JP2009298950A - Cellulose acylate film and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose acylate film having a large absolute value of Re, a small absolute value of Rth, and a low temperature dependency of retardation. <P>SOLUTION: The cellulose acylate film includes a composition comprising at least one cellulose acylate having an acyl group (substituent A) containing an aromatic group and having a substitution degree of the substituent A satisfying Expressions (I) and (II) below, and at least one ultraviolet absorbent, and is characterized by being stretched. Expression (I) is 0.30≤DSA2+DSA3-DSA6; and Expression (II) is 0.75≤DSA2+DSA3+DSA6, wherein DSA2, DSA3 and DSA6 represent the substitution degrees of the substituent A at the 2-, 3- and 6-positions of the cellulose acylate, respectively. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cellulose acylate film useful as an optical film for an image display device and the like, and its use, specifically, a retardation film, an antireflection film, a polarizing plate, and the like using the cellulose acylate film, and The present invention relates to an image display device.

In recent years, with the widespread use of liquid crystal display devices, demands for display performance and durability have increased, and response speeds have been improved, and a wider viewing angle such as contrast and color balance when viewed from an oblique direction with respect to the display image. It has become a problem to compensate with. In order to solve these problems, various liquid crystal modes have been developed, and accordingly, there is an urgent need to develop a retardation film as an optical compensation film for the purpose of compensating the viewing angle corresponding to each mode. .
For example, in a so-called in-plane switching (IPS) mode in which a lateral electric field is applied to a liquid crystal, in-plane retardation (Re) is 190 nm to 390 nm as one of means for improving the viewing angle of color tone and black display. An optical compensation film having a Nz (= Rth / Re + 0.5) value of 0.3 to 0.65 has been proposed (see Patent Document 1). Such a film, that is, a film having a large Re and a small Rth of about 0 is manufactured by, for example, bonding a heat-shrinkable film to a polymer film and subjecting it to heat stretching, and then peeling the heat-shrinkable film. (See Patent Documents 2 and 3). However, this method has problems such as consuming a large amount of heat-shrinkable film and a complicated manufacturing method.
Cellulose acylate films are widely used as polarizing plate protective films for liquid crystal display devices because of their transparency and toughness. For example, an optical film formed of cellulose substituted with an aromatic acyl group such as cellulose acetate benzoate has also been proposed (see Patent Documents 4 and 5). However, these films cannot provide optical characteristics that can contribute to optical compensation of an IPS liquid crystal display device or the like, an absolute value of Re, and an absolute value of Rth that is small and about zero. Recently, an optical film formed from cellulose acetate propionate has been proposed (see Patent Document 6). However, these films have a problem that the fluctuation of retardation due to humidity is large.
JP-A-11-305217 Japanese Patent Laid-Open No. 2000-23310 JP-A-5-157911 JP 2006-328298 A JP 2008-20857 A JP 2000-352620 A

  The present invention relates to a cellulose acylate film having a large absolute value of in-plane retardation (Re), a small absolute value of Rth, and low humidity dependency of retardation, and a retardation film and an antireflection film using the same. It is an object to provide a polarizing plate and an image display device.

Means for solving the above problems are as follows.
[1] At least one cellulose acylate having an acyl group containing an aromatic group (substituent A) and the degree of substitution of the substituent A satisfying the following formulas (I) and (II); A cellulose acylate film comprising a composition containing at least one absorbent and stretched:
Formula (I) 0.30 ≦ DSA2 + DSA3-DSA6
Formula (II) 0.75 ≦ DSA2 + DSA3 + DSA6
In the formula, DSA2, DSA3, and DSA6 represent the degree of substitution of the substituent A at the 2-position, 3-position, and 6-position of cellulose acylate, respectively.
[2] The cellulose acylate film of [1], wherein the cellulose acylate satisfies the following formula (III):
Formula (III) 2.5 ≦ DS ≦ 3.0
In formula (III), DS represents the total degree of substitution.

式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵はそれぞれ独立に水素原子又は一価の有機基を表し；Ｒ¹¹、Ｒ¹²及びＲ¹³の少なくとも１つは総炭素数４〜２０の分岐又は直鎖のアルキル基を表し；Ｒ¹¹、Ｒ¹²及びＲ¹³はそれぞれ互いに異なる。 [3] The cellulose acylate film of [1] or [2], wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (1):

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; at least one of R ¹¹ , R ¹² and R ¹³ has a total carbon number of 4 to Represents 20 branched or straight chain alkyl groups; R ¹¹ , R ¹² and R ¹³ are different from each other;

式中、Ｒ²¹は総炭素数１〜２０の分岐もしくは直鎖のアルキル基又はアリール基を表し；Ｒ²²及びＲ²³はそれぞれ独立に、水素原子又は総炭素数１〜２０の分岐もしくは直鎖のアルキル基を表し；Ｙ²は電子吸引基を表し；Ｙ²はＲ²¹と結合して環を形成してもよい。 [4] The cellulose acylate film of [1] or [2], wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (2):

In the formula, R ²¹ represents a branched or straight chain alkyl group or aryl group having 1 to 20 carbon atoms; R ²² and R ²³ each independently represents a hydrogen atom or a branched or straight chain having 1 to 20 carbon atoms. Y ² represents an electron-withdrawing group; Y ² may combine with R ²¹ to form a ring.

