JP2014210905A - Cellulose acylate film, and polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cellulose acylate film capable of further enhancing performance of a liquid crystal display device by improving optical characteristics and durability of a polarizing plate, and to provide a polarizing plate and a liquid crystal display device using the cellulose acylate film.SOLUTION: The cellulose acylate film contains a cellulose acylate and at least one compound represented by general formula (I). The polarizing plate and the liquid crystal display device use the cellulose acylate film. R, R, and Reach represent a hydrogen atom, a C1-20 alkyl group, a C3-20 cycloalkyl group, a C2-20 alkenyl group, or a C6-20 aromatic group, where one of R, R, and Ris an aralkyl group or a cycloalkyl group. The total number of ring structures present in R, R, and Ris 3 or more.

Description

  The present invention relates to a cellulose acylate film, a polarizing plate using the same, and a liquid crystal display device.

  The cellulose acylate film is used in various liquid crystal display devices as an optical member of a liquid crystal display device, for example, a support for an optical compensation film, a protective film for a polarizing plate, and the like.

  In addition to being used indoors, such as for TV applications, the liquid crystal display device has been increasingly used outdoors, for example, mainly for portable devices. Therefore, development of a liquid crystal display device that can withstand use at higher temperatures and higher humidity than before has been demanded. However, when the liquid crystal display device is used under high temperature and high humidity, there is a problem that unevenness due to contraction of the polarizer occurs or the display performance deteriorates due to a decrease in polarization performance. In addition, liquid crystal display devices are increasingly required to withstand various usages even under severe use conditions, and higher levels of durability than ever have been required year after year.

  Patent Document 1 discloses that a resin film containing an organic acid having an acid dissociation constant of 2 to 7 in a specific solvent (including a cellulose acylate film) can improve the durability of a polarizer under high temperature and high humidity. Is described. Patent Document 2 also discloses a cellulose acylate film containing a barbituric acid derivative known as an organic acid, but there is no description regarding the durability of the polarizer.

JP 2011-118135 A JP 2011-126968 A

As a result of studies by the present inventors, in further improving the durability of the polarizer under high temperature and high humidity, adverse effects caused by the addition of various additives, for example, when coloring a film by light or providing a hard coat layer It was found that both new problems such as improved adhesion and reduced metal corrosivity are necessary.
The present invention improves the optical properties and durability of a polarizing plate, in particular, the adhesion when a film is inhibited from being colored by light or a hard coat layer is provided, and can improve the performance of a liquid crystal display device. It is an object to provide a rate film, a polarizing plate using the rate film, and a liquid crystal display device.

In order to solve the above-mentioned problems, the present inventors have studied the relationship between various additives and various performances. As a result, it has been found that when a barbituric acid derivative having a specific structure is added to the cellulose acylate film, coloring over time due to light irradiation can be suppressed. As a result of further investigation including substituents and combinations thereof, it was found that the ring structure that barbituric acid has as a substituent was important, and further investigation was repeated. From these examination results, the present inventors can improve the durability of the polarizing plate by using a cellulose acylate film containing a barbituric acid having a specific structure as a protective film for the polarizer. I found it.
In addition, since the barbituric acid derivative having the above specific structure exhibits almost no corrosive properties, is excellent in solubility in a solvent used during film formation, and has little volatilization, the cellulose acylate film is used in terms of production. Also had an advantage.

That is, the said subject was achieved by the following means.
<1> A cellulose acylate film containing cellulose acylate and at least one compound represented by the following general formula (I).

[In General Formula (I), R ¹ , R ³ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. Represents a group or an aromatic group having 6 to 20 carbon atoms. The alkyl group, cycloalkyl group, alkenyl group and aromatic group may have a substituent. However, any one of R ¹ , R ³ and R ⁵ is an aralkyl group or a cycloalkyl group, and the total number of ring structures present in R ¹ , R ³ and R ⁵ is 3 or more. ]
<2> The cellulose acylate film according to <1>, wherein in general formula (I), R ⁵ is an aralkyl group or a cycloalkyl group.
<3> The cellulose acylate film according to <1> or <2>, in which, in the general formula (I), R ¹ , R ^3, and R ⁵ each have one or more ring structures.
<4> The cellulose acylate film according to any one of <1> to <3>, wherein in general formula (I), R ¹ , R ^3, and R ⁵ each have one or more aromatic ring structures.
<5> The cellulose acylate film according to any one of <1> to <4>, wherein in the general formula (I), all of the ring structures of R ¹ , R ^3, and R ⁵ are aromatic ring structures.
<6> The cellulose acylate film according to any one of <1> to <5>, wherein the total acyl substitution degree (A) of the cellulose acylate satisfies the following formula.

          1.5 ≦ A ≦ 3.0

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

          2.0 ≦ B ≦ 3.0

<8> The cellulose acylate film according to <7>, wherein the total degree of acetyl substitution (B) is 2.5 or more and less than 2.97.
<9> The cellulose acylate film according to any one of <1> to <8>, containing at least one polycondensation ester compound.
A <10> polycondensation ester compound is obtained by polycondensation of at least one dicarboxylic acid represented by the following general formula (a) and at least one diol represented by the following general formula (b). The cellulose acylate film according to <9>, which is a compound.

[In General Formula (a), X represents a divalent aliphatic group having 2 to 18 carbon atoms or a divalent aromatic group having 6 to 18 carbon atoms. In general formula (b), Z represents a divalent aliphatic group having 2 to 8 carbon atoms. ]
The cellulose acylate film according to <9> or <10>, wherein the <11> polycondensed ester compound has a number average molecular weight of 500 to 2,000.
<12> The cellulose acylate film according to any one of <9> to <11>, wherein a terminal of the polycondensation ester compound is sealed.
<13> The cellulose acylate film according to any one of <1> to <12>, containing at least one monosaccharide or a carbohydrate compound composed of 2 to 10 monosaccharide units.
<14> The cellulose acylate film according to <13>, wherein the carbohydrate compound has an alkyl group, an aryl group, or an acyl group as a substituent.
<15> A polarizing plate having at least the cellulose acylate film according to any one of <1> to <14> and a polarizer.
<16> A liquid crystal display device comprising at least the polarizing plate according to <15> and a liquid crystal cell.

  In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after that as a lower limit value and an upper limit value.

  Further, in this specification, “group” described as each group is used in a meaning including both an unsubstituted form and a form having a substituent unless otherwise specified. For example, “alkyl group” means an alkyl group which may have a substituent. In the present specification, the “aliphatic group” is a linear, branched or cyclic aliphatic group which may be saturated or unsaturated (does not become an aromatic ring).

  In this specification, when a plurality of substituents and linking groups (hereinafter referred to as substituents and the like) are defined simultaneously or alternatively, the respective substituents and the like may be the same as or different from each other.

In the cellulose acylate film of the present invention, coloration with time due to light irradiation is further suppressed. Moreover, if it uses as a protective film of the polarizer in a polarizing plate, durability of a polarizing plate can be improved more.
As a result, the cellulose acylate film can improve the performance of the liquid crystal display device by improving the optical properties and durability of the polarizing plate, in particular, the adhesion when the film is prevented from being colored by light and the hard coat layer is provided. It has become possible to provide a polarizing plate and a liquid crystal display device using the same.

It is the schematic which shows an example which showed the internal structure of the liquid crystal display device typically. It is the schematic which shows an example when the cellulose acylate film of a three-layer structure is poured by simultaneous co-casting using a co-casting die.

  Hereinafter, the present invention will be described in detail with reference to embodiments.

<< Cellulose Acylate Film >>
The cellulose acylate film of the present invention contains cellulose acylate and at least one compound represented by the following general formula (I).
The cellulose acylate film of the present invention can exhibit the effect of suppressing the deterioration of the polarizing plate and is suitable for use as a protective film.

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

In general formula (I), R ¹ , R ³ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Or represents a C6-C20 aromatic group. The alkyl group, cycloalkyl group, alkenyl group and aromatic group may have a substituent. However, any one of R ¹ , R ³ and R ⁵ is an aralkyl group or a cycloalkyl group, and the total number of ring structures present in R ¹ , R ³ and R ⁵ is 3 or more.

The number of carbon atoms in the alkyl group in the ^R 1, ^{R 3} and ^{R 5} to 10, more preferably 1 to 5, more preferably 1 to 3, particularly preferably a methyl group or an ethyl group. However, in the case of the alkyl group which the aryl group substituted, ie, an aralkyl group, 7-20 are preferable, as for carbon number of an aralkyl group, 7-12 are more preferable, and 7-10 are more preferable.
The number of carbon atoms of the cycloalkyl groups represented by ^R 1, ^{R 3} and ^{R 5,} preferably from 3 to 10, more preferably 4 to 8, more preferably 5 or 6. Specific examples of the cycloalkyl group include, for example, cyclopropyl, cyclopentyl, and cyclohexyl, and cyclohexyl is particularly preferable.
The number of carbon atoms of the alkenyl group in the ^R 1, ^{R 3} and ^{R 5} are preferably 2 to 10, 2 to 5 is more preferred. For example, vinyl and allyl are mentioned.
The aromatic group in R ¹ , R ³ and R ⁵ may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. 6-16 are preferable and, as for carbon number of an aromatic group, 6-12 are more preferable.
As the aromatic group, especially the aromatic hydrocarbon group, phenyl and naphthyl are preferable, and phenyl is more preferable.

Each of the above groups for R ¹ , R ³ and R ⁵ may have a substituent.
The substituent is not particularly limited, and may be an alkyl group (preferably having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl and the like), alkenyl groups (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl and the like), alkynyl groups (preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl and the like) ), A cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, etc. 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), f B-ring group (preferably a heterocyclic group having 0 to 20 carbon atoms, wherein the ring-constituting hetero atom is preferably an oxygen atom, a nitrogen atom or a sulfur atom, and is a 5- or 6-membered ring fused with a benzene ring or a hetero ring. The ring may be a saturated ring, an unsaturated ring, or an aromatic ring. For example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy Group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group (preferably having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methyl Phenoxy, 4-methoxyphenoxy, etc.),

An alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, etc. , 4-methoxyphenylthio, etc.), sulfonyl groups (preferably alkyl or aryl sulfonyl groups, preferably having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, toluenesulfonyl, etc.), acyl groups ( Including alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, and heterocyclic carbonyl group, carbon number is preferably 20 or less, for example, acetyl, pivaloyl, acryloyl, metachloroyl, benzoyl, nicotinoyl, etc.), alkoxy Rubonyl group (preferably having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, for example, phenyloxycarbonyl, naphthyloxycarbonyl, etc.) An amino group (including an amino group, an alkylamino group, an arylamino group and a heterocyclic amino group, preferably having 0 to 20 carbon atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N- Ethylamino, anilino, 1-pyrrolidinyl, piperidino, morpholinyl, etc.), sulfonamide groups (preferably alkyl or aryl sulfonamide groups, preferably having 0 to 20 carbon atoms, for example, N, N-dimethylsulfonamide, N -Phenylsulfonamide etc.), sulfamoyl group Preferably, it is an alkyl or aryl sulfamoyl group, preferably having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), an acyloxy group (preferably having 1 to 20 carbon atoms). , For example, acetyloxy, benzoyloxy, etc.), carbamoyl groups (preferably alkyl or aryl carbamoyl groups, preferably having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino Group (preferably having 1 to 20 carbon atoms, for example, acetylamino, acryloylamino, benzoylamino, nicotinamide, etc.), cyano group, hydroxy group, mercapto group or halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine) Atoms).

The above substituent may be further substituted with the above substituent. Examples thereof include a perfluoroalkyl group such as trifluoromethyl, an aralkyl group, and an alkyl group substituted with an acyl group.
In addition, these substituents are applied not only to the substituents that each of R ¹ , R ³ , and R ⁵ may have, but also to the substituents in the compounds described in the present specification.

Here, among the above substituents that each of R ¹ , R ³ and R ⁵ may have, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a halogen atom, and an acyl group are preferable. An alkyl group, an aryl group, an alkoxy group, and an acyl group are more preferable, and an alkyl group and an alkoxy group are more preferable.

In the compound represented by the general formula (I), any one of R ¹ , R ³ and R ⁵ is an aralkyl group or a cycloalkyl group, and any one of them is preferably an aralkyl group.
Among these, those in which R ⁵ is an aralkyl group or a cycloalkyl group are preferable.

R ⁵ is preferably an aryl group, an alkyl group which may be substituted by an acyl group or a cycloalkyl group, an alkyl group substituted by an aryl group (ie, an aralkyl group, hereinafter referred to as an aralkyl group), or an acyl group substituted An alkyl group (preferably an alkyl group substituted with an acyl group and an aryl group) or a cycloalkyl group is more preferred, an aralkyl group or a cycloalkyl group is further preferred, and an aralkyl group is particularly preferred.
Hereinafter, the preferable alkyl group and cycloalkyl group in R ⁵ will be further described.

Among the alkyl groups, examples of the unsubstituted alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, and n-octyl.
Examples of the aralkyl group that is an alkyl group substituted with an aryl group include benzyl, phenethyl, and 3-phenylpropyl.

The acyl group in the alkyl group substituted with an acyl group is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group, more preferably a cycloalkylcarbonyl group or an arylcarbonyl group having a ring structure, particularly an arylcarbonyl group. preferable.
Examples of the alkylcarbonyl group include acetyl, propionyl, butyryl, and pivaloyl. Examples of the cycloalkylcarbonyl group include cyclopropylcarbonyl, cyclopentylcarbonyl, and cyclohexylcarbonyl. Examples of the arylcarbonyl group include, for example, , Benzoyl, toluoyl and naphthoyl.
Examples of the alkyl group substituted with an acyl group include a 2-acylethyl group, a 3-acylpropyl group, and a 2-acylpropyl group, with a 2-acylethyl group being preferred.
In the present invention, the alkyl group substituted with an acyl group is preferably an alkyl group substituted with an aryl group together with an acyl group. In this case, the aryl group is preferably a phenyl group.
Examples of the alkyl group substituted with an acyl group and an aryl group include 1-phenyl-2-benzoylethyl and 1-tolyl-2-benzoylethyl.

Examples of the cycloalkyl group and the aralkyl group include the groups exemplified for R ¹ , R ³ and R ⁵ .

Among the compounds represented by the general formula (I), preferred compounds are listed as follows.
A compound in which any one of R ¹ , R ³ and R ⁵ is an aralkyl group. Among the aralkyl groups, one in which one or two aryl groups are substituted on the alkyl group (two aryl groups are substituted) In this case, it is preferable to substitute the same carbon atom. Further, an alkyl group substituted with an aryl group and an acyl group (preferably an aryloyl group) is also preferable.
A compound in which any one of R ¹ , R ³ and R ⁵ is a group containing a cycloalkyl group, and preferably the group containing a cycloalkyl group is a cycloalkyl group

In the ring structure in the case where “the total number of ring structures present in R ¹ , R ³ and R ⁵ is 3 or more”, the basic skeleton itself of the substituent of R ¹ , R ³ or R ⁵ has a ring structure. In addition to the case, as already exemplified, a form in which the substituent of R ¹ , R ³ or R ⁵ has a ring structure is also included.
The ring structure is preferably a cyclic saturated hydrocarbon structure or an aromatic ring structure (aromatic hydrocarbon structure or aromatic heterocyclic structure). The ring structure may be a condensed ring structure.
When the ring structure is a cyclic saturated hydrocarbon structure, the cyclic saturated hydrocarbon structure is preferably present as a cycloalkyl group having 3 to 20 carbon atoms. More specifically, it is more preferably present as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group, and particularly preferably as a cyclohexyl group.
Moreover, when the said ring structure is an aromatic ring structure, it is preferable that it is an aromatic hydrocarbon structure. The aromatic hydrocarbon structure preferably exists as an aryl group having 6 to 20 carbon atoms. More specifically, it is more preferably present as a phenyl group or a naphthyl group, and particularly preferably as a phenyl group.

In the compound represented by the general formula (I), R ¹ , R ³ and R ⁵ are each an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms from the viewpoint of dissolution stability during film formation. Or it is more preferable that it is a C6-C20 aryl group. Further, R ¹ , R ³ and R ⁵ each preferably have one or more ring structures, and more preferably each have one ring structure.

