned rayed ^*change be set to Δ b ^*be used as the painted index caused by light.

Evaluate with following benchmark.

A: Δ b ^*be less than 0.05

B: Δ b ^*more than 0.05 and be less than 0.10

C: Δ b ^*more than 0.10 and be less than 0.15

D: Δ b ^*more than 0.15

Obtained result is gathered and is shown in table 6 described later.

Embodiment 2

Use cellulose acylate film made in embodiment 1, make Polarizer as follows and evaluate the weather resistance of Polarizer, and the blooming made with hard coat evaluate fast light adhesion.

(the saponification process of polarization board protective film)

At 55 DEG C, the polarization board protective film making to comprise cellulose acylate film 101 made in embodiment 1 floods 3 minutes in the aqueous sodium hydroxide solution of 2.3mol/L.Clean in the washing bath of room temperature, in then using the sulfuric acid of 0.05mol/L to carry out at 30 DEG C and.Again clean in the washing bath of room temperature, and then utilize the warm braw of 100 DEG C to carry out drying.So, each polarization board protective film is carried out to the saponification process on surface.

(making of Polarizer)

Iodine is adsorbed on the polyvinyl alcohol film of extension, makes polaroid.

Use polyethenol series solid, will be manufactured by embodiment 1, and the polarization board protective film 101 having carried out above-mentioned saponification process is attached at the side of polaroid.To commercially available tri cellulose acetate membrane (Fuji Tyke (FUJITAC) TD80UF; Fujiphoto (share) manufactures) also carry out identical saponification process; then polyethenol series solid is used; being on the face of the polaroid of opposition side with being pasted with through the side of the polarization board protective film 101 of saponification process, attach the above-mentioned commercially available tri cellulose acetate membrane of saponification process.

Now, with polaroid through axle, to make with by embodiment 1 and the slow axis completing the polarization board protective film of saponification process becomes parallel mode is configured.In addition, being also configured in an orthogonal manner through the slow axis of axle with the commercially available tri cellulose acetate membrane that completes saponification process of polaroid.

So make Polarizer 101 of the present invention.

For polarization board protective film 102 ~ polarization board protective film 118, polarization board protective film 131 ~ polarization board protective film 135, polarization board protective film 141 ~ polarization board protective film 145, polarization board protective film 201 ~ polarization board protective film 205 and the polarization board protective film c10 ~ polarization board protective film c13 compared, polarization board protective film c21, polarization board protective film c22, and polarization board protective film c30 ~ polarization board protective film c33, also the making of saponification process and Polarizer is carried out in mode in the same manner as described above respectively, and make Polarizer 102 ~ Polarizer 118 of the present invention respectively, Polarizer 131 ~ Polarizer 135, Polarizer 141 ~ Polarizer 145, Polarizer 201 ~ Polarizer 205, Polarizer c10 ~ Polarizer c13 relatively, Polarizer c21, Polarizer c22, and Polarizer c30 ~ Polarizer c33.

(evaluation of Polarizer weather resistance)

Polarizer endurance test be with via tackiness agent by Polarizer the form be attached on glass carry out as following.

Make 2 modes becoming Air Interface side with cellulose acylate film of the present invention and Polarizer is attached at sample (about 5cm × 5cm) on glass.In the orthogonal transmitance of veneer measures, the side of the cellulose acylate film of the present invention of this sample is measured after light source sets.Measure 2 samples respectively, using the orthogonal transmitance of its mean value as the Polarizer in embodiment.The orthogonal transmitance of Polarizer is the automatic light polarizing film determinator VAP-7070 using Japanese light splitting (share) to manufacture, and measures in the scope of 380nm ~ 780nm, and measured value when adopting 410nm.Thereafter, correspond to film thickness condition under through time preserve after, measure orthogonal transmitance in the same way.Obtain through time before and after the change of orthogonal transmitance, it can be used as Polarizer weather resistance and evaluate with following benchmark.

Moreover the relative humidity of not carrying out under the environment of damping is the scope of 0%RH ~ 20%RH.

Obtained result is shown in table 6 described later.