式中、Ｙ³は、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基又はフェニル基を表し、これらのアルキル基、アルケニル基及びフェニル基は置換基を有していてもよく；Ｒ³は、水素原子、アルキル基、アルケニル基、フェニル基、シクロアルキル基、アルキルカルボニル基、アルキルスルホニル基、又は−ＣＯ（ＮＨ）_n-1−Ｄ基を表し、Ｄはアルキル基、アルケニル基又は置換基を有していてもよいフェニル基を表し；ｍ及びｎはそれぞれ、１又は２を表す。 [5] The cellulose acylate film of [1] or [2], wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (3):

In the formula, Y ³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group or a phenyl group, and these alkyl group, alkenyl group and phenyl group may have a substituent; R ³ Represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group, or a substituent. Represents a phenyl group which may have a group; m and n each represent 1 or 2;

式中、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵及びＲ⁴⁶はそれぞれ独立して、水素原子又はＣＯＲを表し；Ｒは、総炭素数１〜２０の分岐もしくは直鎖のアルキル基、又は芳香族を含む基である。 [6] The cellulose acylate film of [1] or [2], wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (4):

In the formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents a hydrogen atom or COR; R represents a branched or straight chain alkyl group having 1 to 20 carbon atoms in total. Or a group containing an aromatic group.

[7] The cellulose acylate film according to any one of [1] to [6], wherein the cellulose acylate further has an aliphatic acyl group (substituent B).
[8] The cellulose acylate film of [7], wherein the substitution degree DSB of the substituent B satisfies the following formula (IV):
Formula (IV) 0.80 ≦ DSB ≦ 2.25.
[9] The cellulose acylate film of [7] or [8], wherein the substituent B is an aliphatic acyl group having 2 to 4 carbon atoms.
[10] The cellulose acylate film according to any one of [7] to [9], wherein the substituent B is an acetyl group.
[11] The cellulose acylate film of any one of [1] to [10], wherein the substituent A is a benzoyl group.
[12] The cellulose acylate film according to any one of [1] to [11], which is a retardation film.
[13] An antireflection film comprising the cellulose acylate film of any one of [1] to [12] and an antireflection layer.
[14] A polarizing plate having a polarizing film and the cellulose acylate film of any one of [1] to [13].
[15] An image display device having at least the cellulose acylate film of any one of [1] to [14].

According to the present invention, it is possible to provide a cellulose acylate film having a large absolute value of in-plane retardation (Re), a small absolute value of Rth, and a small humidity dependency of retardation.
The cellulose acylate film of the present invention is useful as various members of a liquid crystal display device, and provides a retardation film, an antireflection film, a polarizing plate, and an image display device for optical compensation of the liquid crystal display device. And
Cellulose acylate film with large in-plane retardation (Re) absolute value, small Rth absolute value, and low retardation humidity dependency

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
[Cellulose acylate film]
The cellulose acylate film of the present invention is a stretched film made of a composition containing at least one cellulose acylate having at least an acyl group containing an aromatic group (substituent A) and at least one ultraviolet absorber. .
-Cellulose acylate Cellulose has a free hydroxyl group at the 2nd, 3rd and 6th positions per β-1,4-linked glucose unit. In the present invention, when the substitution degrees at the 2-position, 3-position and 6-position of the substituent A in the cellulose acylate are DSA2, DSA3 and DSA6, respectively, in the present invention, the cellulose acylate satisfying the following formulas (I) and (II) Is used.
Formula (I) 0.30 ≦ DSA2 + DSA3-DSA6
Formula (II) 0.75 ≦ DSA2 + DSA3 + DSA6
As a result of intensive studies by the present inventors, an acyl group containing an aromatic group (substituent A) exists, and the degree of substitution at the 2-position, 3-position and 6-position of the substituent A is a film produced thereby. It has been found that the values of Re and Rth are greatly affected. More specifically, with respect to Rth, the substituent A present at the 2nd and 3rd positions has an effect of increasing Rth negatively, and the substituent A present at the 6th position functions to increase Rth positively. On the other hand, regarding Re, the substituent A existing at the 2-position, 3-position and 6-position has the effect of increasing its absolute value when stretched regardless of the position. I found it. However, if the stretching process is performed until the absolute value of Re is in the desired range, Rth becomes significantly higher due to the action of the substituent A present at the 2-position and 3-position, and the absolute value of Rth is reduced. It is difficult to obtain a stretched film having a large absolute value of Re while keeping it small. In the present invention, the composition containing an ultraviolet absorber together with cellulose acylate satisfying the above formulas (I) and (II) is formed into a film, and further subjected to a stretching treatment, whereby the absolute value of Rth is small and the Re This makes it possible to provide a cellulose acylate film having a large absolute value.