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

In the general formula (Ia), L ¹ , L ³ and L ⁵ each independently represent a single bond or a divalent linking group having 1 or more carbon atoms. L ¹ , L ³ and L ⁵ are more preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and a single bond or a methylene group. Is particularly preferred. In view of dissolution stability, at least one of L ¹ , L ³ and L ⁵ is preferably an alkylene group having 1 to 6 carbon atoms, and preferably a methylene group or an ethylene group.
The divalent linking group represented by L ¹ , L ³ and L ⁵ may have a substituent, and each of the above-mentioned groups R ¹ , R ³ and R ⁵ has the substituent. Also good substituents are mentioned.

In the general formula (Ia), Ar ¹ , Ar ³ and Ar ⁵ each independently represent an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. Ar ¹ , Ar ³ and Ar ⁵ may have a substituent, and examples of the substituent include the substituents which each of the aforementioned R ¹ , R ³ and R ⁵ may have. Such a substituent is synonymous with the substituent which may be substituted when R ¹ , R ³ and R ⁵ are aromatic groups, and the preferred range is also the same.
Ar ¹ , Ar ³ and Ar ⁵ do not have a substituent, or when they have a substituent, the substituent preferably has no ring structure.

250-1200 are preferable, as for the molecular weight of the compound represented by general formula (I) and general formula (Ia), 300-800 are more preferable, and 350-600 are especially preferable.
By setting the molecular weight in such a preferable range, it is possible to obtain a highly transparent film excellent in suppressing volatilization from the film in the compound of the present invention.

  Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

It is known that the compound represented by the general formula (I) of the present invention can be synthesized using a synthesis method of barbituric acid in which a urea derivative and a malonic acid derivative are condensed. For barbituric acid having two substituents on the nitrogen atom, heat N, N 'disubstituted urea and malonic acid chloride or a combination of malonic acid and an activator such as acetic anhydride. For example, Journal of the American Chemical Society, 61, 1015 (1939), Journal of Medicinal Chemistry, 54, 2409 (2011), Tetrahedron 40, 29. 1999), and the method described in International Publication No. 2007/150011 pamphlet can be preferably used.
In addition, the malonic acid used for the condensation may be unsubstituted or substituted, and if malonic acid having a substituent corresponding to R ⁵ is used, a barbituric acid is constructed to construct the general formula of the present invention. The compound represented by (I) can be synthesized. Further, when an unsubstituted malonic acid and a urea derivative are condensed, a 5-position unsubstituted barbituric acid is obtained. By modifying this, a compound represented by the general formula (I) of the present invention is synthesized. May be.

As a method for modifying the 5-position, an addition reaction such as a nucleophilic substitution reaction with an alkyl halide or the like or a Michael addition reaction can be used. In addition, a method in which an alkylidene or arylidene compound is produced by dehydration condensation with an aldehyde or a ketone and then a double bond is reduced can be preferably used. For example, a reduction method using zinc is described in Tetrahedron Letters, 44, 2203 (2003), and a reduction method using catalytic reduction is Tetrahedron Letters, 42, 4103 (2001) or Journal of the American Chemical, 119, 12849 (1997), a reduction method using NaBH ₄ is described in Tetrahedron Letters, 28, 4173 (1987), etc., respectively. These are all synthetic methods that can be preferably used in the case of having an aralkyl group at the 5-position or a cycloalkyl group.
In addition, the synthesis | combining method of the compound represented with general formula (I) used for this invention is not limited above.

The content of the compound represented by the general formula (I) in the cellulose acylate film is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. It is more preferably 2 to 15 parts by mass, and particularly preferably 0.3 to 10 parts by mass.
By making the addition amount of the compound represented by the general formula (I) in the above range, it is possible to effectively reduce the moisture permeability and suppress the generation of haze.

<Cellulose acylate>
In the present invention, cellulose acylate is used as the main component of the film. Here, in the present specification, the “main component” refers to a component having a highest mass fraction in an embodiment in which there is one component as a raw material and in an embodiment having two or more components. One type of cellulose acylate may be used, or two or more types may be used. The acyl substituent of the cellulose acylate may be, for example, a cellulose acylate composed of an acetyl group alone, or a cellulose acylate having a plurality of different acyl substituents, or a mixture of different cellulose acylates. May be.

  Cellulose acylate raw material cellulose used in the present invention includes cotton linter and wood pulp (hardwood pulp, conifer pulp), and any cellulose acylate obtained from any raw material cellulose can be used and mixed in some cases. May be used. Detailed descriptions of these raw material celluloses can be found in, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), and Japan Institute of Invention and Publications. The cellulose described in 2001-1745 (pages 7-8) can be used.

  In the present invention, the acyl group of cellulose acylate may be only one type, or two or more types of acyl groups may be used. The cellulose acylate used in the present invention preferably has an acyl group having 2 to 4 carbon atoms as a substituent. When two or more kinds of acyl groups are used, one of them is preferably an acetyl group, and the other acyl group having 2 to 4 carbon atoms is preferably a propionyl group or a butyryl group. These cellulose acylates can produce a solution having a preferable solubility, and in particular, a non-chlorine organic solvent can be used to produce a good solution. Further, a solution having a low viscosity and good filterability can be produced.

First, the cellulose acylate preferably used in the present invention will be described in detail.
Glucose units having a β-1,4 bond constituting cellulose have free hydroxy groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by acylating part or all of these hydroxy groups with an acyl group.
The degree of acyl substitution indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and all the 2-position, 3-position and 6-position hydroxy groups of all glucose units are When acylated, the total acyl substitution degree is 3. For example, when all the glucose units are all acylated in all glucose units, the total acyl substitution degree is 1. Similarly, the total acyl substitution degree is 1 when all of either the 6-position or the 2-position are acylated in each glucose unit in all hydroxy groups of all glucose.
That is, the degree of acylation is indicated by 3 when all hydroxy groups in the glucose molecule are all acylated.
For details of the method for measuring the degree of acyl substitution, see Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995) and the method specified in ASTM-D817-96.

  The total acyl substitution degree (A) of the cellulose acylate used in the present invention is preferably 1.5 or more and 3 or less (1.5 ≦ A ≦ 3.0), more preferably 2.0 to 2.97, 2 It is more preferably from 0.5 to less than 2.97, particularly preferably from 2.70 to 2.95.

In the cellulose acetate using only acetyl group as the acyl group of cellulose acylate, the total degree of acetyl substitution (B) is preferably 2.0 or more and 3 or less (2.0 ≦ B ≦ 3.0), preferably 2 0.02 to 2.97 is more preferable, 2.5 or more and less than 2.97 is more preferable, 2.55 or more and less than 2.97 is particularly preferable, 2.60 to 2.96 is particularly preferable, and 2.70 to 2.95 is most preferred.
In addition, the compound represented by the general formula (I) of the present invention is particularly effective for cellulose acylate having a total degree of acetyl substitution (B) exceeding 2.50.

  The acyl group having 2 or more carbon atoms of the cellulose acylate used in the present invention may be an aliphatic acyl group or an aromatic acyl group, and is not particularly limited. They are, for example, alkyl carbonyl esters, alkenyl carbonyl esters, aromatic carbonyl esters, or aromatic alkyl carbonyl esters (aralkyl carbonyl esters) of cellulose, which may have a substituent. The acyl group having 2 or more carbon atoms is acetyl, propionyl, butanoyl, pentanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexanecarbonyl Oleoyl, benzoyl, naphthylcarbonyl, or cinnamoyl. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, or cinnamoyl is more preferable, and more preferably 2 carbon atoms such as acetyl, propionyl, or butanoyl. ~ 4 acyl groups, more preferably acetyl (i.e., when the cellulose acylate is cellulose acetate).

  In the acylation of cellulose, when an acid anhydride or acid chloride is used as an acylating agent, an organic carboxylic acid solvent or a halogen solvent (for example, acetic acid or methylene chloride) is preferably used as the organic solvent as a reaction solvent.

As the catalyst, when the acylating agent is an acid anhydride, a protic catalyst such as sulfuric acid is preferably used, and when the acylating agent is an acid chloride (for example, CH ₃ CH ₂ COCl), Basic compounds are used.

  The most common industrial synthesis method for cellulose mixed fatty acid esters is a fatty acid corresponding to an acyl group such as an acetyl group (for example, acetic acid corresponding to an acetyl group, propionic acid corresponding to a propionyl group, and a good acid corresponding to a pentanoyl group. This is a method of acylating cellulose using a mixed organic acid component containing valeric acid or the like or an acid anhydride of the fatty acid.

  Cellulose acylate can be synthesized, for example, by the method described in JP-A-10-45804.

  From the viewpoint of moisture permeability, the cellulose acylate film of the present invention preferably contains 5 to 99% by mass of cellulose acylate in the total solid content, more preferably 20 to 99% by mass, and more preferably 50 to 95% by mass. It is particularly preferred.

<Other additives>
In the cellulose acylate film of the present invention, a retardation adjusting agent (retardation developing agent and retardation reducing agent), a plasticizer (polycondensation ester compound (polymer), a polyhydric alcohol polyhydric ester, a phthalic acid ester, Additives such as phosphate esters, ultraviolet absorbers, antioxidants, matting agents, and the like can also be added.
In the present specification, the compound group may be described by incorporating a “system”, for example, as in the case of a phosphate ester compound. Means the same.

(Retardation reducing agent)
The polymer retardation reducing agent is preferably at least one selected from a phosphoric polyester polymer, a styrene polymer, an acrylic polymer, and a copolymer thereof, and at least one negative selected from an acrylic polymer and a styrene polymer. More preferred are polymers having intrinsic birefringence.

Further, a low molecular weight retardation reducing agent which is a non-phosphate ester compound is also preferably used.
The low molecular weight retardation reducing agent that is a non-phosphate ester compound is not particularly limited, but the compounds described in paragraph numbers 0066 to 0085 of JP-A-2007-272177 are preferred for details.

  The retardation reducing agent is more preferably an Rth reducing agent from the viewpoint of realizing a suitable Nz factor. Examples of the Rth reducing agent include acrylic polymers and styrene polymers, and low molecular compounds represented by general formulas (3) to (7) described in JP-A-2007-272177.

  The content of the retardation reducing agent in the cellulose acylate film is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the cellulose acylate. The part by mass is particularly preferred. By making the addition amount 30 parts by mass or less with respect to 100 parts by mass of cellulose acylate, compatibility with cellulose acylate can be improved, and the transparency of the cellulose acylate film can be improved. When using two or more types of retardation reducing agents, the total amount is preferably within the above range.

(Retardation expression agent)
The cellulose acylate film of the present invention preferably contains at least one retardation developer in order to develop a retardation value.
Although there is no restriction | limiting in particular as a retardation expression agent, The compound which shows a retardation expression property from what consists of a rod-shaped or a disk-shaped compound, and the said non-phosphate ester compound can be mentioned. As the rod-like or discotic compound, a compound having at least two aromatic rings can be preferably used as a retardation developer.
In the cellulose acylate film, the content of the retardation developer composed of a rod-like compound is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate. Further preferred. Further, the content of the discotic compound contained in the retardation enhancer in the cellulose acylate film is preferably less than 3 parts by mass, more preferably less than 2 parts by mass with respect to 100 parts by mass of the cellulose acylate. Less than part is particularly preferred.
Since the discotic compound is superior to the rod-like compound in terms of the retardation (Rth retardation) in the film thickness direction, it is preferably used when a particularly large Rth retardation is required. Two or more retardation developers may be used in combination.
The retardation developer preferably has a maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.

  Details of the retardation enhancer are described on page 49 of published technical bulletin 2001-1745.

(Plasticizer (hydrophobizing agent))
The cellulose acylate film of the present invention has, as a plasticizer (hydrophobizing agent), a polyhydric alcohol polyhydric ester compound (hereinafter also referred to as polyhydric alcohol ester plasticizer), a polycondensed ester compound (hereinafter polycondensed ester). It is preferable to include at least one compound selected from among a plasticizer and a carbohydrate compound (hereinafter also referred to as a carbohydrate derivative plasticizer).
The plasticizer is preferably one that can reduce the moisture content in the cellulose acylate film without lowering the glass transition temperature (Tg) of the cellulose acylate film as much as possible. By using such a plasticizer, it is possible to suppress the additive in the cellulose acylate film from diffusing into the polarizer layer under high temperature and high humidity, thereby improving the deterioration of the polarizer performance.
The plasticizer used in the present invention will be described in detail below.

(Polyhydric alcohol ester plasticizer)
In this invention, the polyhydric alcohol which is a synthetic raw material of a polyhydric alcohol ester plasticizer is represented by the following general formula (c).

Formula (c)
Rα- (OH) m

  In general formula (c), Rα represents an m-valent organic group, and m represents a positive integer of 2 or more.

  Among the compounds represented by the general formula (c), adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol , Hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, or xylitol is preferable. Call, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane or xylitol, it is more preferred.

  The polyhydric alcohol ester plasticizer is preferably a polyhydric alcohol having 5 or more carbon atoms, preferably a polyhydric alcohol ester synthesized from a polyhydric alcohol having 5 to 20 carbon atoms and a monocarboxylic acid.

  There is no restriction | limiting in particular in the monocarboxylic acid used for the synthesis | combination of a polyhydric alcohol ester plasticizer, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid etc. are mentioned. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferable in terms of improving moisture permeability and retention.

  Examples of the monocarboxylic acid include the following compounds, but the present invention is not limited thereto.

  The aliphatic monocarboxylic acid is preferably a linear or branched fatty acid having 1 to 32 carbon atoms. As for carbon number, 1-20 are more preferable, and 1-10 are especially preferable. When acetic acid is contained, the compatibility with the cellulose derivative is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  The aliphatic monocarboxylic acid is acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, At least one kind of saturation selected from myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and lactelic acid A fatty acid or at least one unsaturated fatty acid selected from undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid is preferred.

  The alicyclic monocarboxylic acid is preferably at least one selected from cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  The aromatic monocarboxylic acid is an aromatic monocarboxylic acid having two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid, etc. introduced by introducing an alkyl group into the benzene ring of benzoic acid such as benzoic acid or toluic acid. At least one selected from monocarboxylic acids and their derivatives is preferred. Of these, benzoic acid is preferred.

  The molecular weight of the polyhydric alcohol ester plasticizer is not particularly limited, but is preferably 300 to 3000, and more preferably 350 to 1500. By setting it as such molecular weight, it is excellent in suppression of volatilization from a film, and can make moisture permeability and compatibility with a cellulose derivative favorable.

  The carboxylic acid used for the synthesis of the polyhydric alcohol ester plasticizer may be one kind or a mixture of two or more kinds. Moreover, all the hydroxy groups in the polyhydric alcohol may be esterified, or a part of them may be left as they are.

  Specific examples of the polyhydric alcohol ester plasticizer are shown below, but the present invention is not limited thereto.

(Polycondensed ester plasticizer)
The cellulose acylate film of the present invention preferably contains a polycondensation ester plasticizer. By containing a polycondensation ester plasticizer, a cellulose ester film excellent in humidity stability and polarizing plate durability can be obtained.
The polycondensation ester plasticizer is obtained by polycondensing at least one dicarboxylic acid represented by the following general formula (a) and at least one diol represented by the following general formula (b).

  In general formulas (a) and (b), X represents a divalent aliphatic group having 2 to 18 carbon atoms or a divalent aromatic group having 6 to 18 carbon atoms, and Z represents a divalent carbon number of 2 to 2. Represents an aliphatic group of 8;

  Here, the divalent aliphatic group having 2 to 18 carbon atoms in X may be saturated or unsaturated, and may be a divalent chain or cyclic aliphatic group (for example, a cycloalkylene group). Any of these may be used. Moreover, when it is a bivalent chain aliphatic group, it may be linear or branched. 2-12 are more preferable and, as for carbon number of a bivalent aliphatic group, 2-6 are more preferable. Among them, the divalent aliphatic group having 2 to 18 carbon atoms is preferably a divalent chain saturated aliphatic group, more preferably a chain alkylene group, and even more preferably a linear alkylene group. Examples of the chain aliphatic group having 2 to 18 carbon atoms include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecylene, propylene, 2-methyltrimethylene, 2, Examples include 2-dimethyltrimethylene, cyclopentylene, cyclohexylene and the like.