-through time condition-

Sample 101 ~ sample 118, sample 201 ~ sample 205, sample c10 ~ sample c13 and sample c30 ~ sample c33:

80 DEG C, under the environment of relative humidity 90%RH, 168 hours and 336 hours

Sample 131 ~ sample 135 and sample c21:

80 DEG C, under the environment of relative humidity 90%RH, 120 hours and 240 hours

Sample 141 ~ sample 145 and sample c22

60 DEG C, under the environment of relative humidity 95%RH, 500 hours and 1000 hours

A: through time before and after the change of orthogonal transmitance less than 0.6%

B: through time before and after orthogonal transmitance be changed to 0.6% ~ 1.0%

C: through time before and after the change of orthogonal transmitance more than 1.0%

Obtained result is gathered and is shown in table 6 described later.

(making with the blooming of hard coat)

After each composition mixing described in following table, utilize aperture to be that the polypropylene strainer of 30 μm filters, and prepare hard coat coating fluid.

With micro-plate gravure coating method, be under the condition of 30m/min in conveyance speed, by above-mentioned hard coat coating solution on the air side surface of above-mentioned manufactured each cellulose acylate film.Carry out drying in 150 seconds at 60 DEG C after, one side carries out nitrogen wash (purge) (oxygen concn is less than 0.5%), one side uses the air-cooled metal halide lamp (Ai Gufei (Eye Graphics) (share) manufacture) of 160W/cm, and irradiation illumination is 400mW/cm ², irradiation dose is 150mJ/cm ²ultraviolet coating layer is hardened, and form hard coat (thickness is 6 μm).

So, the air side surface of each cellulose acylate film forms hard coat, and makes the cellulose acylate film with hard coat respectively.

Moreover, in following table 6, with the blooming No. with hard coat corresponding to it, general film No. is added to the blooming No. of individual layer and represents.

(evaluation of fast light adhesion)

First; the super xenon Ageing machine SX75 utilizing this to add (Suga) trier (share) company to manufacture, 60 DEG C, irradiated to the polarization board protective film with hard coat of above-mentioned made each embodiment and comparative example under the environment of relative humidity 50% 96 little time.

Then, under the condition of temperature 25 DEG C, relative humidity 60%, damping in 2 hours is carried out respectively to the polarization board protective film with hard coat.On the surface of side with hard coat; square for the polarization board protective film 1cm with hard coat; utilize cutting knife be chessboard trellis respectively with vertical 11 of 1mm interval incision, the otch of horizontal 11; add up to and carve the square foursquare grid of 100 1mm, then the polyester adhesive tape (No.31B) that day east electrician (share) manufactures is attached on this face.After 30 minutes, rapid stripping tape in vertical direction, and check the quantity of the grid peeled off, evaluate with the benchmark in following 4 stages.Carry out 3 identical contiguity evaluations and average.Show the result in following table.

A: peeling off in 100 liters is less than 10 liters.

B: confirm 11 liters ~ 20 liters peel off in 100 liters.

C: confirm 21 liters ~ 30 liters peel off in 100 liters.

D: confirm more than 31 liters peel off in 100 liters.

These results are gathered and is shown in Table 6.

[table 6]

A) mass parts relative to acylated cellulose 100 mass parts is represented.

Herein, H-A, H-1 and H-2 in table 6 are following compound.

[changing 33]

According to the result of above-mentioned table 6; as the cellulose acylate film of the present invention containing the compound represented by general formula (I) of the present invention polarization board protective film through time Polarizer weather resistance all excellent; effectively can suppress the deterioration of polaroid; and then, caused by light through time painted few.

Relative to this; as the polarization board protective film c10 ~ polarization board protective film c12 of the cellulose acylate film containing above-mentioned comparative compound and H-A, H-1 or H-2 and polarization board protective film c30 ~ polarization board protective film c32 compared with polarization board protective film of the present invention, all cannot realize Polarizer weather resistance with suppress caused by light through time painted and deposit.In addition; the polarization board protective film being added with these comparative compounds is coated with the c10 ~ cellulose acylate film c12 of the cellulose acylate film with hard coat of hard coat and cellulose acylate film c30 ~ cellulose acylate film c32 compared with polarization board protective film of the present invention; all not good enough with the fast light adhesion of hard coat, cannot realize Polarizer weather resistance and fast light adhesion and deposit.

As neither containing compound represented by general formula (I) of the present invention, also not containing polarization board protective film c13, the polarization board protective film c21 of the cellulose acylate film of the comparison of the compound compared, polarization board protective film c22 and polarization board protective film c33 compared with the polarization board protective film as cellulose acylate film of the present invention, Polarizer weather resistance is all not good enough.