  As described above, when the value of (DSA2 + DSA3-DSA6) is in the above range, the Rth due to the substituent A existing at the 2nd and 3rd positions is negatively increased, and the Rth due to the substituent A present at the 6th position is A stretched film having a balance between the positively increasing function and a negative or small absolute value of Rth is obtained. (DSA2 + DSA3-DSA6) is naturally 2 or less, but from the viewpoint of ease of manufacture, (DSA2 + DSA3-DSA6) is preferably about 0.8 or less. On the other hand, as described above, when the value of (DSA2 + DSA3 + DSA6) is within the above range, a stretched film having a large absolute value of Re can be obtained by the action of the substituent A present at the 2-position, 3-position and 6-position. Of course, (DSA2 + DSA3 + DSA6) is 3 or less. From the viewpoint of film moldability, it is preferably substituted by a substituent B described later, and from that viewpoint, (DSA2 + DSA3 + DSA6) is preferably about 2 or less.

Depending on the application, adjusting each value within the above range, selecting an ultraviolet absorber, adjusting the draw ratio, or combining two or more of these, a stretched film with desired properties Can be obtained.
For example, in order to obtain a stretched film having a stretch ratio of about 30 to 90%, Rth of about −35 to 35 nm, and Re of about 150 to 350 nm, (DSA2 + DSA3−DSA6) is 0.3 to 0.8. Yes, (DSA2 + DSA3 + DSA6) is preferably a cellulose acylate of 0.75 to 1.5.

In addition, there may be a plurality of types of acyl groups including an aromatic group, and when there are a plurality of types, the degree of substitution is the total. From the viewpoint of synthesis, it is preferable that the acyl group containing an aromatic group is one kind.
In the present invention, the substitution degree and substitution degree distribution of the substituents are determined by ¹ H-NMR or ¹³ using the methods described in Cellulose Communication 6, 73-79 (1999) and Chirality 12 (9), 670-674. It can be determined by C-NMR.

Further, the total substitution degree DS by the acyl group in the cellulose acylate (not only the substitution degree by the substituent A but also the substitution degree by the substituent B described later) is the humidity dependence of retardation. Affects sex. From the viewpoint of reducing the humidity dependency of the retardation expressed by the stretching treatment, the total substitution degree DS with an acyl group is preferably as large as possible (the maximum value of the total substitution degree is 3). Specifically, the total substitution degree DS preferably satisfies the following formula (III).
Formula (III) 2.5 ≦ DS ≦ 3.0
The total substitution degree DS is more preferably 2.5 to 2.95, and more preferably 2.5 to 2.9.
The humidity dependence of Re, that is, ΔRe / Re is influenced not only by the value of DS but also by the value of (DSA2 + DSA3−DSA6). For example, even if the DS value satisfies the formula (III), it does not satisfy the value of (DSA2 + DSA3-DSA6), that is, (DSA2 + DSA3-DSA6) does not satisfy the above formula (I), When the value is small, the humidity dependency of the retardation becomes remarkable. This is because ΔRe is largely unaffected by the substitution position, but Re increases as the value of (DSA2 + DSA3−DSA6) increases, and as a result, ΔRe / Re decreases.

(Acyl group containing aromatic group (Substituent A))
In the present invention, the acyl group containing an aromatic group (substituent A) may be directly bonded to the ester bond or may be bonded via a linking group. Direct bonding is preferred. Here, the linking group represents an alkylene group, an alkenylene group, or an alkynylene group, and the linking group may have a substituent. As the linking group, preferably an alkylene group having 1 to 10 atoms, an alkenylene group, and an alkynylene group, more preferably an alkylene group having 1 to 6 atoms and an alkenylene group, and most preferably an alkylene and alkenylene group having 1 to 4 atoms. is there.