  The divalent aromatic group having 6 to 18 carbon atoms in X may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. As a bivalent aromatic group, 6-15 are preferable and, as for carbon number, 6-12 are more preferable. The aromatic ring in the divalent aromatic hydrocarbon group is preferably a benzene ring, naphthalene ring, anthracene ring, biphenyl ring or terphenyl ring, and more preferably a benzene ring, naphthalene ring or biphenyl ring. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group preferably contains at least one of an oxygen atom, a nitrogen atom or a sulfur atom as a ring constituent atom. The aromatic heterocycle is furan ring, pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine ring, thiazoline ring, thiadiazole Ring, oxazoline ring, oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, acridine ring, phenanthroline ring, phenazine ring, tetrazole ring, benz An imidazole ring, benzoxazole ring, benzthiazole ring, benzotriazole ring or tetrazaindene ring is preferred, and a pyridine ring, triazine ring or quinoline ring is more preferred.

Z represents a divalent aliphatic group having 2 to 8 carbon atoms. The divalent aliphatic group having 2 to 8 carbon atoms may be saturated or unsaturated, and may be any divalent chain or cyclic aliphatic group (for example, a cycloalkylene group). Also good. Further, when it is a divalent chain aliphatic group, it may be a divalent straight chain or a branched chain. As for carbon number of a bivalent aliphatic group, 2-6 are more preferable, and 2-4 are more preferable. Among them, the divalent aliphatic group having 2 to 8 carbon atoms is preferably a divalent chain saturated aliphatic group, more preferably a chain alkylene group, and even more preferably a linear alkylene group. Examples of the chain alkylene group having 5 to 10 carbon atoms include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, propylene, 2-methyltrimethylene, 2,2- Examples include dimethyltrimethylene.
Examples of the divalent cycloalkylene group include cyclopentylene and cyclohexylene.

The aliphatic diol represented by the general formula (b) is more preferably at least one selected from ethylene glycol, 1,2-propanediol, and 1,3-propanediol, and crystals of a polycondensation ester plasticizer From the viewpoint of preventing the formation, at least one selected from ethylene glycol and 1,2-propanediol is particularly preferable.
The aliphatic diol residue of the polycondensed ester plasticizer preferably contains 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol% of ethylene glycol residues.

  The polycondensation ester plasticizer includes at least one dicarboxylic acid (also referred to as an aromatic dicarboxylic acid) in which X is the above divalent aromatic group, and a diol (also referred to as an aliphatic diol) in which Z is the above aliphatic group. The compound obtained from at least one of the above is preferred. The average carbon number of the aliphatic diol used is preferably 2.5 to 8.0. In addition, a mixture of at least one aromatic dicarboxylic acid and at least one dicarboxylic acid (also referred to as aliphatic dicarboxylic acid) in which X is the above divalent aliphatic group, and at least one average carbon number is 2.5. Also preferred are polycondensate ester plasticizers obtained from ˜8.0 aliphatic diols.

  In the description of the polycondensate ester plasticizer, the calculation of the average carbon number of the dicarboxylic acid or dicarboxylic acid residue uses the total carbon number of all dicarboxylic acid residues or all dicarboxylic acid residues in the polycondensate ester plasticizer used. It is a value obtained by dividing the number of moles of dicarboxylic acid or the number of moles of dicarboxylic acid residues in the polycondensate ester plasticizer. For example, when it is composed of 50 mol% each of adipic acid residues and phthalic acid residues in all dicarboxylic acid residues, the average carbon number of dicarboxylic acid residues is 7.0. The average carbon number of the diol or diol residue is calculated similarly. For example, when composed of 50 mol% of ethylene glycol residues and 50 mol% of 1,2-propanediol residues, the average carbon number of diol residues is 2.5.

The number average molecular weight of the polycondensed ester plasticizer is preferably 500 to 2000, more preferably 600 to 1500, and still more preferably 700 to 1200. If the number average molecular weight of the polycondensed ester is 600 or more, the volatility is low, and it is excellent in suppressing film failure and process contamination due to volatilization under high temperature conditions during stretching of the cellulose ester film.
Moreover, if it is 2000 or less, compatibility with a cellulose ester will become high and it will be excellent in suppression of the bleed-out at the time of film forming and heat-stretching.
The number average molecular weight of the polycondensed ester plasticizer can be measured and evaluated by gel permeation chromatography. Further, in the case of a polyester polyol having an unsealed terminal, it can also be calculated from the amount of hydroxy groups per mass (hereinafter also referred to as hydroxyl value). In the present invention, the hydroxyl value can be obtained by acetylating a polyester polyol and then measuring the amount (mg) of potassium hydroxide necessary for neutralizing excess acetic acid.

When a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid is used as the dicarboxylic acid component, the average carbon number of the dicarboxylic acid component is preferably 5.5 to 10.0, more preferably 5.6 to 8. .
By setting the average carbon number to 5.5 or more, a polarizing plate having superior durability can be obtained. Moreover, it is excellent by the compatibility to a cellulose ester by making an average carbon number into 10 or less, and it is excellent in suppression of a bleed-out in the film forming process of a cellulose ester film.

The polycondensation ester obtained using an aromatic dicarboxylic acid contains an aromatic dicarboxylic acid residue.
The ratio of the aromatic dicarboxylic acid residue in the dicarboxylic acid residue of the polycondensation ester plasticizer used in the present invention is preferably 40 mol% or more, more preferably 40 mol% to 95 mol%.

By setting the ratio of the aromatic dicarboxylic acid residue in the dicarboxylic acid residue to 40 mol% or more, a cellulose ester film exhibiting sufficient optical anisotropy can be obtained, and a polarizing plate excellent in durability can be obtained. . In addition, by setting the ratio of aromatic dicarboxylic acid residues in dicarboxylic acid residues to 95 mol% or less, it has excellent compatibility with cellulose esters, and suppresses bleed-out even during the formation of cellulose ester films and during heat stretching. Excellent.
A dicarboxylic acid residue is a partial structure of a polycondensed ester. For example, a dicarboxylic acid residue formed from dicarboxylic acid HOC (═O) —X—CO ₂ H is —C (═O) —X—C (═O ) −.

  Aromatic dicarboxylic acids that can be used for the synthesis of polycondensation ester plasticizers are phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid. At least one selected from 2,8-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid is preferable. Among them, at least one selected from phthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid is more preferable, at least one selected from phthalic acid and terephthalic acid is more preferable, and terephthalic acid is more preferable.

  By using terephthalic acid as the aromatic dicarboxylic acid for the synthesis of polycondensate ester odorant, it is more compatible with cellulose ester, and suppresses bleed-out even during film formation and heat stretching of cellulose ester film. It can be set as the outstanding cellulose-ester film. Moreover, aromatic dicarboxylic acid may be used 1 type, or may use 2 or more types. When two types are used, it is preferable to use phthalic acid and terephthalic acid.

Further, it is preferable to use two kinds of aromatic dicarboxylic acids of phthalic acid and terephthalic acid in combination because the polycondensation ester odorant at normal temperature can be softened and handling becomes easy.
The polycondensate ester plasticizer preferably has a terephthalic acid residue content in the dicarboxylic acid residue of 40 mol% to 100 mol%.
By setting the terephthalic acid residue ratio to 40 mol% or more, a cellulose ester film exhibiting sufficient optical anisotropy can be obtained.

The polycondensation ester obtained using an aliphatic dicarboxylic acid contains an aliphatic dicarboxylic acid residue.
Aliphatic dicarboxylic acids used in the synthesis of polycondensate ester plasticizers are oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane At least one selected from dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid is preferred.

The average carbon number of the aliphatic dicarboxylic acid residue is preferably 5.5 to 10.0, more preferably 5.5 to 8.0, and even more preferably 5.5 to 7.0. If the average carbon number of the aliphatic dicarboxylic acid residue is 10.0 or less, the heat loss of the compound can be reduced, and the occurrence of surface failure that may be caused by process contamination due to bleed-out during drying of the cellulose acylate web is prevented. be able to. Moreover, it is preferable that the aliphatic dicarboxylic acid residue has an average carbon number of 5.5 or more because it is excellent in compatibility and precipitation of the polycondensed ester hardly occurs.
Specifically, the aliphatic dicarboxylic acid residue in the polycondensed ester plasticizer preferably includes a succinic acid residue. When the polycondensation ester plasticizer contains two or more aliphatic dicarboxylic acid residues, the aliphatic dicarboxylic acid residue preferably contains a succinic acid residue and an adipic acid residue.

The polycondensed ester plasticizer contains a diol residue.
The diol residue formed by the diol compound (HO—Z—OH) represented by the general formula (b) is —O—Z—O—.
The polycondensed ester plasticizer preferably contains an aliphatic diol residue having an average carbon number of 2.5 to 7.0, and contains an aliphatic diol residue having an average carbon number of 2.5 to 4.0. Is more preferable.
When the average carbon number of the aliphatic diol residue is less than 7.0, the compatibility with the cellulose ester is improved, bleed-out is less likely to occur, and the heat loss of the compound is less likely to increase, and the cellulose acylate web is dried. It is difficult for a sheet-like failure that may be caused by process contamination at the time to occur. Further, the synthesis is easy if the average carbon number of the aliphatic diol residue is 2.5 or more.

The terminal of the polycondensed ester plasticizer may be left as a diol or carboxylic acid without being sealed (that is, the polymer chain length terminal is —OH or —CO ₂ H), and further, monocarboxylic acid or A so-called end capping may be performed by reacting a monoalcohol with respect to the —CO ₂ H end. In addition, by sealing the terminal of the polycondensation ester plasticizer, the state at normal temperature is unlikely to become a solid form, and the handling becomes good. Moreover, the cellulose-ester film excellent in humidity stability and polarizing plate durability is obtained.

  The monocarboxylic acid used for sealing is preferably at least one selected from acetic acid, propionic acid, butanoic acid, and benzoic acid. The monoalcohol used for sealing is preferably at least one selected from methanol, ethanol, propanol, isopropanol, butanol, and isobutanol, and most preferably methanol. When the carbon number of the monocarboxylic acid used at the terminal of the polycondensed ester is 7 or less, the loss on heating of the compound is reduced, and the occurrence of planar failure is excellent.

  Specific examples J-1 to J-41 of polycondensation ester plasticizers are listed in Table 1 below, but the present invention is not limited thereto.

  Here, in the abbreviations in Table 1, PA represents phthalic acid, TPA represents terephthalic acid, AA represents adipic acid, SA represents succinic acid, and 2,6-NPA represents 2,6-naphthalenedicarboxylic acid.

  The polycondensation ester plasticizer can be synthesized by either a conventional method of polyesterification reaction of diol and dicarboxylic acid or hot melt condensation method by transesterification, or interfacial condensation method of acid chlorides of these acids and glycols. It can be easily synthesized by the method. Polycondensation esters are described in detail in Koichi Murai, “Plasticizers, Theory and Applications” (Koshobo Co., Ltd., published on the first edition, March 1, 1973). These compounds are used. You can also

  In the present invention, as polycondensation ester plasticizers, JP-A Nos. 05-155809, 05-155810, JP-A-5-97073, JP-A-2006-259494, JP-A-07-330670, JP-A-2006. The compounds described in JP-A No. 342227 and JP-A No. 2007-003679 can also be used.

(Carbohydrate derivative plasticizer)
The cellulose acylate film of the present invention preferably further contains a carbohydrate derivative plasticizer. By containing a carbohydrate derivative plasticizer, a cellulose ester film excellent in humidity stability and polarizing plate durability can be obtained.
The carbohydrate derivative plasticizer is preferably a monosaccharide or a carbohydrate derivative containing 2 to 10 monosaccharide units.

  The monosaccharide or polysaccharide preferably constituting the carbohydrate derivative plasticizer has a part or all of the substitutable groups in the molecule (for example, hydroxy group, carboxyl group, amino group, mercapto group, etc.) substituted with substituents. . Examples of the substituent that the carbohydrate derivative plasticizer may have include an alkyl group, an aryl group, and an acyl group. Details will be described later. Moreover, an ether structure formed by substitution with an alcohol, an ester structure formed by substitution of a hydroxy group with an acyl group, an amide structure or an imide structure formed by substitution with an amino group, and the like can be given.

  Carbohydrates containing monosaccharides or 2-10 monosaccharide units are erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, talose, trehalose, iso Trehalose, neotrehalose, trehalosamine, cobibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactosamine, lactitol, lactulose, melibiose, primeverose, lutinose, silabiose, sucrose , Vicyanose, cellotriose, cacotriose, gentianose, isomaltotriose, isopano , Maltotriose, manninotriose, melezitose, panose, planteose, raffinose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, baltopentaose, velval course, maltohexaose, α- Cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol or sorbitol is preferred.

  Preferably, ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, sucralose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin Xylitol, sorbitol, more preferably arabinose, xylose, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, β-cyclodextrin, or γ-cyclodextrin, particularly preferably xylose, glucose, Fructose, mannose, galactose, maltose, cellobiose, sucrose, xylitol, or sorbitol

The substituent of the carbohydrate derivative plasticizer is an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, Propyl, hydroxyethyl, hydroxypropyl, 2-cyanoethyl, benzyl group, etc.), aryl groups (preferably 6-24 carbon atoms, more preferably 6-18, particularly preferably 6-12 aryl groups such as phenyl, naphthyl, etc. ), An acyl group (including an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, preferably an acyl group having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, toluyl Phthalyl, such as Nafutoru) is preferred. Further, as a preferred structure formed by substitution with an amino group, an amide structure (preferably an amide having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as formamide, acetamide, etc. Etc.) or an imide structure (preferably an imide having 4 to 22 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms, such as succinimide and phthalimide).
The substituent that the carbohydrate derivative plasticizer has is preferably at least one selected from an alkyl group, an aryl group, and an acyl group, and more preferably an acyl group.

Preferable examples of the carbohydrate derivative plasticizer include the following, but the present invention is not limited thereto.
Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabutyrate, glucose pentab Rate, fructose pentabylate, mannose pentabylate, galactose pentabylate, maltose octabutyrate, cellobiose octabutyrate, sucrose octabutyrate, xylitol pentabylate, sorbitol hexabutyrate, xylose tetrabenzoate, glucose pentabenzoate, At least one selected from fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, and sorbitol hexabenzoate.

  More preferably, xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, Glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexa Propionate, xylose tetrabenzoate, Le courses pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, at least one selected from xylitol pentabenzoate and sorbitol hexa benzoate.

More preferably, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate Nate, cellobiose octapropionate, sucrose octapropionate, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose octabenzoate, xylitol pentabenzoate, And sorbitol hex At least one selected from the group consisting of benzoate.
The carbohydrate derivative plasticizer preferably has a pyranose structure or a furanose structure.

As the carbohydrate derivative plasticizer used in the present invention, the following compounds are also preferred. However, the present invention is not limited to these.
In the following structural formulas, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different.
In Tables 2 to 5 below, those which are hydroxy groups in one molecule (R is a hydrogen atom) are acylated with two types of acylating agents and introduced with these two types of acylating agents. One of the Rs is shown as “Substituent 1”, and the other R is shown as “Substituent 2”, and the degree of substitution represents the number of all hydroxy groups in one molecule.

  As the carbohydrate derivative plasticizer, commercially available products such as those manufactured by Tokyo Kasei Co., Ltd. and Aldrich can be obtained, and commercially available carbohydrates are described in known esterification reactions (for example, described in JP-A-8-245678). Can be easily synthesized.

As for content of the plasticizer in the cellulose acylate film of this invention, 1-20 mass parts is preferable with respect to 100 mass parts of cellulose acylates. By setting the plasticizer content to 1 part by mass or more with respect to 100 parts by mass of cellulose acylate, the effect of improving the durability of the polarizer can be easily obtained, and by setting it to 20 parts by mass or less, bleeding out can also be suppressed. . The more preferable content of the plasticizer in the cellulose acylate film is 2 to 15 parts by mass, particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the cellulose acylate.
Two or more kinds of these plasticizers may be added. Also when adding 2 or more types, the specific example and preferable range of addition amount are the same as the above.

(Deterioration inhibitor)
A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. Further, an ultraviolet absorber is one of deterioration preventing agents. These deterioration inhibitors and the like are disclosed in JP-A-60-235852, JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-107854. 118233, 6-148430, 7-11056, 7-11055, 7-11056, 8-29619, 8-239509, JP-A-2000-204173 There is.
In addition, any of the commercially available stabilizers described in pages 21 to 69 of “Polymer Additive Handbook” (CMC Publishing) can be preferably used.