Its result, the Polarizer of the application of the invention, and the liquid crystal indicator of excellent performance as shown above can be made.

Embodiment 3

[change of total substitution value (B) of acylated cellulose]

In cellulose acylate film 101 in embodiment 1; add rhodia 100.0 mass parts that total degree of substitution with acetyl group (B) is 2.77; the total degree of substitution with acetyl group (B) used in the composition of the cellulose acylate solutions in the preparation of the solution of basic unit's dope is replaced to be the rhodia of 2.87; in addition, cellulose acylate film 301 of the present invention is obtained in the mode identical with cellulose acylate film 101.For this cellulose acylate film 301; as change as described in table 7 described later the different rhodia of total degree of substitution with acetyl group (B), the kind of exemplary compounds of adding and fluidizer; in addition, cellulose acylate film c40 and the cellulose acylate film c41 of cellulose acylate film 302 ~ cellulose acylate film 304 of the present invention and comparative example is manufactured in the mode identical with cellulose acylate film 301.

And then; in cellulose acylate film 202 in embodiment 1; the total degree of substitution with acetyl group of same interpolation (B) is rhodia 100.0 mass parts of 2.77; the total degree of substitution with acetyl group (B) used in the composition of the cellulose acylate solutions in the preparation of the solution of basic unit's dope is replaced to be the rhodia of 2.87; in addition, cellulose acylate film 311 of the present invention is obtained in the mode identical with cellulose acylate film 202.For this cellulose acylate film 311; as change as described in table 7 described later the different rhodia of total degree of substitution with acetyl group (B), the kind of exemplary compounds of adding and fluidizer; in addition, cellulose acylate film c42 and the cellulose acylate film c43 of cellulose acylate film 00312 ~ cellulose acylate film 314 of the present invention and comparative example is manufactured in the mode identical with cellulose acylate film 311.

In addition, Polarizer and the blooming with hard coat is made in the same way as in example 2.Except make Polarizer weather resistance through time condition become as except as following, evaluate in the same manner as embodiment 1, embodiment 2.

-through time condition-

Sample 301 ~ sample 304, sample 311 ~ sample 314, sample c40 ~ sample c43:

80 DEG C, under the environment of relative humidity 90%RH, 168 hours and 336 hours

Obtained result is gathered and is shown in following table 7.

[table 8]

Kind	Metal protection evaluation result	Remarks
			A-1	A	The present invention
A-2	A	The present invention
			A-3	A	The present invention
A-4	A	The present invention
			A-5	A	The present invention
A-6	A	The present invention
			A-14	A	The present invention
A-19	A	The present invention
			A-21	A	The present invention
H-1	A	Comparative example
			H-2	B	Comparative example
Nothing	B	Comparative example

According to the result of table 8, the metal protection of compound of the present invention is good, in contrast, the metal protection of the organic acid H-2 compared insufficient, therefore worries the deterioration of producing apparatus, and then being mixed into towards impurity in film of worry caused by this corrosion.

So, according to the result of table 6 ~ table 8, known compound of the present invention for the weather resistance improved effect of Polarizer and painted suppression effective, simultaneously favourable for the degree of freedom manufacturing stabilization or addition.

Embodiment 5

Make Polarizer as follows, and evaluate Polarizer weather resistance.

(preparation of cellulose acylate solutions 5-1)

Following composition is fed in tempering tank, carries out stirring to make each component dissolves, and prepare cellulose acylate solutions 5-1.

(preparation of Mat agent solution 5-2)

Following composition is fed in dispersion machine, carries out stirring to make each component dissolves, and prepare Mat agent solution 5-2.

(preparation of polaroid weather resistance modifying agent solution 5-3)

Be fed in tempering tank by following composition, one side is carried out heating one side and is carried out stirring to make each component dissolves, and prepares polaroid weather resistance modifying agent solution 5-3.

Moreover the Tokyo that above-mentioned reductone (L) is following structure changes into the Ascorbyl palmitate that (share) manufactures.

[changing 34]

(preparation of ultraviolet absorbent solution 5-4)

Be fed in tempering tank by following composition, one side is carried out heating one side and is carried out stirring to make each component dissolves, and prepares polaroid weather resistance modifying agent solution 5-4.