  The aromatic may have a substituent, and the substituent substituted by the aromatic and the substituent substituted by the above-described linking group may be, for example, an alkyl group (preferably having 1 to 20 carbon atoms, Preferably it is 1-12, particularly preferably 1-8, such as methyl, ethyl, propyl, isopropyl, tert-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group and the like), alkenyl group (preferably 2-20 carbon atoms, more preferably 2-12, particularly preferably 2-8, for example, vinyl group , An allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8, for example, a propargyl group, a 3-pentynyl group, etc., an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, For example, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned), an amino group (preferably 0-20 carbon atoms, more preferably 0-10, particularly preferably 0-6, for example, an amino group, a methylamino group. , A dimethylamino group, a diethylamino group, a dibenzylamino group, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as a methoxy group, Ethoxy group, butoxy group and the like), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms) Preferably they are 6-12, for example, a phenyloxy group, 2-naphthyloxy group etc. are mentioned, An acyl group (preferably 1-20 carbon atoms, More preferably, it is 1-16, Most preferably, it is 1-12. For example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, A methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as a phenyloxycarbonyl group). An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 1). 6, particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms). For example, an acetylamino group, a benzoylamino group, etc.), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonylamino Group), aryloxycarbonylamino group (preferably having 7 to 20, more preferably 7 to 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino group), Sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 In particular, the number is 1 to 12, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group), a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16, and particularly preferably 0 to 0). 12, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably 1-20 carbon atoms, more preferably 1-16, Particularly preferably 1 to 12, for example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly Preferably it is 1-12, for example methylthio group, ethyl Thio group, etc.), arylthio group (preferably 6-20 carbon atoms, more preferably 6-16, particularly preferably 6-12, such as phenylthio group), sulfonyl group (preferably The number of carbon atoms is 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a mesyl group and a tosyl group. A sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, for example, methanesulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1). -12, and examples thereof include a ureido group, a methylureido group, and a phenylureido group), and a phosphoric acid amide group (preferably Preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (For example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 carbon atom) -30, more preferably 1-12, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, Benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferred Is from 3 to 40 carbon atoms, more preferably 3 to 30, particularly preferably 3 to 24, e.g., a trimethylsilyl group, etc. triphenylsilyl group), and the like. These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

Aromatic is defined as an aromatic compound in the physics and chemistry dictionary (Iwanami Shoten) 4th edition, page 1208, and the aromatic group in the present invention may be an aromatic hydrocarbon group or an aromatic heterocyclic group, more preferably It is an aromatic hydrocarbon group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12, and most preferably 6 to 10. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a terphenyl group, and the like, and more preferably a phenyl group. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, and a biphenyl group are particularly preferable. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocycle include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline. , Isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, a pyridyl group, a triazinyl group, and a quinolyl group are particularly preferable.

  Preferred examples of the acyl group containing an aromatic group (substituent A) include phenylacetyl group, hydrocinnamoyl group, diphenylacetyl group, phenoxyacetyl group, benzyloxyacetyl group, O-acetylmandelyl group, and 3-methoxyphenylacetyl group. Group, 4-methoxyphenylacetyl group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, ortho -Toluoyl group, meta-toluoyl group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4- Butylbenzoyl group, 4-pentylbenzoy Group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzoyl group, 4-butoxybenzoyl group, 4-hexyloxybenzoyl group, 4-heptyloxy Benzoyl, 4-pentyloxybenzoyl, 4-octyloxybenzoyl, 4-nonyloxybenzoyl, 4-decyloxybenzoyl, 4-undecyloxybenzoyl, 4-dodecyloxybenzoyl, 4-isopropoxy Benzoyl group, 2,3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group 3,4,5-trimethoxybenzoyl group, 2, , 5-trimethoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, 2-biphenylcarbonyl group, 4-biphenylcarbonyl group, 4′-ethyl-4-biphenylcarbonyl group, 4′-octyloxy-4-biphenylcarbonyl Group, piperonylyl group, diphenylacetyl group, triphenylacetyl group, phenylpropionyl group, hydrocinnamoyl group, α-methylhydrocinnamoyl group, 2,2-diphenylpropionyl group, 3,3-diphenylpropionyl group, 3,3 , 3-triphenylpropionyl group, 2-phenylbutyryl group, 3-phenylbutyryl group, 4-phenylbutyryl group, 5-phenylvaleryl group, 3-methyl-2-phenylvaleryl group, 6-phenyl Hexanoyl group, α-methoxyphenylacetyl group, phenoxy Cetyl group, 3-phenoxypropionyl group, 2-phenoxypropionyl group, 11-phenoxydecanoyl group, 2-phenoxybutyryl group, 2-methoxyacetyl group, 3- (2-methoxyphenyl) propionyl group, 3- (p -Toluyl) propionyl group, (4-methylphenoxy) acetyl group, 4-isobutyl-α-methylphenylacetyl group, 4- (4-methoxyphenyl) butyryl group, (2,4-di-t-pentylphenoxy)- Acetyl group, 4- (2,4-di-t-pentylphenoxy) -butyryl group, (3,4-dimethoxyphenyl) acetyl group, 3,4- (methylenedioxy) phenylacetyl group, 3- (3 4-dimethoxyphenyl) propionyl group, 4- (3,4-dimethoxyphenyl) butyryl group, (2,5-dimethoxy) Enyl) acetyl group, (3,5-dimethoxyphenyl) acetyl group, 3,4,5-trimethoxyphenylacetyl group, 3- (3,4,5-trimethoxyphenyl) -propionyl group, acetyl group, 1- Naphthylacetyl group, 2-naphthylacetyl group, α-trityl-2-naphthalene-propionyl group, (1-naphthoxy) acetyl group, (2-naphthoxy) acetyl group, 6-methoxy-α-methyl-2-naphthaleneacetyl group 9-fluoreneacetyl group, 1-pyreneacetyl group, 1-pyrenebutyryl group, γ-oxo-pyrenebutyryl group, styreneacetyl group, α-methylcinnamoyl group, α-phenylcinnamoyl group, 2-methylcinnamoyl group, 2-methoxycinnamoyl group, 3-methoxycinnamoyl group, 2,3-dimethoxycinnamoyl group 2,4-dimethoxycinnamoyl group, 2,5-dimethoxycinnamoyl group, 3,4-dimethoxycinnamoyl group, 3,5-dimethoxycinnamoyl group, 3,4- (methylenedioxy) cinnamoyl group, 3 , 4,5-trimethoxycinnamoyl group, 2,4,5-trimethoxycinnamoyl group, 3-methylidene-2-carbonyl group, 4- (2-cyclohexyloxy) benzoyl group, 2,3-dimethylbenzoyl group 2,6-dimethylbenzoyl group, 2,4-dimethylbenzoyl group, 2,5-dimethylbenzoyl group, 3-methoxy-4-methylbenzoyl group, 3,4-diethoxybenzoyl group, α-phenyl-O— Toluyl group, 2-phenoxybenzoyl group, 2-benzoylbenzoyl group, 3-benzoylbenzoyl group, 4-benzoylbenzoy Group, 2-ethoxy-1-naphthoyl group, 9-fluorene group, 1-fluorene group, 4-fluorene group, 9-anthracene group, such as 1-pyrene carbonyl group.