(Antioxidant)
The cellulose acylate film of the present invention preferably contains an antioxidant.
Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1,1′-bis ( 4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di Phenol- or hydroquinone-based antioxidants such as -tert-butyl-4-hydroxyphenyl) propionate].
Tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl) Phosphorous antioxidants such as -4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, N, N-dioctadecylhydroxylamine, N, It is also preferable to use a hydroxylamine antioxidant such as N-dibenzylhydroxylamine. As the hydroxylamine compound, compounds described in paragraph Nos. 0005 to 0020 and paragraph Nos. 0022 to 0026 of JP-A-8-62767 can be preferably used.

  Further, reductones represented by the following general formula (A) or the following general formula (B) are also preferable as the antioxidant used in the present invention.

In general formula (A), R ^A1 and R ^A2 each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group. X is composed of a carbon atom, an oxygen atom and / or a nitrogen atom, and represents a nonmetallic atom group constituting a 5- to 6-membered ring together with —C (═O) —C (R ^A1 ) ═C (R ^A2 ) —. .

R ^A1 and R ^A2 are preferably a hydroxy group, an amino group, an alkylsulfonylamino group or an arylsulfonylamino group, more preferably a hydroxy group or an amino group, and even more preferably a hydroxy group.

X has at least one —O— bond, and —C (R ^A3 ) (R ^A4 ) —, —C (R ^A5 ) ═, —C (═O) —, —N (Ra) — and — It is preferable to be configured by combining one or more of N =. Here, R ^{A3 to} R ^A5 and Ra are each independently a hydrogen atom, an alkyl group which may have a substituent having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms which may have a substituent, A hydroxy group or a carboxyl group is preferred.

The 5- to 6-membered ring formed through X includes, for example, a cyclopentenone ring (2-cyclopenten-1-one ring; the formed compound becomes reductic acid), a furanone ring [2 (5H) -Furanone ring], dihydropyranone ring [3,4-dihydro-2H-pyran-4-one ring (2,3-dihydro-4H-pyrone ring), 3,6-dihydro-2H-pyran-2-one Ring, 3,6-dihydro-2H-pyran-6-one ring (5,6-dihydro-2-pyrone ring)], 3,4-dihydro-2H-pyrone ring, cyclopentenone ring, furanone A ring and a dihydropyrone ring are preferable, a furanone ring and a dihydropyrone ring are more preferable, and a furanone ring is particularly preferable.
These rings may be condensed, and the condensed ring may be either a saturated ring or an unsaturated ring.

  Of the reductones represented by the above general formula (A), a compound represented by the following general formula (A1) is preferable, and a compound represented by the following general formula (A2) is particularly preferable.

In general formula (A1), R ^a1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and they may have a substituent.
R ^a1 is preferably an alkyl group which may have a substituent, more preferably —CH (OR ^a1 ) CH ₂ OR ^a2 , and in this case, a compound represented by the above general formula (A2).

In general formula (A2), R ^a2 and R ^a3 each independently represent a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group, and R ^a2 and R ^a3 may be bonded to each other to form a ring, The ring to be formed is preferably a 1,3-dioxolane ring, and this ring may further have a substituent. A compound having a dioxolane ring can be synthesized by acetalization or ketalization by reaction of ascorbic acid with ketones or aldehydes, and raw material ketones or aldehydes can be used without particular limitation.

One particularly preferred combination of substituents is a compound in which R ^a2 is an acyl group and R ^a3 is a hydrogen atom, and the acyl group may be either an aliphatic acyl group or an aromatic acyl group. In this case, the number of carbon atoms is preferably 2 to 30, more preferably 4 to 24, and still more preferably 8 to 18. In the case of an aromatic acyl group, the carbon number is preferably 7-24, more preferably 7-22, and still more preferably 7-18. Preferred acyl groups include butanoyl, hexanoyl, 2-ethylhexanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, palmitoleyl, myristolyl, oleoyl, benzoyl, 4-methylbenzoyl and 2-methylbenzoyl. it can.

  In addition to the compound represented by the general formula (A), a compound represented by the following general formula (B) is also preferable.

In general formula (B), R ^B1 and R ^B2 are each independently a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, acyl group, carboxy group, amino group, alkoxy group, alkoxycarbonyl group or R ^B3 and R ^B4 each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, or a mercapto group.

The alkyl group in R ^B1 and R ^B2 preferably has 1 to 10 carbon atoms. The alkyl group is preferably methyl, ethyl or t-butyl.
The alkyl group in R ^B1 and R ^B2 preferably has 1 to 10 carbon atoms.
The alkenyl group in R ^B1 and R ^B2 preferably has 2 to 10 carbon atoms. The alkenyl group is preferably vinyl or allyl, and vinyl is preferred.
The cycloalkyl group in R ^B1 and R ^B2 preferably has 3 to 10 carbon atoms. The cycloalkyl group is preferably cyclopropyl, cyclopentyl, or cyclohexyl.
These alkyl group, alkenyl group and cycloalkyl group may have a substituent, and the substituent is preferably at least one selected from a hydroxy group, a carboxyl group and a sulfo group.
When the alkenyl group is vinyl, a vinyl group substituted with a carboxyl group is also preferable.

The aryl group in R ^B1 and R ^B2 preferably has 6 to 12 carbon atoms. The aryl group may have a substituent, and the substituent is preferably at least one selected from an alkyl group, a hydroxy group, a carboxyl group, a sulfo group, a halogen atom, a nitro group, and a cyano group.
The acyl group in R ^B1 and R ^B2 is preferably formyl, acetyl, isobutyryl or benzoyl.
The amino group in R ^B1 and R ^B2 includes an amino group, an alkylamino group, and an arylamino group, and includes amino, methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino, phenylamino, and N-methyl-N-phenyl. Amino is preferred.

The alkoxy group for R ^B1 and R ^B2 preferably has 1 to 10 carbon atoms. The alkoxy group is preferably methoxy or ethoxy.
The alkoxycarbonyl group in R ^B1 and R ^B2 is preferably methoxycarbonyl.
In the heterocyclic group in R ^B1 and R ^B2 , the ring-constituting hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and the ring structure is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be an aromatic heterocyclic group, a saturated heterocyclic group, or a condensed ring.
The heterocyclic ring in the heterocyclic group is preferably a pyridine ring, pyrimidine ring, pyrrole ring, furan ring group, thiophene ring, pyrazole ring, piperidine ring, piperazine ring or morpholine ring.

R ^B1 and R ^B2 are more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The amino group in R ^B3 and R ^B4 includes an amino group, an alkylamino group, and an arylamino group, and is preferably an amino group or an alkylamino group such as methylamino, ethylamino, n-butylamino, or hydroxyethylamino.
The acylamino group in R ^B3 and R ^B4 is preferably acetylamino or benzoylamino.
The alkylsulfonylamino group in R ^B3 and R ^B4 is preferably methylsulfonylamino.
The arylsulfonylamino group in R ^B3 and R ^B4 is preferably benzenesulfonylamino or p-toluenesulfonylamino.
The alkoxycarbonylamino group in R ^B3 and R ^B4 is preferably methoxycarbonylamino.

R ^B3 and R ^B4 are more preferably a hydroxy group, an amino group, an alkylsulfonylamino group or an arylsulfonylamino group.

The antioxidant used in the present invention is more preferably a reductone, and specific examples thereof include compounds exemplified in paragraph Nos. 0014 to 0034 of JP-A-6-27599, and paragraph Nos. 0012 to 6-2 of JP-A-6-110163. The compounds exemplified in 0020 and the compounds exemplified in paragraph numbers 0022 to 0031 of JP-A No. 8-114899 can be exemplified.
Of these, myristic acid ester, palmitic acid ester and stearic acid ester of L-ascorbic acid are particularly preferable.

The timing for adding the antioxidant to the cellulose acylate film is not particularly limited as long as it is added at the time of film formation. For example, you may add at the time of the synthesis | combination of a cellulose acylate, and may mix with a cellulose acylate at the time of dope preparation.
The content of the antioxidant in the cellulose acylate film is preferably 0.0001 to 5.0 parts by mass with respect to 100 parts by mass of the cellulose acylate. By setting the content of the antioxidant within the above range, a sufficient antioxidant effect and polarizer durability can be obtained. The content of the antioxidant in the cellulose acylate film is more preferably 0.001 to 1.0 part by mass, and more preferably 0.01 part by mass to 100 parts by mass of the cellulose acylate. 0.5 parts by mass.

(Radical scavenger)
The cellulose acylate film of the present invention preferably contains a radical scavenger. By containing the radical scavenger, decomposition of the compound represented by the general formula (I) is suppressed, and better polarizer durability can be obtained.

  As the radical scavenger usable in the present invention, a compound (HALS) represented by the following general formula (H) is preferable.

In General Formula (H), R ^H1 and R ^H2 each independently represent a hydrogen atom or a substituent, and R ^{H01 to} R ^H04 each independently represent an alkyl group.

The substituent in R ^H1 is not particularly limited, but is preferably an alkyl group or a substituent bonded to the piperidine ring through a nitrogen atom or an oxygen atom. The substituent bonded to the piperidine ring by a nitrogen atom or an oxygen atom is preferably an amino group, an acylamino group, a hydroxy group, an alkoxy group, an aryloxy group or an acyloxy group. These groups may have a substituent.
The substituent in R ^H1 is preferably an alkyl group, an aryl group or an amino group having a heterocyclic group, and further a hydroxy group, an alkoxy group or an acyloxy group.

The substituent in R ^H2 is not particularly limited, but an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, among which methyl, ethyl, isopropyl, tert, -Butyl, n-octyl, 2-ethylhexyl, n-decyl, n-hexadecyl), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12, more preferably 2 to 8 and even more preferably Is vinyl, allyl, 2-butenyl or 3-pentenyl), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12, more preferably 2 to 8 and even more preferably propargyl, Is 3-pentynyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, more preferably 3 to 12, more preferably 3). ~ 8, cyclopropyl, cyclopentyl or cyclohexyl). An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20, more preferably 6 to 12, more preferably phenyl, biphenyl or naphthyl), an amino group (amino group, alkylamino group, arylamino) Group, preferably 0 to 20 carbon atoms, more preferably 0 to 10, more preferably 0 to 6, and still more preferably amino, methylamino, dimethylamino, diethylamino, phenylamino, N-methyl- N-phenylamino or dibenzylamino), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 8, and still more preferably methoxy, ethoxy, butoxy), cyclo Alkyloxy group (the cycloalkyl ring in the cycloalkyloxy group is preferred) Or a 3- to 8-membered ring, preferably having 3 to 20 carbon atoms, and the cycloalkyloxy group is preferably cyclopropyloxy, cyclopentyloxy, cyclohexyloxy), acyl group (including alkylcarbonyl group and arylcarbonyl group, preferably Has 2 to 20 carbon atoms, more preferably 2 to 16, more preferably 2 to 8, more preferably acetyl, propionyl, 2-ethylhexanoyl or benzoyl), a hydroxy group or an oxy radical group (-O. ) Is preferred.

R ^{H01 to} R ^H04 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably ethyl or methyl, and further preferably all of R ^{01 to} R ⁰⁴ are methyl.

  The compound represented by the general formula (H) is 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1 -Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4 -Stearoyloxy-2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2, 6,6-pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 1-ben L-2,2,6,6-tetramethylpiperidin-4-ylmaleate, bis (2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (2,2,6 , 6-Tetramethylpiperidin-4-yl) sebacate, bis (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate, bis (1-allyl-2,2, 6,6-tetramethyl-piperidin-4-yl) phthalate, 1-acetyl-4-acetoxy-2,2,6,6-tetramethylpiperidine, trimellitic acid-tris (2,2,6,6-tetramethyl Piperidin-4-yl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,

Dibutylmalonic acid-bis (1,2,2,6,6-pentamethyl-piperidin-4-yl) ester, dibenzylmalonic acid-bis (1,2,3,6-tetramethyl-2,6-diethyl- Piperidin-4-yl) ester, dimethyl-bis (2,2,6,6-tetramethylpiperidin-4-yloxy) -silane, tris (1-propyl-2,2,6,6-tetramethylpiperidine-4) -Yl) -phosphite, tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate, N, N'-bis (2,2,6,6-tetramethylpiperidine -4-yl) -hexamethylene-1,6-diamine, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, Trakis (1,2,2,6,6-pentamethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, N, N′-bis- (2,2,6,6- Tetramethylpiperidin-4-yl) -hexamethylene-1,6-diacetamide, 1-acetyl-4- (N-cyclohexylacetamide) -2,2,6,6-tetramethyl-piperidine, 4-benzylamino- 2,2,6,6-tetramethylpiperidine, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N′-dibutyl-adipamide, N, N ′ -Bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl- (2-hydroxy) propylenediamine, N, N'-bis- (2,2,6, 6-tetramethylpi Lysine-4-yl) -p-xylylene-diamine, 4-bis (2-hydroxyethyl) amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6 , 6-pentamethylpiperidine and α-cyano-β-methyl-β- [N- (2,2,6,6-tetramethylpiperidin-4-yl)]-amino-acrylic acid methyl ester Species are preferred.

  More preferably, N, N ′, N ″, N ′ ″-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine N, N′-bis (2,2,6,6-tetramethyl -4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate (CHASASSORB 2020FDL, manufactured by BASF), dibutylamine and 1 , 3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{(1,1,3,3-tetramethyl Butyl) Ami -1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl- 4-piperidyl) imino}] (BAMIS CHIMASSORB 944FDL), 1,6-hexanediamine-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4 , 6-trichloro-1,3,5-triazine polycondensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6, -tetramethyl-4 -Piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and other high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton;

Or a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2, Mixed esterified product of 6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane High molecular weight HALS in which a piperidine ring is bonded via an ester bond can be preferably used, but the present invention is not limited to these.
Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} and a polycondensate of dimethyl succinate with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, a number The average molecular weight (Mn) is preferably 2,000 to 5,000.

  As the radical scavenger, a compound represented by the following structure (Hα) (trade name, Sunlizer HA-622, manufactured by Sort Co., Ltd.) and a compound represented by the following structure (Hβ) are also suitable.

In addition, m in the said structure (H (alpha)) is 2-30.
The compound of the said structure (H (alpha)) or (H (beta)) is a product name, CHIMASSORB 2020FDL (CAS-No.192268-64-7), CHIMASSORB 944FDL (CAS-No) made from BASF (former Ciba Specialty Chemicals Co., Ltd.). 71878-19-8) and TINUVIN 770DF (CAS-No. 52829-07-9), trade names of Sun Chemical Co., Ltd., Siasorb UV-3346 (CAS-No. 82541-48-7), and Siasorb UV -3529 (CAS-No. 193098-40-7) is commercially available.

  Moreover, the compound represented by the following general formula (H1) can be particularly preferably used for the cellulose acylate film of the present invention because of its low basicity and small side effects on polarization performance.

In General Formula (H1), Z ^H1 represents an alkyl group, a cycloalkyl group, or an aryl group, and Y ^H1 represents a hydrogen atom or a substituent. R ^H01 to R ^H04 has the same meaning as ^R H01 ^{to R H04} of the formula (H), in the preferred embodiment is also the same.
Z ^H1 is preferably an alkyl group or cycloalkyl group which may have a substituent, more preferably an unsubstituted alkyl group having a branched structure, an alkyl group or cycloalkyl group having an aryl group as a substituent, and a cycloalkyl group being Further preferred. In addition, there is no limitation in particular in the substituent which ^ZH1 has.
The number of carbon atoms of the alkyl group in Z ^H1 is preferably 1 to 20, 1 to 14 is more preferred. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20 in the Z ^H1, more preferably 3 to 14. ^The number of carbon atoms of the aryl group in ^{Z H1} 6-20 preferably 6-14 more preferred.
Y ^H1 is preferably a substituent. The substituent in Y ^H1 is not particularly limited, but is preferably a substituent bonded to the piperidine ring by a nitrogen atom or an oxygen atom, and may have an amino group, a hydroxy group, or an alkoxy group (having a carbon number). , Preferably 1-20, more preferably 1-14), an aryloxy group (carbon number is preferably 6-20, more preferably 6-12), or an acyloxy group (carbon number is preferably 2-20). And more preferably 2-14), an amino group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or a heterocyclic group as a substituent, a hydroxy group, and 1 carbon atom. More preferred is an alkoxy group having 10 to 10 carbon atoms or an acyloxy group having 2 to 10 carbon atoms.