[changing 35]

< curtain coating >

After respectively the ultraviolet absorbent solution 5-4 of the above-mentioned Mat agent solution 5-2 of 1.3 mass parts, the polaroid weather resistance modifying agent solution 5-3 of 3.3 mass parts and 4.0 mass parts being filtered; online mixing tank is used to mix; and then add the cellulose acylate solutions 5-1 of 91.4 mass parts, then use online mixing tank to mix.Utilize bandcast device, make above-mentioned prepared dope carry out curtain coating on the curtain coating supporter (supporter temperature is 22 DEG C) of stainless steel.Strip under the state that residual solvent amount in dope is roughly 20 quality %, tenter machine is utilized to grip the two ends of the width of film, at the temperature of 120 DEG C, extend 1.10 times (10%) in the direction of the width with the state that residual solvent amount is 5 quality % ~ 10 quality % and carry out drying.Thereafter, transport between the roller of thermal treatment unit, carry out drying further thus, and obtain cellulose acylate film 501.The thickness of the cellulose acylate film obtained is 23 μm, and width is 1480mm.

And then; in above-mentioned cellulose acylate film 501; as change as described in following table 9 the kind of exemplary compounds of adding and the kind of addition and fluidizer and addition; in addition, cellulose acylate film 502 ~ cellulose acylate film 521 of the present invention is manufactured in the mode identical with cellulose acylate film 501.

In addition, in cellulose acylate film 501, unmixed polaroid weather resistance modifying agent solution 503, in addition, with the cellulose acylate film c61 of the mode comparison identical with cellulose acylate film 501.

Herein, in above-mentioned table 9, the new starting material used are as follows.

[use starting material]

Reductone L:6-O-palmitoyl-L-AA (Tokyo changes into industry (share) manufacture)

F-10 described in the paragraph 0166 of triaizine compounds T: Japanese Patent Laid-Open 8-333325 publication

A-50 described in the paragraph 0026 of hydroxylamine compounds H1: Japanese Patent Laid-Open 8-62767 publication

[changing 36]

Hydroxylamine compounds H2: dibenzylhydroxylamine (Tokyo changes into industry (share) manufacture)

Polyamine A:N, N, N ', N " and, N "-five (2-hydroxypropyl) Diethylenetriamine (Tokyo changes into industry (share) manufacture)

Polyamine B: tetraethylene-pentamine (Tokyo changes into industry (share) manufacture)

Amine C: three (n-octyl) amine (Tokyo changes into industry (share) manufacture)

Lucky this moral (Chelest) 3PA: lucky this moral (share) company manufactures

Lucky this moral (Chelest) PH-540: lucky this moral (share) company manufactures

Ai Di Coase tower ripple (Adekastab) PEP-36: rising sun electrification (share) manufactures

Yi Jialesi (IRGANOX) 1010: BASF AG manufactures

HP-136: BASF AG manufactures

Yi Jialesi (IRGANOX) MD 1024: BASF AG manufactures

Refined (TINUVIN) 123 of ground slave: BASF AG manufactures

Refined (TINUVIN) 770 of ground slave: BASF AG manufactures

Ai Di Coase tower ripple (Adekastab) LA-81: rising sun electrification (share) manufactures

Te Kulang (Techrun) DO: the long rapids company that changes into manufactures

Amber Eem (Poem) K-37V: reason is ground VITAMIN (share) company and manufactured

Si Tahaomu (STAFOAM) DL: day, oil (share) company manufactured

Na Yimin (NYMEEN) L-202: day, oil (share) company manufactured

Ai Pomin (Epomin) SP-006: Japanese catalyzer (share) company manufactures

Hydrophobizers 1: the polycondensate (end is acetyl ester group and molecular-weight average is 800) of phthalic acid/ethylene glycol

Use the cellulose acylate film 501 ~ cellulose acylate film 521 made in the above described manner and the cellulose acylate film c61 compared, make Polarizer in the same way as in example 2.

In these Polarizers; carry out the evaluation of weather resistance in the same way as in example 2; result is relative to the Polarizer using the cellulose acylate film c61 compared; use the Polarizer of cellulose acylate film 501 ~ cellulose acylate film 521 of the present invention through time before and after orthogonal transmitance change reduce, the deterioration of polarizing properties is inhibited.

Its result, the Polarizer of the application of the invention, and the liquid crystal indicator of excellent performance as shown above can be made.