  More preferably, the substituent A is phenylacetyl, hydrocinnamoyl, diphenylacetyl, phenoxyacetyl, benzyloxyacetyl, O-acetylmandelyl, 3-methoxyphenylacetyl, 4-methoxyphenylacetyl. Group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, ortho-toluoyl group, meta-toluoyl Group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4-butylbenzoyl group, 4-pentyl Benzoyl group, 4-hexylbenzo Group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzoyl group, 4-butoxybenzoyl group, 4-hexyloxybenzoyl group, 4-heptyloxybenzoyl group, 4- Pentyloxybenzoyl group, 4-octyloxybenzoyl group, 4-nonyloxybenzoyl group, 4-decyloxybenzoyl group, 4-undecyloxybenzoyl group, 4-dodecyloxybenzoyl group, 4-isopropyloxybenzoyl group, 2, 3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 2,4,4 5-trimethoxybenzoyl group, 3,4,5-trimethoxyben Yl group, a 1-naphthoyl group, 2-naphthoyl group, 2-biphenyl group, 4-biphenylcarbonyl group, or 4'-ethyl-4-biphenylcarbonyl group, 4'-octyloxy-4-biphenyl group.

  More preferably, the substituent A is a phenylacetyl group, a diphenylacetyl group, a phenoxyacetyl group, a cinnamoyl group, a 4-methoxy-cinnamoyl group, a benzoyl group, a phenylbenzoyl group, a 4-ethylbenzoyl group, a 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4-butylbenzoyl group, 4-pentylbenzoyl group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2, 4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 3,4,5-trimethoxybenzoyl group, 2,4,5-trimethoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, 2-biphenylcarbonyl Group, or 4-biphenylcarbonyl group.

More preferably, the substituent A is a benzoyl group, a phenylbenzoyl group, a 4-heptylbenzoyl group, a 2,4,5-trimethoxybenzoyl group, or a 3,4,5-trimethoxybenzoyl group.
The substituent A possessed by the cellulose acylate may be one kind or two or more kinds.

The cellulose acylate may further have an acyl group other than an acyl group containing an aromatic group (substituent A), specifically an aliphatic acyl group (substituent B).
(Aliphatic acyl group (substituent B)
In the present invention, the aliphatic acyl group (substituent B) may be any of linear, branched or cyclic aliphatic acyl groups and is an aliphatic acyl group containing an unsaturated bond. Also good. Preferably it is a C2-C20, More preferably, it is C2-C10, More preferably, it is a C2-C4 aliphatic acyl group. Preferable examples of the substituent B are an acetyl group, a propionyl group, and a butyryl group, and among them, an acetyl group is preferable. By using the substituent B as an acetyl group, a film having an appropriate glass transition point (Tg), elastic modulus and the like can be obtained. By having an aliphatic acyl group having a small number of carbon atoms, such as an acetyl group, an appropriate strength as a film can be obtained without lowering Tg, elastic modulus and the like.
The substitution degree DSB of the substituent B preferably satisfies the following formula (IV): Formula (IV) 0.80 ≦ DSB ≦ 2.25
DSB is preferably 1.0 to 2.25, more preferably 1.2 to 2.25. By setting it as the said range, the solubility of the diacetyl cellulose used as a raw material can be kept high, and a synthesis | combination becomes easy and it is preferable.

  Although the specific example of the cellulose acylate which can be used for this invention below is shown, it is not limited to the following examples.