In the compound represented by the general formula (H1), the nitrogen (N) of the piperidine ring particularly has an ether bond with an alkyl group or an aryl group which may have a substituent represented by ^ZH1 . There is a feature. The compound having the piperidine skeleton represented by the general formula (H1) including the structure of “N—O—Z ^H1 ” is referred to as “NOZ ^H1 type” in the present specification.

In addition, a compound in which only hydrogen is directly bonded to nitrogen (N) of the piperidine ring is referred to as “NH type”, and a compound in which only a methyl group is directly bonded to nitrogen (N) is referred to as “NCH ₃ type”. The NH type and NCH ₃ type are more basic than the NOZ ^H1 type. In the present invention, the use of a weakly basic NOZ ^H1- type compound makes it possible to more effectively prevent deterioration of the polarizer performance when the cellulose acylate film of the present invention is incorporated into a polarizing plate and used for a long time under high temperature and high humidity. Can be suppressed.

The NOZ ^H1- type compound represented by the general formula (H1) is not limited as long as it has a predetermined piperidine skeleton, but the compound represented by the following general formula (H1-1) or (H1-2) preferable.

In the general formula ^{(H1-1), (H1-2),} R H01 ~R H04 has the same meaning as ^R H01 ^{to R H04} in the formula (H), in the preferred range is also the same. Z ^H2 represents an alkyl group or an aryl group which may have a substituent. R ^H11 and R ^H12 each independently represents an alkyl group, an aryl group, an acyl group, or a heterocyclic group. R ^H13 represents a hydrogen atom, an alkyl group, an acyl group, or an aryl group.

A preferable range of Z ^H2 is the same as Z ^{H1 in the} general formula (H1).
R ^H11 is more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a propyl group or a butyl group.
R ^H12 is more preferably an alkyl group or a heterocyclic group, particularly preferably an alkyl group having 1 to 6 carbon atoms or a heterocyclic group containing a nitrogen atom having 1 to 2 ring members, and particularly preferably triazine.
R ^H13 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an acyl group having 1 to 12 carbon atoms, and particularly preferably an acyl group having 1 to 12 carbon atoms.

Each of the above groups in R ^{H11 to} R ^H13 may be substituted with a substituent. As such a substituent, for example, you may have a substituent remove ^| excluding ^YH1 from general formula (H1).

  The compound represented by the general formula (H1-1) or (H1-2) is preferably a compound represented by the following general formulas (H1-a) to (H1-c).

In the general formulas (H1-a) to (H1-c), Z ^H1 and Z ^H2 are the same as those described above, and preferred ranges are also the same. R ^{H01 to} R ^H04 have the same meaning as R ^{H01 to} R ^H04 in the general formula (H), and the preferred range is also the same.
In general formula (H1-c), R ^{H05 to} R ^H06 each independently represents an alkyl group, R ^Ha and R ^Hb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and W ^H1 represents Represents a substituent.

  Although the preferable example of a compound represented by the said general formula (H) is shown below, this invention is not limited to these.

Compound HA-11 (product name “TINUVIN 152”, manufactured by Ciba Specialty Chemicals, CAS-No. 191743-75-6) and compound HA-12 (product name “FLAMESTTAB NOR 116 FF”, Ciba Specialty) -Chemicals Co., Ltd. and CAS-No. 191680-81-6) are easily available from a market.
The following compound HA-13 (product name “TINUVIN 123”, manufactured by Ciba Specialty Chemicals, CAS-No. 129757-67-1) can also be preferably used as a radical scavenger.

  In addition, although the compound represented with the said general formula (H) may be obtained commercially as mentioned above, you may use what was manufactured by the synthesis | combination. There is no restriction | limiting in particular as a synthesis method of the compound represented by the said general formula (H), It is compoundable by the method in a normal organic synthesis. Moreover, as a purification method, distillation, recrystallization, reprecipitation, and a method using a filter agent / adsorbent can be appropriately used. Furthermore, what is usually commercially available at a low price is not a compound represented by the general formula (H) alone but may be a mixture. In the present invention, as long as it functions as a radical scavenger, it is produced. It can be used regardless of the method, composition, melting point, acid value and the like.

The molecular weight of the compound represented by the general formula (H) is not limited. However, from the viewpoint of suppressing volatilization from the cellulose acylate film, it is preferable that the compound is somewhat polymerized as shown below. By adjusting to an appropriate molecular weight, a film having excellent compatibility with cellulose acylate and high transparency can be obtained.
Therefore, the molecular weight of the compound represented by the general formula (H) is preferably 300 to 100,000, more preferably 500 to 50,000, and particularly preferably 700 to 30,000.

The timing at which the compound represented by the general formula (H) is added to the cellulose acylate film is not particularly limited as long as it is added at the time of film formation. For example, you may add at the time of the synthesis | combination of a cellulose acylate, and may mix with a cellulose acylate at the time of dope preparation.
The content of the compound represented by the general formula (H) in the cellulose acylate film is preferably 0.0001 to 5.0 parts by mass with respect to 100 parts by mass of the cellulose acylate. By setting the content of the compound represented by the general formula (H) in the cellulose acylate film within the above range, a sufficient antioxidant effect and polarizer durability characteristics can be obtained. The content of the compound represented by the general formula (H) in the cellulose acylate film is more preferably 0.001 to 1.0 part by mass, and more preferably 100 parts by mass of the cellulose acylate. 0.01 parts by mass to 0.5 parts by mass.

(UV absorber)
In the present invention, an ultraviolet absorber may be added to the cellulose acylate solution from the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal. As the ultraviolet absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and less visible light absorption having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. The ultraviolet absorber used in the present invention is preferably at least one selected from hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, and nickel complex compounds.

  The hindered phenol compound is not particularly limited, but 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-) Preference is given to at least one selected from tert-butyl-4-hydroxybenzyl) benzene and tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate.

The benzotriazole compound is not particularly limited, but 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol], (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5 -Triazine, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4 -Hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl)- Selected from 5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] At least one is preferred.
The content of the ultraviolet light inhibitor in the cellulose acylate film is preferably 1 ppm to 1.0% on a mass basis, and more preferably 10 ppm to 1000 ppm.

(Other deterioration inhibitors)
Additives known as peroxide decomposers, radical inhibitors, and metal deactivators may be used as cellulose acylate degradation inhibitors. Examples of these stabilizers include compounds described in JP-A 2006-251746, paragraphs 0074 to 0081 and 0082 to 0117.
Further, amines are also known as deterioration inhibitors. For example, compounds described in paragraph Nos. 0009 to 0080 of JP-A No. 5-194789, tri-n-octylamine, triisooctylamine, tris (2- And aliphatic amines such as ethylhexyl) amine and N, N-dimethyldodecylamine.
It is also preferable to use polyvalent amines having two or more amino groups. As the polyvalent amine, those having two or more primary or secondary amino groups are preferable. Examples of the compound having two or more amino groups include nitrogen-containing heterocyclic compounds (compounds having a pyrazolidine ring, piperazine ring, etc.), polyamine compounds (chain or cyclic polyamines such as diethylenetriamine, tetraethylenepentamine, N, N′-bis (aminoethyl) -1,3-propanediamine, N, N, N ′, N ″, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine, a compound containing cyclam as a basic skeleton), etc. Is mentioned.

  Specific examples of the polyvalent amino include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, aminoethylethanolamine, polyethyleneimine, polyallylamine, polyvinylamine, N ′ , N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentakis (2-hydroxy Propyl) diethylenetriamine and the like. Examples of commercially available products include Epomin SP-006, SP-012, and SP-018 manufactured by Nippon Shokubai Co., Ltd.

(Matting agent)
A matting agent may be added to the cellulose acylate film of the present invention from the viewpoint of film slipperiness and stable production. The matting agent may be an inorganic compound matting agent or an organic compound matting agent.
The inorganic compound matting agent is an inorganic compound containing silicon (for example, silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, etc.), titanium oxide, zinc oxide, aluminum oxide, barium oxide. , Zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin / antimony oxide, calcium carbonate, talc, clay, calcined kaolin and calcium phosphate, and more preferably from silicon-containing inorganic compound and zirconium oxide Although it is at least one selected, it is particularly preferable to use silicon dioxide from the viewpoint of further reducing the turbidity of the cellulose acylate film.

As the fine particles of silicon dioxide, commercially available products having a trade name such as Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. As the fine particles of zirconium oxide, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
The matting agent of the organic compound is not particularly limited, but at least one polymer selected from silicone resins, fluororesins and acrylic resins is preferable, and among them, silicone resins are preferable. Among the silicone resins, those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 (manufactured by Toshiba Silicone Co., Ltd.) A commercial product having a trade name can be used.

The timing for adding these matting agents to the cellulose acylate film is not particularly limited as long as it is added at the time of film formation. For example, an additive may be contained at the stage of mixing cellulose acylate and a solvent, or an additive may be added after preparing a mixed solution with cellulose acylate and a solvent.
Further, it may be added and mixed immediately before casting the dope, and the mixing is preferably carried out by installing a screw-type kneading on-line. Specifically, it is preferable to use a static mixer such as an in-line mixer. Further, as the in-line mixer, for example, a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer) (manufactured by Toray Engineering) is preferable.

  As for in-line addition, the method described in JP-A-2003-053752 can be used in order to eliminate density unevenness, particle aggregation, and the like. Furthermore, the method described in JP-A-2003-014933 may be used in order to obtain a retardation film with little additive bleed-out, no delamination phenomenon between layers, and excellent slipperiness and excellent transparency. it can.

  The content of the matting agent in the cellulose acylate film is particularly preferably 0.05 to 1.0% by mass. By setting such a value, the haze of the cellulose acylate film does not increase, and when actually used in a liquid crystal display device, it contributes to suppression of inconveniences such as a decrease in contrast and generation of bright spots. Further, the above-mentioned creaking and scratch resistance can be realized. From these viewpoints, the content of the matting agent in the cellulose acylate film is particularly preferably 0.05 to 1.0% by mass.

(Peeling accelerator)
A known peeling accelerator may be added to the cellulose acylate film of the present invention.
The peeling accelerator is preferably an organic acid, a polyvalent carboxylic acid derivative, a surfactant or a chelating agent. For example, compounds described in paragraph numbers 0048 to 0081 of JP 2006-45497 A, compounds described in paragraph numbers 0077 to 0086 of JP 2002-322294 A, paragraph numbers 0030 to 0056 of JP 2012-72348 A. The compounds described in 1. can be preferably used.

  Examples of the organic acid include compounds described in JP-A-2002-322294, paragraphs 0079 to 0082, and examples thereof include citric acid, oxalic acid, adipic acid, succinic acid, malic acid, and tartaric acid.

  Furthermore, as the organic acid, amino acids are also preferable, for example, asparagine, aspartic acid, adenine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, glutamic acid, serine, tyrosine, tryptophan, threonine, norleucine, valine, phenylalanine, Examples include methionine, lysine, and leucine.

  The organic acid may be used as a free acid, and examples thereof include alkali metal salts, alkaline earth metal salts, and heavy metal salts including transition metals. Among the metals of each salt, examples of the alkali metal include lithium, potassium, and sodium, and examples of the alkaline earth metal include calcium, magnesium, barium, and strontium. Examples of heavy metals including transition metals include aluminum, zinc, tin, nickel, iron, lead, copper, and silver. Further, a salt of a substituted or unsubstituted amine having 5 or less carbon atoms is also preferable. Examples of the amine of the salt include ammonium, methylamine, ethylamine, propylamine, butylamine, dimethylamine, trimethylamine, triethylamine, hydroxyethylamine, bis Examples thereof include (hydroxyethyl) amine and tris (hydroxyethyl) amine. Preferred metals are sodium for alkali metals and calcium and magnesium for alkaline earth metals. These alkali metals and alkaline earth metals can be used alone or in combination of two or more thereof, and alkali metals and alkaline earth metals may be used in combination.

As the polyvalent carboxylic acid derivative, an ester compound and an amide compound are preferable.
The carboxylic acid component is a polyvalent carboxylic acid, and the carboxylic acid may be either aliphatic or aromatic carboxylic acid, but is preferably an aliphatic carboxylic acid. The aliphatic carboxylic acid may be saturated or unsaturated, but is preferably a linear, branched or cyclic aliphatic carboxylic acid, and may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a hydroxy group, an amino group, an alkoxy group, an alkenyloxy group, an acyloxy group, and an acylamino group.
Examples of aromatic carboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, 1,3,5-benzenetricarboxylic acid, and aliphatic carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Examples thereof include sebacic acid, and examples of the aliphatic carboxylic acid having a substituent include malic acid, citric acid, and tartaric acid.

In the polyvalent carboxylic acid ester, a group bonded to the oxygen atom of the ester functional group —C (═O) —O—, which is an alcohol component, is a substituted or unsubstituted alkyl group [for example, methyl, ethyl, isopropyl, t- butyl, _{2-ethylhexyl,} etc. _{-CH 2 CH 2 O- (CH 2} CH 2) n-C 2 H 5 ], an alkenyl group (e.g., vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl , Oleyl, etc.) are preferable, and the total carbon number of the alcohol component (group bonded to an oxygen atom) is preferably 1 to 200, more preferably 1 to 100, and further preferably 1 to 50. The substituent that the alkyl group and alkenyl group may have is preferably an alkoxy group, an alkenyloxy group, a hydroxy group, or an acyloxy group, and more preferably an alkoxy group. The alkoxy group or alkenyloxy group preferably contains a (poly) oxyalkylene group. In particular, the (poly) oxyalkylene group is a poly (oxyethylene) group, a (poly) oxypropylene group, or a (poly) oxy group. A butylene group is preferred.
Further, the starting alcohol in the alcohol component may be monovalent or polyvalent, and examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin and pentaerythritol, and these hydroxy group moieties. Those in which (—OH) is a polyoxyalkyleneoxy group [for example, — (OCH ₂ CH ₂ ) n—OH, — (OC ₃ H ₆ ) nOH] are also preferred.

In the polycarboxylic acid amide, the amine compound of the amine component may be either primary or secondary, and is not particularly limited. The substituent that substitutes the nitrogen atom of —C (═O) —N <of the amide functional group is an alkyl group [for example, methyl, ethyl, isopropyl, t-butyl, 2-ethylhexyl, —CH ₂ CH ₂ O— ( CH ₂ CH ₂ ) n—C ₂ H ₅ etc.], an alkenyl group (for example, vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl, etc.) is preferred, and the total number of carbon atoms of the amine compound as the amine component Is preferably 1 to 200, more preferably 1 to 100, and still more preferably 1 to 50. The substituent that the alkyl group and alkenyl group may have is preferably an alkoxy group, an alkenyloxy group, a hydroxy group, an acyloxy group, an amino group, or an acylamino group, and more preferably an alkoxy group. The alkoxy group or alkenyloxy group preferably contains a (poly) oxyalkylene group. In particular, the (poly) oxyalkylene group is a poly (oxyethylene) group, a (poly) oxypropylene group, or a (poly) oxy group. A butylene group is preferred. Moreover, it is also preferable that such a polyoxyalkylene partial structure contains a polyoxyalkylene group branched via glycerin.
The amine compound as a raw material in the amine component may be monovalent or polyvalent.

  Among polyvalent carboxylic acid derivatives, organic acid monoglyceride having a carboxyl group that can be released without being reacted is particularly preferable. Examples of commercially available products thereof include Poem K-37V (glycerine citrate oleic acid) manufactured by Riken Vitamin Co., Ltd. Ester), Kao's Step SS (glycerin stearic acid / palmitic acid succinate), and the like.

  As the surfactant, a compound described in paragraph Nos. 0050 to 0051 of JP-A-2006-45497 and a compound described in paragraph Nos. 0127 to 0128 of JP-A No. 2002-322294 can be preferably used. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, Examples include polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid partial ester, and polyetheramine. Moreover, as a commercial item, Naimine L-202, Starhome DO, Starhome DL (Nippon Oil), etc. are mentioned.