Although be illustrated in the lump the present invention and its example, but can think that if contriver does not specify, then in any details illustrated, all do not limit the invention of contriver, the spirit of the invention shown in claim of enclosing and scope should not be violated and make an explanation widely.

The application advocates the right of priority of having carried out the Japanese Patent Patent 2013-173992 of patent application in Japan in 23, on Augusts of Japanese Patent Patent 2013-080013 and 2013 of having carried out the Japanese Patent Patent 2013-050503 of patent application, on April 5th, 2013 having carried out patent application in Japan in Japan based on 13, on the March of Japanese Patent Patent 2012-190013 and 2013 of to have carried out patent application in Japan on August 30th, 2012, carries out in this manual with reference to and these content is enrolled as a part for the record of this specification sheets.

The explanation of symbol

1: top layer dope

2: core layer (basic unit) uses dope

3: casting head altogether

4: curtain coating supporter

21A, 21B: Polarizer

22: colored filter substrate

23: liquid crystal layer

24: array substrate

25: light guiding plate

26: light source

31a, 31b: cellulose acylate film (polarization board protective film)

32: polaroid

Claims (16)

1. a cellulose acylate film, it comprises:

Acylated cellulose; And

At least a kind of compound represented by following general formula (I),

[in general formula (I), R ¹, R ³and R ⁵separately represent hydrogen atom, carbon number be 1 ~ 20 alkyl, carbon number be 3 ~ 20 cycloalkyl, carbon number be 2 ~ 20 thiazolinyl or carbon number be 6 ~ 20 aromatic series base; Described alkyl, cycloalkyl, thiazolinyl and aromatic series base can have substituting group; Wherein, R ¹, R ³and R ⁵in any one be aralkyl or cycloalkyl, and R ¹, R ³and R ⁵in existing ring structure add up to more than 3].

2. cellulose acylate film according to claim 1, wherein in described general formula (I), R ⁵for aralkyl or cycloalkyl.

3. cellulose acylate film according to claim 1 and 2, wherein in described general formula (I), R ¹, R ³and R ⁵there is the ring structure of more than 1 respectively.

4. cellulose acylate film according to any one of claim 1 to 3, wherein in described general formula (I), R ¹, R ³and R ⁵there is the aromatic ring structure of more than 1 respectively.

5. cellulose acylate film according to any one of claim 1 to 4, wherein in described general formula (I), R ¹, R ³and R ⁵the ring structure had is aromatic ring structure.

6. cellulose acylate film according to any one of claim 1 to 5, total acyl substitution (A) of wherein said acylated cellulose meets following formula:

1.5≤A≤3.0。

7. cellulose acylate film according to any one of claim 1 to 6, the acyl group of wherein said acylated cellulose is ethanoyl, and total degree of substitution with acetyl group (B) meets following formula:

2.0≤B≤3.0。

8. cellulose acylate film according to claim 7, wherein said total degree of substitution with acetyl group (B) is more than 2.5, less than 2.97.

9. cellulose acylate film according to any one of claim 1 to 8, it comprises at least a kind of polycondensation ester cpds.

10. cellulose acylate film according to claim 9, wherein said polycondensation ester cpds be make by following general formula ( _a) represented by least a kind of dicarboxylic acid, carry out polycondensation with at least a kind of glycol represented by following general formula (b) and the compound that obtains:

[in general formula (a), X represents the carbon number of divalence to be the fatty group of 2 ~ 18 or the carbon number of divalence is the aromatic series base of 6 ~ 18; In general formula (b), Z represents that the carbon number of divalence is the fatty group of 2 ~ 8].

11. cellulose acylate films according to claim 9 or 10, the number average molecular weight of wherein said polycondensation ester cpds is 500 ~ 2000.

12. cellulose acylate films according to any one of claim 9 to 11, the end of wherein said polycondensation ester cpds is through end-blocking.

13. cellulose acylate films according to any one of claim 1 to 12, it comprises the carbohydrate compound that monose or at least a kind comprise 2 ~ 10 monosaccharide units.

14. cellulose acylate films according to claim 13, wherein said carbohydrate compound has alkyl, aryl or acyl group alternatively base.

15. 1 kinds of Polarizers, it at least comprises cellulose acylate film according to any one of claim 1 to 14 and polaroid.

16. 1 kinds of liquid crystal indicators, it at least comprises Polarizer according to claim 15 and liquid crystal cells.