The cellulose acylate is a compound having a cellulose skeleton obtained by introducing an acyl group (substituent A) containing at least an aromatic group biologically or chemically using cellulose as a raw material.
The raw material cotton of cellulose acylate has a low polymerization degree obtained by acid hydrolysis of wood pulp such as microcrystalline cellulose as well as natural cellulose such as cotton linter and wood pulp (hardwood pulp, conifer pulp). 300) Cellulose can also be used, and in some cases, it may be mixed and used. Detailed descriptions of these raw material celluloses can be found in, for example, “Plastic Materials Course (17) Fibrous Resin” (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970) and Invention Association Publication Technical Report 2001-1745 ( 7 to 8) and “Encyclopedia of Cellulose (page 523)” (edited by Cellulose Society, Asakura Shoten, published in 2000) can be used, and is not particularly limited.

    The cellulose acylate used in the present invention is, for example, a cellulose acetate manufactured by Daicel Corporation (acetyl substitution degree 2.19 (trade name: FL-70)), 1.76 (trade name: LL-10)) as a starting material. Can be obtained by reaction with the corresponding acid chloride. Usually, when cellulose acetate in which some hydroxyl groups are substituted with acetyl groups is used as a starting material and an acid chloride such as benzoyl chloride is reacted to introduce substituent A, it is preferentially introduced at the 6-position. In order to obtain cellulose acylate in which the substituent A is preferentially substituted at the 2-position and 3-position, the cellulose acetate is once deacetylated under basic conditions, and the 2-position and 3-position acetyl groups are preferentially treated. And then acylated with acid chloride, cellulose acylate having substituent A introduced preferentially at the 2-position and 3-position and acetyl group mainly at the 6-position as substituent B is obtained. . Deacetylation can proceed, for example, in the presence of an amine and water. By adjusting the acetyl substitution degree of the cellulose acetate as a starting material, the deacetylation conditions, and the introduction conditions of the substituent A, a cellulose acylate satisfying the above formulas (I) and (II) is produced. be able to.

  Although there is no restriction | limiting in particular about the viscosity average polymerization degree of the said cellulose acylate, 80-700 are preferable, 90-500 are still more preferable, 100-500 are still more preferable. By setting the average degree of polymerization to 500 or less, the viscosity of the cellulose acylate dope solution does not become too high, and the film production by casting tends to be easy. Moreover, it is preferable for the degree of polymerization to be 140 or more because the strength of the produced film tends to be further improved. The average degree of polymerization can be measured by the intrinsic viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, “Journal of the Textile Society”, Vol. 18, No. 1, pages 105-120, 1962). Specifically, it can be measured according to the method described in JP-A-9-95538.

-Ultraviolet absorber In this invention, at least 1 type of an ultraviolet absorber is used. The ultraviolet absorber preferably has at least one absorption maximum in a wavelength range of 250 nm or more, more preferably has at least one absorption maximum in a wavelength range of 250 nm to 360 nm, and in a wavelength range of 300 nm to 355 nm. More preferably, it has at least one absorption maximum. By doing in this way, the difference of the Rth value in each wavelength of 630nm, 550nm, and 450nm becomes large, and a tint change is suppressed.

  When forming a film, it may be exposed to heating (for example, in the case of a solution casting method, during dope casting, a drying step, a stretching step, etc.), the ultraviolet absorbent used in the present invention is difficult to volatilize. From this point of view, the molecular weight is preferably about 250 to 1,000. More preferably, it is about 260-800, More preferably, it is about 270-800, Most preferably, it is about 300-800. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.

The addition amount of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.1 to 10% by mass, and preferably 0.2 to 10% by mass with respect to cellulose acylate. It is particularly preferred.
Moreover, there is no restriction | limiting about the time which adds these ultraviolet absorbers. Taking the solution casting method as an example, it may be at any stage in the dope preparation process or at the end of the dope preparation process.

  Examples of the ultraviolet absorber that can be used in the present invention include compounds represented by the following formulas (1) to (4). These compounds are preferable in that they reduce only Rth and hardly change Re when added to cellulose acylate. However, it is not limited to these.

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; at least one of R ¹¹ , R ¹² and R ¹³ has a total carbon number of 4 to Represents 20 branched or straight chain alkyl groups; R ¹¹ , R ¹² and R ¹³ are different from each other;

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; at least one of R ¹¹ , R ¹² and R ¹³ has a total carbon number of 4 Represents a branched or straight chain alkyl group of ˜20; R ¹¹ , R ¹² and R ¹³ are different from each other;
Examples of the organic group include a group selected from the following substituent group G.
Substituent group G:
An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, For example, propargyl, 3-pentynyl, etc.), aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon number) -20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), substituted or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably carbon 0 to 10, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, and dibenzylamino).