  The chelating agent is a compound capable of coordinating (chelating) with a polyvalent metal ion such as a metal ion such as an iron ion or an alkaline earth metal ion such as a calcium ion. An aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid Any of various chelating agents represented by phosphonocarboxylic acid may be used. Examples of chelating agents include JP-B-6-8956, JP-A-11-190892, JP-A-2000-18038, JP-A-2010-158640, JP-A-2006-328203, JP-A-2005-68246, JP-A-2006. The compounds described in each publication of -306969 can be used.

  Specifically, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ethylene glycol bis (2-aminoethyl ether) tetra Acetic acid, 1,3-diaminopropanetetraacetic acid, phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetra Methylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid), DL-alanine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, glutamic acid-N, N-diacetic acid, serine-N, N -Diacetic acid, polya Acrylic acid, isoamylene - maleic acid copolymer, acrylic acid - maleic acid copolymer, acrylic acid - methacrylic acid copolymer, silicic acid, gluconic acid, hydroxybenzyl iminodiacetonitrile acid, iminodiacetic acid, and the like. It is also preferable to use an oil-soluble chelating agent. As commercial products, Tekran DO (Nagase ChemteX Corporation), Kirest MZ-2, Kirest MZ-8 (Chillest Corporation) can be used.

<Configuration and physical properties of cellulose acylate film>
(Layer structure of film)
The cellulose acylate film of the present invention may be a single layer or a laminate of two or more layers.
When the cellulose acylate film of the present invention is a laminate of two or more layers, a two-layer structure or a three-layer structure is more preferable, and a three-layer structure is preferable. The three-layer structure is preferably composed of a single core layer (hereinafter also referred to as a base layer) and skin layers (skin A layer and skin B layer) facing each other with the core layer interposed therebetween (skin B layer / core layer / skin A layer).
The skin A layer and the skin B layer are collectively referred to as a skin layer (or surface layer).

  In the cellulose acylate film of the present invention, the acyl substitution degree of the cellulose acylate in each layer may be uniform, or a plurality of cellulose acylates may be mixed in one layer, but the cellulose acylate in each layer It is preferable from the viewpoint of adjusting optical properties that the acyl substitution degree is all constant. In addition, when the cellulose acylate film of the present invention has a three-layer structure, it is preferable from the viewpoint of production cost that the cellulose acylate contained in the surface layers on both sides is a cellulose acylate having the same acyl substitution degree.

(Elastic modulus)
The range of the elastic modulus of the cellulose acylate film of the present invention is not particularly limited, but is preferably 1.0 GPa to 5.0 GPa and more preferably 2.0 GPa to 4.5 GPa from the viewpoint of manufacturing suitability and handling properties. The compound represented by the general formula (I) of the present invention has an action of improving the elastic modulus by hydrophobizing the film by being added to the cellulose acylate. That is, the addition of the compound represented by the general formula (I) of the present invention is advantageous from the viewpoint of elastic modulus.

(Photoelastic coefficient)
The absolute value of the photoelastic coefficient of the cellulose acylate film of the present invention is preferably 8.0 × 10 ⁻¹² m ² / N or less, more preferably 6 × 10 ⁻¹² m ² / N or less, and further preferably 5 ×. 10 ⁻¹² m ² / N or less. By reducing the photoelastic coefficient of the resin film, it is possible to suppress the occurrence of unevenness under high temperature and high humidity when the resin film is incorporated into a liquid crystal display device as a polarizing plate protective film. The photoelastic coefficient is measured and calculated by the following method unless otherwise specified.
The lower limit of the photoelastic modulus is not particularly limited, but 0.1 × 10 ⁻¹² m ² / N or more is practical.

(Photoelastic modulus calculation method)
The film was cut into 3.5 cm x 12 cm, and the Re at each load of 250 g, 500 g, 1000 g, and 1500 g was measured with an ellipsometer (M150 [trade name], JASCO Corporation), and the Re change with respect to the stress. The photoelastic coefficient is measured by calculating from the slope of the straight line.

(Moisture content)
The moisture content of the cellulose acylate film can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. The equilibrium moisture content is calculated by measuring the moisture content of the sample that has reached equilibrium after being left in the temperature and humidity for 24 hours by the Karl Fischer method and dividing the moisture content (g) by the sample mass (g). .

  The water content of the cellulose acylate film of the present invention at 25 ° C. and 80% relative humidity is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably less than 3% by mass. By reducing the water content of the cellulose acylate film, when the cellulose acylate film is incorporated in a liquid crystal display device as a polarizing plate protective film, it is excellent in suppressing black display quality deterioration of the liquid crystal display device under high temperature and high humidity. The lower limit of the moisture content is not particularly limited, but is practically 0.1% by mass or more.

(Moisture permeability)
The moisture permeability of the cellulose acylate film is determined according to the moisture permeability test (cup method) of JIS Z0208 by measuring the mass of water vapor passing through the sample for 24 hours in an atmosphere at a temperature of 40 ° C. and a relative humidity of 90% RH. it can be evaluated by converting the value of the area 1 m ^2.
The moisture permeability of the cellulose acylate film of the present invention is preferably 500~2000g ^/ m 2 · day, more preferably from ^{900~1300g / m 2 · day, 1000~1200g} / m 2 · day is particularly preferred.

(Haze)
The cellulose acylate film of the present invention has a haze of preferably 1% or less, more preferably 0.7% or less, and particularly preferably 0.5% or less. By setting the haze to the above upper limit or less, there is an advantage that the transparency of the film becomes higher and the optical film is easier to use. The lower limit of haze is not particularly limited, but 0.001% or more is practical. The haze is measured according to JIS K7136 using a haze meter (HGM-2DP, Suga Test Instruments) in an environment of 25 ° C. and 60% relative humidity in a cellulose acylate film 40 mm × 80 mm.

(Film thickness)
10-100 micrometers is preferable, as for the average film thickness of the cellulose acylate film of this invention, 15-80 micrometers is more preferable, and 20-70 micrometers is more preferable. By making it 20 μm or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 70 micrometers or less, it is easy to respond to a humidity change and it is easy to maintain an optical characteristic.
In addition, when the cellulose acylate film of the present invention has a laminated structure of three or more layers, the thickness of the core layer is preferably 3 to 70 μm, more preferably 5 to 60 μm. When the film of the present invention has a laminated structure of three or more layers, the thickness of the surface layers (skin A layer and skin B layer) on both sides of the film is more preferably 0.5 to 20 μm, particularly 0.5 to 10 μm. Preferably, 0.5 to 3 μm is most preferable.

(Film width)
The film width of the cellulose acylate film of the present invention is preferably 700 to 3000 mm, more preferably 1000 to 2800 mm, and particularly preferably 1300 to 2500 mm.

<Method for producing cellulose acylate film>
Although the manufacturing method of the cellulose acylate film of this invention is not specifically limited, It is preferable to manufacture with the melt film forming method or the solution film forming method. Production by a solution casting method (solvent casting method) is more preferable. The cellulose acylate film of the present invention is preferably produced by a solvent cast method. Examples of production of a cellulose acylate film using a solvent cast method are described in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, and 2,492. No. 977, No. 2,492,978, No. 2,607,704, No. 2,739,069 and No. 2,739,070, British Patent No. 640731 and Refer to each specification of No. 736892, and Japanese Patent Publication Nos. 45-4554, 49-5614, JP-A-60-176634, 60-203430 and 62-1115035. Can do. The cellulose acylate film may be subjected to a stretching treatment. With respect to the stretching method and conditions, for example, refer to JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do.

(Casting method)
As a method for casting a solution, a method in which a prepared dope is uniformly extruded from a pressure die onto a metal support, and a method in which a film thickness of the dope once cast on the metal support is adjusted with a blade is used. Although there is a method using a reverse roll coater that adjusts with a reverse rotating roll, a method using a pressure die is preferred. The pressure die includes a coat hanger type and a T die type, and any of them can be preferably used. In addition to the methods mentioned here, it can be carried out by various known methods for casting a cellulose triacetate solution, and each condition is set in consideration of differences in the boiling point of the solvent used. Thus, the same effects as those described in the respective publications can be obtained.

-Co-casting In the formation of the cellulose acylate film of the present invention, it is preferable to use a lamination casting method such as a co-casting method (multilayer simultaneous casting), a sequential casting method, a coating method, etc. It is particularly preferable to use it from the viewpoint of stable production and production cost reduction.
In the case of producing a cellulose acylate film having two or more layers by the co-casting method, first, a cellulose acetate solution (dope) for each layer is prepared. Subsequently, the dope for each layer is extruded onto a casting support (band or drum) by extruding the dope from a casting giusa having a function of simultaneously extruding the casting dope for each layer from another slit or the like. The film is cast at the same time, peeled off from the support at an appropriate time, and dried to form a film. FIG. 2 is a cross-sectional view showing a state in which the co-casting giesser 3 is used to simultaneously extrude and cast the surface layer dope 1 and the core layer dope 2 on the casting support 4.

・ Sequential casting method In the sequential casting method, a casting dope for the first layer is first extruded from a casting gear on a casting support, and cast without drying or drying. The dope for casting for the second layer is extruded from the caster for casting on the second layer, and if necessary, the dope is cast and laminated successively up to the third layer and peeled off from the support at an appropriate time. Take and dry to form a film.

-Coating method Generally, the coating method involves forming a core layer film into a film by a solution casting method, preparing a coating solution to be applied to the surface layer, and using a suitable coating machine, one side at a time or both sides simultaneously. In this method, a coating film is applied to the film and dried to form a film having a laminated structure.

Endlessly running casting supports (metal supports) used to produce cellulose acylate films include drums whose surfaces are mirror-finished by chrome plating and stainless steel belts that are mirror-finished by surface polishing. (May be called a band) is used. One or more pressure dies may be installed above the metal support. When two or more are installed, the dope amount to be cast may be distributed to each die. The dope may be fed from a plurality of precision quantitative gear pumps to the die at respective ratios. The temperature of the dope (resin solution) used for casting is preferably −10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all solution temperatures in the process may be the same or different at different points in the process.
Moreover, there is no restriction | limiting in particular about the material of the said metal support body, However, It is more preferable that it is a product made from SUS (for example, SUS316).

(Peeling)
The production of the cellulose acylate film of the present invention preferably includes a step of peeling the dope film from the metal support.

(Extension process)
In the manufacturing method of the cellulose acylate film of this invention, it is preferable to include the process of extending | stretching formed into a film. The stretching direction of the cellulose acylate film may be either the film transport direction or the direction (width direction) perpendicular to the transport direction, but the direction that is perpendicular to the film transport direction (width direction) is used for the subsequent film. From the viewpoint of the polarizing plate processing process.

  Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

  When the cellulose acylate film of the present invention is used as a protective film for a polarizer, in order to suppress light leakage when the polarizing plate is viewed obliquely, the transmission axis of the polarizer and the in-plane of the resin film of the present invention Need to be arranged in parallel. Since the transmission axis of the roll film-like polarizer produced continuously is generally parallel to the width direction of the roll film, it is composed of the roll film-like polarizer and the roll film-like cellulose acylate film. In order to continuously bond the protective film, the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the film. Therefore, it is preferable to stretch more in the width direction. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched.

  Stretching in the width direction is preferably 5 to 100%, more preferably 5 to 80%, particularly preferably 5 to 40%. In addition, unstretched means that stretching is 0%. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state including the residual solvent amount, and the residual solvent amount = (residual volatile matter mass / heat-treated film mass) × 100% is preferably stretched at 0.05 to 50%. be able to. It is particularly preferable to perform 5 to 80% stretching in a state where the residual solvent amount is 0.05 to 5%.

(Dry)
In the manufacturing method of the cellulose acylate film of this invention, the process of drying a cellulose acylate film and the process of extending | stretching the resin film of this invention after drying at the temperature of glass transition temperature (Tg) -10 degreeC or more are included. Is preferable from the viewpoint of retardation development.

  The dope drying on the metal support involved in the production of the cellulose acylate film of the present invention is generally performed from the surface side of the metal support (drum or belt), that is, from the surface of the web on the metal support. A method in which hot air is applied, a method in which hot air is applied from the back of the drum or belt, a temperature-controlled liquid is brought into contact with the back of the belt or drum opposite the dope casting surface, and the drum or belt is heated to transfer the surface to the surface. Although there is a back surface liquid heat transfer method for controlling the temperature, the back surface liquid heat transfer method is preferable. The surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. In order to promote drying and lose fluidity on the metal support, the temperature is preferably set to 1 to 10 ° C lower than the boiling point of the lowest boiling solvent among the solvents used. This is not the case when the cast dope is cooled and peeled off without drying.

  The film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness.

  The length of the cellulose acylate film obtained as described above is preferably wound at 100 to 10,000 m per roll, more preferably 500 to 7000 m, and still more preferably 1000 to 6000 m. When winding, it is preferable to give knurling to at least one end, the knurling width is preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 μm, more preferably 1 to 200 μm. is there. This may be a single push or a double push.

  When used as an optical compensation film for a large-screen liquid crystal display device, for example, the film width is preferably set to 1470 mm or more. In addition, the polarizing plate protective film of the present invention is produced not only in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also in a long shape by continuous production. The film of the aspect wound up in the shape is also included. The polarizing plate protective film of the latter mode is stored and transported in that state, and is cut into a desired size and used when it is actually incorporated into a liquid crystal display device or bonded to a polarizer or the like. Similarly, it is cut into a desired size when it is actually incorporated into a liquid crystal display device after being bonded to a polarizer or the like made of a polyvinyl alcohol film or the like that has been made into a long shape. Used. As one mode of the optical compensation film wound up in a roll shape, a mode in which the roll length is rolled up to 2500 m or more can be mentioned.

<< Polarizing plate >>
The polarizing plate of this invention has a polarizer and the cellulose acylate film of this invention at least.
The polarizing plate of the present invention preferably has a polarizer and the film of the present invention on one or both sides of the polarizer. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When the cellulose acylate film of the present invention is used as a polarizing plate protective film, the method for producing the polarizing plate is not particularly limited, and can be produced by a general method. There is a method in which the obtained cellulose acylate film is treated with an alkali and bonded to both surfaces of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed. Examples of the adhesive used to bond the protective film-treated surface and the polarizer include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and the like.

  The cellulose acylate film of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer and the slow axis of the cellulose acylate film of the present invention are substantially orthogonal. In the liquid crystal display device of the present invention, it is preferable that the transmission axis of the polarizing plate and the slow axis of the cellulose acylate film of the present invention are substantially orthogonal. Here, being substantially orthogonal means that the direction of the main refractive index nx of the cellulose acylate film of the present invention and the direction of the transmission axis of the polarizing plate intersect at an angle of 90 ° ± 10 °. However, it is preferable that they intersect at an angle of 90 ° ± 5 °, more preferably at an angle of 90 ° ± 1 °. By adjusting the angle in this way at the time of bonding, light leakage under a polarizing plate crossed Nicol can be further reduced. The slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRA DH, manufactured by Oji Scientific Instruments).

  The polarizing plate of the present invention is produced not only in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also in a long shape by continuous production and wound up into a roll. The polarizing plate of the aspect (for example, roll length 2500m or more or 3900m or more aspect) is also included. In order to use for a large-screen liquid crystal display device, the width of the polarizing plate is preferably 1470 mm or more. The specific configuration of the polarizing plate of the present invention is not particularly limited, and a known configuration can be employed. For example, the configuration described in FIG. 6 of JP-A-2008-262161 can be employed.

<< Liquid Crystal Display >>
The liquid crystal display device of the present invention has a liquid crystal cell and the polarizing plate of the present invention.
The liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing plates is an IPS, OCB or A VA mode liquid crystal display device is preferable. The internal structure of a typical liquid crystal display device is shown in FIG. There is no restriction | limiting in particular as a concrete structure of the liquid crystal display device of this invention, A well-known structure is employable. Further, the configuration described in FIG. 2 of JP-A-2008-262161 can also be preferably employed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited thereto.

[Synthesis of Compound Represented by General Formula (I)]
The compound represented by the general formula (I) of the present invention was synthesized as follows.
Synthesis examples of typical compounds are shown below.

Synthesis example 1
Exemplary compound (A-1) was synthesized by the following reaction scheme.

1) Synthesis of intermediate N-benzyl-N'-phenylurea A 5 L glass flask equipped with a thermometer, reflux condenser and stirrer was charged with 321 g of benzylamine and 2 L of acetonitrile, cooled in a water bath and stirred with isocyanide. 358 g of phenyl acid was added dropwise at such a rate that the internal temperature of the reaction solution became 40 ° C. or lower. After stirring for 2 hours as it was, 2 L of water was added and suction filtered, and the precipitated crystals were collected by filtration and washed 3 times with 1 L of water. The obtained crystals were dried at 80 ° C. under reduced pressure to obtain 610 g of an intermediate N-benzyl-N′-phenylurea.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, 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 Compound (A-1) In a 300 ml glass flask equipped with a thermometer, a reflux condenser and a stirrer, 5.0 g of N-benzyl-N′-phenylurea, 8.16 g of phenylmalonic acid, acetic acid 10 mL and 15 mL of acetic anhydride were charged, and the mixture was heated with stirring to an internal temperature of 60 ° C., and the stirring was continued at 60 ° C. for 1.5 hours. Thereafter, the mixture was cooled to room temperature, and 100 mL of diisopropyl ether was added. After cooling in an ice-water bath and stirring for 1 hour, the crystals precipitated by suction filtration were collected by filtration, washed with cooled diisopropyl ether and dried to obtain 4.2 g of Exemplified Compound (A-1).
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl ₃ ), δ: 7.50-7.10 (m, 15H), 5.13 (dd, 2H), 4.80 (s, 1H)

  Illustrative compound (A-3) can be synthesized, for example, by the following reaction scheme.

Synthesis example 2
(A) Synthesis of Exemplary Compound (A-3) in Route 1 Intermediate N-benzyl-N′- synthesized in Synthesis Example 1 was added to a 300 ml glass flask equipped with a thermometer, a reflux condenser and a stirrer. 5.0 g of phenylurea, 6.4 g of benzylmalonic acid, 10 mL of toluene and 15 mL of acetic anhydride were charged and heated while stirring so that the internal temperature became 75 ° C., and the stirring was continued at 75 ° C. for 2 hours. Thereafter, the mixture was cooled to 50 ° C., and 50 mL of a 1 mol / dm ³ aqueous sodium hydroxide solution was added. The organic phase was discarded, and the aqueous phase was cooled in an ice water bath, and 10 mL of 6M hydrochloric acid was added dropwise with stirring. Furthermore, after stirring at 0 ° C. for 1 hour, the crystals precipitated by suction filtration were collected by filtration, washed with water and dried to obtain 7.5 g of exemplary compound (A-3).
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl ₃ ), δ: 7.55 to 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 Exemplary Compound (A-3) in Route 2 Exemplary compound (A-3) was synthesized as follows.

1) Synthesis of intermediate 1-benzyl-3-phenylbarbituric acid N-benzyl-N'-phenyl synthesized in Synthesis Example 1-1 in a 300 ml glass flask equipped with a thermometer, reflux condenser and stirrer 5.0 g of urea, 2.5 g of malonic acid, 20 mL of toluene, and 5.6 g of acetic anhydride were charged, and the mixture was heated to 80 ° C. while stirring, and the stirring was continued at 80 ° C. for 3 hours. Thereafter, the mixture was cooled to 50 ° C., 15 mL of water was added for liquid separation, and the aqueous phase was discarded. While stirring the organic layer at room temperature, 5 mL of isopropanol was added dropwise. Further, the mixture was stirred at 10 ° C. or lower for 0.5 hour, suction filtered, and the precipitated crystals were collected by filtration, washed with cooled isopropanol, and then dried to obtain 4.6 g of intermediate 1-benzyl-3-phenylbarbituric acid. Obtained.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, 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-phenylbarbituric acid 1-benzyl-3-phenylbarbituric acid in a 300 ml glass flask equipped with a thermometer, reflux condenser and stirrer 0 g, 1.6 g of benzaldehyde and 40 mL of acetic acid were added, 1 drop of sulfuric acid was added, and the mixture was heated with stirring so that the internal temperature became 100 ° C., and the stirring was continued at 100 ° C. for 3 hours. Thereafter, the mixture was cooled to 50 ° C., a mixed solution of 39 mL of isopropanol and 17 mL of water was added, and the mixture was stirred at 10 ° C. or lower for 1 hour, suction filtered, and the precipitated crystals were collected by filtration, washed with methanol, intermediate 1-benzyl- 3.9 g of 5-benzylidene-3-phenylbarbituric acid was obtained.
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, CDCl ₃ ), δ: 8.70 (s, 1H), 8.10 (d, 2H), 7.58-7.20 (m, 15H), 5.20 (s, 2H)

3) Synthesis of Exemplified Compound (A-3) Into a 50 ml autoclave was charged 3.5 g of 1-benzyl-5-benzylidene-3-phenylbarbituric acid and 8 mL of methanol, and 0.1 g of Pd-C (10%) was added. While stirring, H ₂ was charged and heated to an internal temperature of 50 ° C., and stirring was continued at 50 ° C. for 3 hours. Thereafter, Pd-C was separated by filtration, cooled to 5 ° C., further added with 4 mL of water, stirred at 5 ° C. for 1 hour, suction filtered and the precipitated crystals were collected by filtration, and mixed with methanol / water = 1/1. After washing with a solvent, it was dried to obtain 3.0 g of exemplary compound (A-3).
The structure of the obtained compound was confirmed by ¹ H-NMR spectrum, IR spectrum and mass spectrum.
In addition, it confirmed that the structure of the obtained compound corresponded with the thing obtained by the synthesis example 2 by the < ¹ > H-NMR spectrum.

The compounds other than the above used in the examples were synthesized by a method similar to the above, the method described in the aforementioned literature, or a method analogous thereto.
Here, the exemplary compound (A-2) had a melting point of 139 ° C., the exemplary compound (A-4) had a melting point of 88 ° C., and the exemplary compound (A-5) had a melting point of 113 ° C.

Example 1
A cellulose acylate film was prepared as follows, and film coloring by light was evaluated as light resistance.

(Preparation of cellulose acylate)
A cellulose acylate having a total acetyl substitution degree (B) of 2.87 was prepared. This was carried out by adding sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) as a catalyst, adding carboxylic acid as a raw material for the acyl substituent, and carrying out an acylation reaction at 40 ° C. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

(Preparation of surface layer dope)
-Preparation of cellulose acylate solution The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution.

―――――――――――――――――――――――――――――――――――
Composition of cellulose acylate solution ――――――――――――――――――――――――――――――――――――
Cellulose acetate having a total acetyl substitution degree (B) of 2.87 and a polymerization degree of 370
100.0 parts by mass Daipet Kogyo Monopet (registered trademark) SB (plasticizer)
9.0 parts by weight SAIB-100 (plasticizer) manufactured by Eastman Chemical Co., Ltd. 3.0 parts by weight Methylene chloride (first solvent) 353.9 parts by weight Methanol (second solvent) 89.6 parts by weight n-butanol ( Third solvent) 4.5 parts by mass ―――――――――――――――――――――――――――――――――――

  Monopet (registered trademark) SB manufactured by Daiichi Kogyo Kagaku is benzoic acid ester of sucrose, and SAIB-100 manufactured by Eastman Chemical Co. is acetic acid and isobutyric acid ester of sucrose.

-Preparation of matting agent solution The following composition was put into a disperser and stirred to dissolve each component to prepare a matting agent solution.

―――――――――――――――――――――――――――――――――――
Composition of matting agent solution ―――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972,
Nippon Aerosil Co., Ltd.) 2.0 parts by weight Methylene chloride (first solvent) 69.3 parts by weight Methanol (second solvent) 17.5 parts by weight n-butanol (third solvent) 0.9 parts by weight The cellulose Acylate solution 0.9 parts by mass ―――――――――――――――――――――――――――――――――――

-Preparation of ultraviolet absorber solution The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare an ultraviolet absorber solution.

―――――――――――――――――――――――――――――――――――
Composition of UV absorber solution ―――――――――――――――――――――――――――――――――――
The following ultraviolet absorber (UV-1) 20.0 parts by mass Methylene chloride (first solvent) 61.0 parts by mass Methanol (second solvent) 15.4 parts by mass n-butanol (third solvent) 0.8 parts by mass 12.8 parts by mass of the cellulose acylate solution ―――――――――――――――――――――――――――――――――――

  1.3 parts by mass of the matting agent solution and 3.4 parts by mass of the UV absorber solution are mixed using an in-line mixer after filtration, and further 95.3 parts by mass of a cellulose acylate solution is added. Were mixed to prepare a surface layer solution.

(Preparation of dope for base layer)
-Preparation of cellulose acylate solution The following composition was put into a mixing tank and stirred to dissolve each component to prepare a base layer dope.

―――――――――――――――――――――――――――――――――――
Composition of cellulose acylate solution ――――――――――――――――――――――――――――――――――――
Cellulose acetate having a total acetyl substitution degree (B) of 2.87 and a polymerization degree of 370
100.0 parts by mass Daipet Kogyo Monopet (registered trademark) SB (plasticizer)
9.0 parts by weight SAIB-100 (plasticizer) manufactured by Eastman Chemical Co., Ltd. 3.0 parts by weight Illustrative compound (A-1) 4.0 parts by weight The ultraviolet absorber (UV-1) 2.0 parts by weight Methylene Chloride (first solvent) 297.7 parts by mass Methanol (second solvent) 75.4 parts by mass n-butanol (third solvent) 3.8 parts by mass ――――――――――――――― ――――――――――――――――――――

(Casting)
Using a drum casting apparatus, the base layer dope prepared as described above and the surface layer dope on both sides of the dope for the stainless steel casting support (support temperature −9 ° C.) are uniformly formed from the casting port. It was cast into. Stripped in a state where the amount of residual solvent in the dope of each layer is about 70% by mass, fixed both ends in the width direction of the film with a pin tenter, and 1.28 in the width direction in a state of residual solvent amount of 3-5% by mass. The film was dried while being stretched twice (28%). Then, it further dried by conveying between the rolls of a heat processing apparatus, and obtained the cellulose acylate film 101 of this invention. The obtained cellulose acylate film 101 had a thickness of 60 μm and a width of 1480 mm.

  In the said cellulose acylate film 101, it replaced with exemplary compound A-1, and changed the kind and addition amount of a compound as shown in below-mentioned Table 6 similarly to the cellulose acylate film 101 of this invention. Cellulose acylate films 102 to 118 and comparative cellulose acylate films c10 to c13 were produced, respectively.

  Moreover, in the said cellulose acylate film 101, it casted and dried so that the film thickness of the obtained cellulose acylate film might be 40 micrometers, and a width | variety might be 1480 mm, and the cellulose acylate film 131 of this invention was obtained. In this cellulose acylate film 131, the cellulose acylate film of the present invention was prepared in the same manner as the cellulose acylate film 131 except that the type of the compound was changed as shown in Table 6 described below instead of the exemplified compound A-1. 132 to 135 and a comparative cellulose acylate film c21 were produced.

  Similarly, in the cellulose acylate film 101, the resulting cellulose acylate film was cast and dried so that the film thickness was 25 μm and the width was 1480 mm, and the cellulose acylate film 141 of the present invention was obtained. In the cellulose acylate film 141, the cellulose acylate film of the present invention was used in the same manner as the cellulose acylate film 141 except that the type of the compound was changed as shown in Table 6 described below instead of the exemplified compound A-1. 142 to 145 and comparative cellulose acylate film c22 were produced.

  Furthermore, in the cellulose acylate film 101, cellulose acylate was used except that 12 parts by mass of the following polycondensation polymer (A), which is a polycondensation ester plasticizer, was added instead of Monopet (registered trademark) SB and SAIB-100. The cellulose acylate film 201 of the present invention was obtained in the same manner as the rate film 101. In this cellulose acylate film 201, the cellulose acylate of the present invention was prepared in the same manner as the cellulose acylate film 201 except that the type of the compound was changed as shown in Table 6 described below instead of the exemplified compound A-1. Films 202 to 205 and comparative cellulose acylate films c30 to c33 were produced, respectively.

  Polycondensation polymer (A): Polyester comprising adipic acid and ethanediol (terminal is a hydroxy group) (number average molecular weight = 1000)

Each cellulose acylate film was evaluated for film coloring by light.
The obtained results are shown in Table 6 below together with the results of Examples 2 and 3.
In addition, these cellulose acylate films are also called a polarizing plate protective film below.

(Evaluation of film coloring by light)
For each cellulose acylate film produced as described above, using a super xenon weather meter (SX75 manufactured by Suga Test Instruments Co., Ltd.), irradiance 150 W / m ² , black panel temperature 63 ° C., relative humidity 50% Light irradiation was performed for 120 hours under the condition of RH. Thereafter, the hue b ^* was measured using a spectrophotometer UV3150 manufactured by Shimadzu Corporation. When the value of the hue b ^* increases to the minus side, the transmitted light becomes bluish, and when the value of the hue b ^* increases to the plus side, the yellowness increases.
Further, the change in b ^* of each cellulose acylate film before and after the light irradiation was Δb ^{*, which} was used as an index for coloring with light.
Evaluation was performed according to the following criteria.

A: Δb ^* is 0.05 or less B: Δb ^* exceeds 0.05 to 0.10 or less C: Δb ^* exceeds 0.10 to 0.15 or less D: Δb ^* exceeds 0.15

  The obtained results are collectively shown in Table 6 described later.

Example 2
Using the cellulose acylate film prepared in Example 1, a polarizing plate was prepared as follows to evaluate the durability of the polarizing plate, and an optical film with a hard coat layer was prepared to provide light-resistant adhesion. evaluated.

(Saponification treatment of polarizing plate protective film)
The polarizing plate protective film made of the cellulose acylate film 101 produced in Example 1 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. Thus, the surface saponification process was performed with respect to each polarizing plate protective film.

(Preparation of polarizing plate)
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
The polarizing plate protective film 101 produced in Example 1 and subjected to the saponification treatment was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Film Co., Ltd.) is also subjected to the same saponification treatment, and is opposite to the side where the saponified polarizing plate protective film 101 is pasted using a polyvinyl alcohol adhesive. The commercially available cellulose triacetate film having been saponified was attached to the surface of the polarizer on the side.
At this time, the transmission axis of the polarizer and the slow axis of the polarizing plate protective film prepared in Example 1 and subjected to the saponification treatment were arranged in parallel. Further, the transmission axis of the polarizer and the slow axis of the commercially available cellulose triacetate film after saponification treatment were also arranged so as to be orthogonal to each other.
Thus, the polarizing plate 101 of the present invention was produced.

  The polarizing plate protective films 102 to 118, 131 to 135, 141 to 145, 201 to 205 and the comparative polarizing plate protective films c10 to c13, c21, c22, and c30 to c33 were respectively subjected to saponification treatment in the same manner as described above. Polarizing plates were prepared, and polarizing plates 102 to 118, 131 to 135, 141 to 145, and 201 to 205 of the present invention, and comparative polarizing plates c10 to c13, c21, c22, and c30 to c33 were prepared.

(Evaluation of polarizing plate durability)
The polarizing plate durability test was performed as follows in a form in which the polarizing plate was attached to glass through an adhesive.
Two samples (about 5 cm × 5 cm) each having a polarizing plate pasted on glass so that the cellulose acylate film of the present invention is on the air interface side are prepared. In the single plate orthogonal transmittance measurement, the sample is set with the cellulose acylate film side of the present invention facing the light source. Two samples were measured respectively, and the average value was taken as the orthogonal transmittance of the polarizing plate in the examples. The orthogonal transmittance of the polarizing plate was measured in the range of 380 nm to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the measured value at 410 nm was adopted. Then, after storing over time under conditions according to the film thickness, the orthogonal transmittance was measured in the same manner. The change of the orthogonal transmittance before and after aging was determined, and this was evaluated as the polarizing plate durability according to the following criteria.
In addition, the relative humidity in the environment without humidity control was in the range of 0 to 20% RH.
The obtained results are shown in Table 6 below.

-Aging condition-
Samples 101-118, 201-205, c10-c13, and c30-c33:
168 hours and 336 hours in an environment of 80 ° C. and 90% relative humidity Samples 131 to 135, and c21:
120 hours and 240 hours in an environment of 80 ° C. and relative humidity 90% RH Samples 141 to 145, and c22
500 hours and 1000 hours in an environment of 60 ° C. and a relative humidity of 95% RH

A: Change in orthogonal transmittance before and after aging is less than 0.6% B: Change in orthogonal transmittance before and after aging is 0.6 to 1.0%
C: Change in orthogonal transmittance before and after aging exceeds 1.0%

  The obtained results are collectively shown in Table 6 described later.