An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like),
An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), an acyl group ( Preferably it has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl and the like, and an alkoxycarbonyl group (preferably carbon). 2 to 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 20 carbon atoms). More preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxy And acyloxy groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy). An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 carbon atoms). -20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, Phenyloxycarbonylamino, etc.), sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzene Sulfonylamino, etc.), a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfuryl). And carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as carbamoyl and methylcarbamoyl). , Diethylcarbamoyl, phenylcarbamoyl, etc. It is. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably carbon 6 to 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably carbon atoms). 1 to 16, particularly preferably 1 to 12 carbon atoms such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon atoms). 1 to 12, for example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 to 1 carbon atoms) 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, an imidazoli , Pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably Are those having 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.

Further, each of ^{R 11, R 12, R 13} , R 14 and R ¹⁵ may be the same or different, it may be linked to each other to form a ring, if possible, R ^11, R ¹² and At least one of R ¹³ represents an unsubstituted branched or straight chain alkyl group having a total carbon number of 4 to 20, and R ¹¹ , R ¹² and R ¹³ are different from each other.

R ¹¹ and R ¹³ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted or unsubstituted amino groups, alkoxy groups, aryloxy groups, hydroxy groups, and halogen atoms, more preferably hydrogen atoms. An atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group and a halogen atom, more preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms (preferably 4 to 12 carbon atoms).

R ¹² is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, or a halogen atom, more preferably a hydrogen atom or an alkyl group. Group, aryl group, alkyloxy group, aryloxy group and halogen atom, more preferably hydrogen atom and carbon 1-12 alkyl group, particularly preferably hydrogen atom and methyl group, most preferably hydrogen atom. is there.

R ¹⁴ and R ¹⁵ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted or unsubstituted amino groups, alkoxy groups, aryloxy groups, hydroxy groups, and halogen atoms, more preferably hydrogen atoms. An atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, and a halogen atom, more preferably a hydrogen atom and a halogen atom, and particularly preferably a hydrogen atom and a chlorine atom.

  Although the specific example of a compound represented by the said General formula (1) below is given, it is not limited to the following specific example.

  Next, the ultraviolet absorber represented by the following general formula (2) will be described in detail.

In the general formula (2), R ²¹ represents a branched or straight chain alkyl group or aryl group having 1 to 20 carbon atoms; R ²² and R ²³ each independently represent a hydrogen atom or 1 to 20 carbon atoms. Represents a branched or straight chain alkyl group; Y ² represents an electron withdrawing group. Y ² may combine with R ²¹ to form a ring.

The alkyl group represented by R ²¹ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 25 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). , Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group). May be branched.
The aryl group represented by R ²¹ is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (for example, phenyl group, p-tolyl group, p-chlorophenyl group, α-naphthyl group). Or β-naphthyl group).

The alkyl group represented by R ²² and R ²³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group). Hexyl group, heptyl group, octyl group, nonyl group, decyl group).
R ²² and R ²³ may be bonded to each other to form a ring. The ring is preferably a 5- to 8-membered ring (preferably a 5- to 6-membered ring), and examples thereof include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, and an isoindoline ring. It may be substituted with a group and may be condensed with another ring (for example, a benzene ring).

Examples of the electron withdrawing group represented by Y include an alkane or arylenesulfonyl group, an acyl group, an arylcarbonyl group, a cyano group, an alkoxycarbonyl group, and an aryloxycarbonyl group. When these groups are further described, preferably an arenesulfonyl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (for example, benzenesulfonyl group, p-toluenesulfonyl group, p-chlorobenzenesulfonyl group, naphthalenesulfonyl group): Preferably an acyl group having 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms (for example, formyl group, acetyl group, propionyl group); preferably aryl having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms A carbonyl group; a nitrile group; preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 9 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, a benzyloxycarbonyl group); preferably Is an ant having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. Le oxycarbonyl group (e.g., phenoxycarbonyl group, p- nitrophenoxy carbonyl group); and the like preferably. Among these, an arylenesulfonyl group having 6 to 15 carbon atoms is particularly preferable, and a benzenesulfonyl group is more preferable. These electron withdrawing groups may form a ring together with R ²¹ .

  Although the specific example of a compound represented by General formula (2) below is given, it is not limited to the following specific example.

  Next, the ultraviolet absorber represented by the general formula (3) will be described in detail.

In the formula, Y ³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a —CO (NH) _n−1 -D group, and D represents an alkyl group, an alkenyl group, or The phenyl group which may have a substituent is represented. m and n represent 1 or 2.

  In the formula (3), examples of the alkyl group include a linear or branched aliphatic group having 1 to 24 carbon atoms; examples of the alkoxy group include an alkoxy group having 1 to 18 carbon atoms. Examples of alkenyl groups include alkenyl groups having 1 to 16 carbon atoms, and more specifically, allyl groups, 2-butenyl groups, and the like. The alkyl group, alkenyl group, and phenyl group may be substituted. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), hydroxy group, phenyl group, (this phenyl Examples of the group include an alkyl group or a halogen atom which may be substituted.

  Although the specific example of a compound represented by the said General formula (3) is given to the following, it is not limited to the following specific example.

Next, the ultraviolet absorber represented by the general formula (4) will be described in detail.