(Preparation of optical film with hard coat layer)
Each component described in the following table was mixed, and then filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for a hard coat layer.

―――――――――――――――――――――――――――――――――――
Composition of hard coat layer solution ―――――――――――――――――――――――――――――――――――
Monomer Pentaerythritol triacrylate /
Pentaerythritol tetraacrylate (mixing mass ratio 3/2)
53.5 parts by weight UV initiator Irgacure ^™ 907
(Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass Ethyl acetate 45 parts by mass ――――――――――――――――――――――――――――― ――――――

On the air side surface of each cellulose acylate film produced as described above, the hard coat layer coating solution was applied by a micro gravure coating method under the condition of a conveyance speed of 30 m / min. After dried for 150 seconds at 60 ° C., with a nitrogen purge (hereinafter oxygen concentration of 0.5%), using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co.), illuminance 400 mW / cm ^2, irradiation The coating layer was cured by irradiating an ultraviolet ray with a quantity of 150 mJ / cm ² to form a hard coat layer (thickness 6 μm).
In this way, a hard coat layer was formed on the air side surface of each cellulose acylate film, and a cellulose acylate film with a hard coat layer was produced.
In Table 6 below, a single-layer optical film No. And corresponding optical film No. 1 with a hard coat layer. Common film No. It is indicated with

(Evaluation of light adhesion)
First, with respect to the polarizing plate protective film with a hard coat layer of each Example and Comparative Example prepared above, in a super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd., in an environment of 60 ° C. and 50% relative humidity. Were irradiated with light for 96 hours.
Next, each polarizing plate protective film with a hard coat layer was conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%. On the surface having the hard coat layer, 11 mm long and 11 wide cuts are made at 1 mm intervals in a grid pattern with a cutter knife against a 1 cm square polarizing plate protective film with a hard coat layer. A total of 100 square squares were cut and a polyester adhesive tape (No. 31B) manufactured by Nitto Denko Corporation was attached to the surface. After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken. The results are shown in the table below.

A: The peeling was 10 mm or less at 100 mm.
B: Peeling of 11 to 20 mm was observed at 100 mm.
C: Peeling of 21 to 30 mm was observed at 100 mm.
D: Peeling of 31 mm or more was observed at 100 mm.

  These results are summarized in Table 6.

  Here, HA, H-1, and H-2 in Table 6 are the following compounds.

  From the results of Table 6 above, the polarizing plate protective film which is the cellulose acylate film of the present invention containing the compound represented by the general formula (I) of the present invention is excellent in polarizing plate durability over time, The deterioration of the polarizer can be effectively suppressed, and further, coloring with time due to light was small.

On the other hand, polarizing plate protective films c10 to c12 and c30 to c32, which are cellulose acylate films containing HA, H-1 or H-2, which are the comparative compounds, are all polarizing plates of the present invention. Compared with the protective film, it was impossible to achieve both durability of the polarizing plate and suppression of coloring with time by light. Moreover, the cellulose acylate films c10 to c12 and c30 to c32 with a hard coat layer obtained by applying a hard coat layer to the polarizing plate protective film to which these comparative compounds are added are all compared with the polarizing plate protective film of the present invention. The light-resistant adhesion with the hard coat layer was inferior, and it was not possible to achieve both polarizing plate durability and light-resistant adhesion.
In the polarizing plate protective films c13, c21, c22 and c33, which are comparative cellulose acylate films containing neither the compound represented by the general formula (I) of the present invention nor the comparative compound, all of the cellulose acylates of the present invention Compared with the polarizing plate protective film which is a film, it was inferior in polarizing plate durability.
As a result, by using the polarizing plate of the present invention, a liquid crystal display device having excellent performance as described above can be produced.

Example 3
[Change of total substitution degree (B) of cellulose acylate]
In the cellulose acylate film 101 in Example 1, the total acetyl substitution degree (B) used in the composition of the cellulose acylate solution in the preparation of the base layer dope solution (B) instead of 2.87 cellulose acetate ( B) A cellulose acylate film 301 of the present invention was obtained in the same manner as the cellulose acylate film 101 except that 100.0 parts by mass of 2.77 cellulose acetate was added. The cellulose acylate film 301 is different from the cellulose acylate film 301 except that the cellulose acetate having a different total acetyl substitution degree (B), the kind of the exemplified compound to be added, and the plasticizer are changed as shown in Table 7 described later. In the same manner, cellulose acylate films 302 to 304 of the present invention and cellulose acylate films c40 and c41 of comparative examples were produced.

  Further, in the cellulose acylate film 202 in Example 1, similarly, the total amount of acetyl substitution (B) used in the composition of the cellulose acylate solution in the preparation of the base layer dope solution was replaced with cellulose acetate of 2.87. A cellulose acylate film 311 of the present invention was obtained in the same manner as the cellulose acylate film 202 except that 100.0 parts by mass of cellulose acetate having an acetyl substitution degree (B) of 2.77 was added. The cellulose acylate film 311 is different from the cellulose acylate film 311 except that the cellulose acetate having a different total acetyl substitution degree (B), the kind of the exemplified compound to be added, and the plasticizer are changed as shown in Table 7 described later. In the same manner as above, cellulose acylate films 00312 to 314 of the present invention and cellulose acylate films c42 and c43 of comparative examples were produced.

  Further, in the same manner as in Example 2, a polarizing plate and an optical film with a hard coat layer were produced. Evaluation was performed in the same manner as in Examples 1 and 2 except that the aging conditions of the polarizing plate durability were as follows.

-Aging condition-
Samples 301-304, 311-314, c40-c43:
168 hours and 336 hours in an environment of 80 ° C. and relative humidity 90% RH

  The results obtained are summarized in Table 7 below.

  From the results of Table 7 above, the polarizing plate using the polarizing plate protective film that is the cellulose acylate film of the present invention containing the compound represented by the general formula (I) of the present invention has a total acetyl substitution degree (B). Regardless, the polarizing plate durability over time was excellent, and deterioration of the polarizer could be effectively suppressed.

Example 4
[Evaluation of metal corrosivity of compounds]
Evaluation on the metal corrosivity of the compound represented by the general formula (I) of the present invention was performed as follows.

(Evaluation on metal corrosivity)
In a pressure vessel, each compound was dissolved at a concentration of 1% by mass with respect to the mixed solvent used in the preparation of the base layer dope, and 20 g of the solution was weighed. The thickness was cut into a width of 2 cm and a length of 3 cm. A test piece of SUS316 was immersed. The pressure vessel was sealed, and after aging at 90 ° C. for 70 hours, the lid of the pressure vessel was opened, and the corrosion of the test piece and the change in the organic acid solution resulting therefrom were observed, and evaluated according to the following criteria.

A: There is no change in the smoothness of the test piece surface, and the solution is colorless or pale yellow and has no insoluble content.
B: Although the change of the smoothness of the test piece surface is small, the solution is colored yellow.
C: The test piece spike cotton is rough and the solution is brown and cloudy.

  The obtained results are shown in Table 8 below.

From the results of Table 8, the compound of the present invention has good metal corrosiveness, whereas the comparative organic acid H-2 has insufficient metal corrosiveness. There is concern about the contamination of impurities.
As described above, from the results of Tables 6 to 8, the compound of the present invention is effective for improving the durability of the polarizing plate and suppressing coloration, and at the same time, is advantageous for the stabilization of production and the degree of freedom of the addition amount. I understand that.

Example 5
A polarizing plate was produced as follows and the polarizing plate durability was evaluated.

(Preparation of cellulose acylate solution 5-1)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 5-1.

―――――――――――――――――――――――――――――――――――
Composition of Cellulose Acylate Solution 5-1 ――――――――――――――――――――――――――――――――――――
-Cellulose acetate with acetyl substitution degree 2.87 and polymerization degree 370
100.0 parts by mass Hydrophobizing agent 1: Polycondensate of phthalic acid / ethanediol
The terminal is an acetyl ester group and the average molecular weight is 800
10.0 parts by mass · Methylene chloride (first solvent) 389.8 parts by mass · Methanol (second solvent) 58.2 parts by mass ――――――――――――――――――― ―――――――――――――――

(Preparation of matting agent solution 5-2)
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution 5-2.

―――――――――――――――――――――――――――――――――――
Composition of matting agent solution 5-2 ――――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972,
Nippon Aerosil Co., Ltd.) 2.0 parts by weight Methylene chloride (first solvent) 75.5 parts by weight Methanol (second solvent) 11.3 parts by weight The cellulose acylate solution 501 0.9 parts by weight ―――――――――――――――――――――――――――――――

(Preparation of polarizer durability improver solution 5-3)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a polarizer durability improving agent solution 5-3.

―――――――――――――――――――――――――――――――――――
Composition of polarizer durability improver solution 5-3 ―――――――――――――――――――――――――――――――――――
Illustrative compound (A-3) 20.0 parts by mass Reductone (L) 1.0 part by mass Methylene chloride (first solvent) 73.5 parts by mass Methanol (second solvent) 6.4 parts by mass ―――――――――――――――――――――――――――――

  In addition, said reductone (L) is 6-O-palmitoyl-L-ascorbic acid by Tokyo Chemical Industry Co., Ltd. with the following structure.

(Preparation of UV absorber solution 5-4)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a polarizer durability improving agent solution 5-4.

―――――――――――――――――――――――――――――――――――
Composition of UV absorber solution 5-4 ――――――――――――――――――――――――――――――――――――
The following ultraviolet absorber (UV-2) 10.0 parts by weight Methylene chloride (first solvent) 78.3 parts by weight Methanol (second solvent) 11.7 parts by weight ――――――――――――― ――――――――――――――――――――――

<Casting>
1.3 parts by mass of the matting agent solution 5-2, 3.3 parts by mass of the polarizer durability improving agent solution 5-3, and 4.0 parts by mass of the ultraviolet absorber solution 5-4, respectively, are filtered and an in-line mixer. Then, 91.4 parts by mass of the cellulose acylate solution 5-1 was added and mixed using an in-line mixer. Using the band casting apparatus, the prepared dope was cast on a stainless steel casting support (support temperature 22 ° C.). The dope is peeled off in a state where the amount of residual solvent in the dope is approximately 20% by mass, both ends in the width direction of the film are held by a tenter, and the amount of residual solvent is 5 to 10% by mass in the width direction at a temperature of 120 ° C. To 1.10 times (10%). Then, it dried further by conveying between the rolls of the heat processing apparatus, and the cellulose acylate film 501 was obtained. The obtained cellulose acylate film had a thickness of 23 μm and a width of 1480 mm.

Furthermore, in the cellulose acylate film 501, the kind and addition amount of the exemplified compound to be added and the kind and addition amount of the plasticizer were changed as shown in the following Table 9 in the same manner as the cellulose acylate film 501, Cellulose acylate films 502 to 521 of the present invention were produced.
Further, in the cellulose acylate film 501, a comparative cellulose acylate film c61 was produced in the same manner as the cellulose acylate film 501, except that the polarizer durability improving agent solution 503 was not mixed.

  Here, the newly used materials in Table 9 are as follows.

[Material used]
Reducton L: 6-O-palmitoyl-L-ascorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
Triazine compound T: F-10 described in paragraph No. 0166 of JP-A-8-333325
Hydroxylamine compound H1: A-50 according to paragraph No. 0026 of JP-A-8-62767

Hydroxylamine compound H2: Dibenzylhydroxylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polyvalent amine A: N, N, N ′, N ″, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polyvalent amine B: Tetraethylenepentamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Amine C: Tri (n-octyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Kirest 3PA: manufactured by Kirest Co., Ltd. Kirest PH-540: manufactured by Kirest Co., Ltd. Adeka Stub PEP-36: manufactured by Asahi Denka Co., Ltd. IRGANOX 1010: manufactured by BASF HP-136: manufactured by BASF IRGANOX MD 1024: manufactured by BASF TINUVIN123: manufactured by BASF TINUVIN770: manufactured by BASF Adeka Stub LA-81: manufactured by Asahi Denka Co., Ltd. Naimine L-202, manufactured by NOF Corporation Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.

  Hydrophobizing agent 1: Polycondensate of phthalic acid / ethanediol (terminal is acetyl ester group and average molecular weight is 800)

  A polarizing plate was produced in the same manner as in Example 2 using the cellulose acylate films 501 to 521 produced as described above and the comparative cellulose acylate film c61.

In these polarizing plates, durability was evaluated in the same manner as in Example 2. As a result, polarizing plates using the cellulose acylate films 501 to 521 of the present invention were polarized using the comparative cellulose acylate film c61. With respect to the plate, the change in the orthogonal transmittance before and after aging was reduced, and the deterioration of the polarization performance was suppressed.
As a result, by using the polarizing plate of the present invention, a liquid crystal display device having excellent performance as described above can be produced.

DESCRIPTION OF SYMBOLS 1 Surface layer dope 2 Core layer (base layer) dope 3 Co-casting gissa 4 Casting support 21A, 21B Polarizing plate 22 Color filter substrate 23 Liquid crystal layer 24 Array substrate 25 Light guide plate 26 Light source 31a, 31b Cellulose acylate film (Polarizing plate protective film)
32 Polarizer

Claims (16)

A cellulose acylate film containing cellulose acylate and at least one compound represented by the following general formula (I).

[In General Formula (I), R ¹ , R ³ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. Represents a group or an aromatic group having 6 to 20 carbon atoms. The alkyl group, cycloalkyl group, alkenyl group and aromatic group may have a substituent. However, any one of R ¹ , R ³ and R ⁵ is an aralkyl group or a cycloalkyl group, and the total number of ring structures present in R ¹ , R ³ and R ⁵ is 3 or more. ] The cellulose acylate film according to claim 1, wherein, in the general formula (I), R ⁵ is an aralkyl group or a cycloalkyl group. The cellulose acylate film according to claim 1 or 2, wherein, in the general formula (I), R ¹ , R ³ and R ⁵ each have one or more ring structures. The cellulose acylate film according to claim ¹ , wherein, in the general formula (I), R ¹ , R ³ and R ⁵ each have one or more aromatic ring structures. The cellulose acylate film according to any one of claims 1 to 4, wherein in the general formula (I), all of the ring structures of R ¹ , R ^3, and R ⁵ are aromatic ring structures. The cellulose acylate film according to any one of claims 1 to 5, wherein the total acyl substitution degree (A) of the cellulose acylate satisfies the following formula.
1.5 ≦ A ≦ 3.0 The cellulose acylate film according to any one of claims 1 to 6, wherein an acyl group of the cellulose acylate is an acetyl group, and a total degree of acetyl substitution (B) satisfies the following formula.
2.0 ≦ B ≦ 3.0   The cellulose acylate film according to claim 7, wherein the total degree of acetyl substitution (B) is 2.5 or more and less than 2.97.   The cellulose acylate film according to any one of claims 1 to 8, comprising at least one polycondensed ester compound. The polycondensation ester compound is a compound obtained by polycondensation of at least one dicarboxylic acid represented by the following general formula (a) and at least one diol represented by the following general formula (b). The cellulose acylate film according to claim 9.

[In General Formula (a), X represents a divalent aliphatic group having 2 to 18 carbon atoms or a divalent aromatic group having 6 to 18 carbon atoms. In general formula (b), Z represents a divalent aliphatic group having 2 to 8 carbon atoms. ]   The cellulose acylate film according to claim 9 or 10, wherein the polycondensed ester compound has a number average molecular weight of 500 to 2,000.   The cellulose acylate film according to claim 9, wherein a terminal of the polycondensed ester compound is sealed.   The cellulose acylate film according to any one of claims 1 to 12, comprising at least one monosaccharide or a carbohydrate compound comprising 2 to 10 monosaccharide units.   The cellulose acylate film according to claim 13, wherein the carbohydrate compound has an alkyl group, an aryl group or an acyl group as a substituent.   A polarizing plate having at least the cellulose acylate film according to claim 1 and a polarizer.   A liquid crystal display device comprising at least the polarizing plate according to claim 15 and a liquid crystal cell.

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