In the formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are a hydrogen atom or COR, and R includes a branched or straight chain alkyl group having 1 to 20 carbon atoms in total, or an aromatic group. It is a group.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and more specifically, a methyl group, an ethyl group, a propyl group, or an isopropyl group. Tert-butyl group, iso-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group and the like. Most preferred is a methyl group.

  When R is a group containing an aromatic group, the aromatic group may be directly bonded to —CO or bonded via a linking group. Here, the linking group represents an alkylene group, an alkenylene group, or an alkynylene group, and the linking group may have a substituent. The linking group is preferably an alkylene group having 1 to 10 carbon atoms, an alkenylene group, and an alkynylene group, more preferably an alkylene group having 1 to 6 carbon atoms and an alkenylene group, more preferably 1 to 4 carbon atoms. Alkylene and alkenylene groups. In addition, the aromatic may have a substituent, and examples of the substituent substituted by the aromatic and the substituent substituted by the above-described linking group include a substituent selected from the above-described substituent group G. Is included.

  The aromatic is defined as an aromatic compound in the Physical and Chemical Dictionary (Iwanami Shoten) 4th edition, page 1208, and may be an aromatic hydrocarbon group or an aromatic heterocyclic group, more preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12, and most preferably 6 to 10. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a terphenyl group. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, and a biphenyl group are particularly preferable. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocycle include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline. , Isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, a pyridyl group, a triazinyl group, and a quinolyl group are particularly preferable.

  Although the specific example of a compound represented by the said General formula (4) is given to the following, it is not limited to the following specific example.

  The ultraviolet absorber used in the present invention is not limited to the compounds of the above general formulas (1) to (4), and various compounds can be used. On the other hand, in some UV absorbers, even if a stretched film is produced using cellulose acylate satisfying the above formulas (I) and (II), the resulting stretched film is compared with the additive-free Rth. Some agents do not decrease and remain negatively large. For example, trityl alcohol is an example, because the cellulose acylate is not oriented in the plane enough to cancel out the negative Rth caused by the orientation of the side chain in the film thickness direction, or cellulose acylate. This is presumably because the side chains of the rate do not sufficiently inhibit the orientation in the film thickness direction. A film produced using an ultraviolet absorber having the above characteristics becomes a stretched film having a large negative Rth (for example, absolute value of 100 nm or more) and a large Re. The use of the agent will be limited.

The cellulose acylate film of the present invention is prepared from a composition containing at least one cellulose acylate and at least one ultraviolet absorber (hereinafter sometimes referred to as “cellulose acylate composition”). Can do.
The cellulose acylate is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more of the entire composition.
Moreover, it is preferable that the said ultraviolet absorber contains 1 mass%-30 mass% of the whole composition, More preferably, 3 mass%-30 mass% are contained, More preferably, 3 mass%-20 mass% are contained.

  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 is more preferred. Both the melt film forming method and the solution film forming method can produce the cellulose acylate film of the present invention in the same manner as a generally performed method. For example, referring to Japanese Patent Application Laid-Open No. 2006-348123 for melt film formation, and Japanese Patent Application Laid-Open No. 2006-241433 for solution film formation.

An example of a method for producing the cellulose acylate film of the present invention by a solution casting method will be described.
In the solution casting method, a cellulose acylate solution (dope) is prepared, and the solution is cast on the surface of a support to form a film. The solvent used for the preparation of the cellulose acylate solution is not particularly limited. Preferred solvents include chlorinated organic solvents such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethylene, and non-chlorinated organic solvents. The non-chlorine organic solvent is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  When preparing the cellulose acylate solution, it is preferable to dissolve the cellulose acylate in an organic solvent in an amount of 10 to 35% by mass. More preferably, it is 13-30 mass%, Most preferably, it is 15-28 mass%. The cellulose acylate solution having such a concentration may be prepared so as to have a predetermined concentration when cellulose acylate is dissolved in a solvent, or a low concentration solution (for example, 9 to 14% by mass) is prepared in advance. After the preparation, a solution having the above concentration may be prepared by a concentration step. Furthermore, after preparing a high-concentration cellulose acylate solution in advance, various cellulose acylate solutions may be prepared by adding various additives.

  Regarding the preparation of the cellulose acylate solution (dope), the dissolution method is not particularly limited, and may be room temperature, or may be carried out by a cooling dissolution method or a high temperature dissolution method, or a combination thereof. Regarding these, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950, JP 2000-53784, JP 11-322946, JP 11-322947, JP 2-276830, JP 2000-273239, JP 11-71463, JP 04-259511, JP The preparation methods of cellulose acylate solutions are described in each publication such as 2000-273184, JP-A-11-323017, and JP-A-11-302388, and these techniques can also be used in the present invention. . The details of these methods, particularly the preparation method using a non-chlorinated solvent-based solvent, are disclosed in JIII Journal of Technical Disclosure (Public Technical No. 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation), pages 22-25. Are described in detail. Furthermore, in the process of preparation of the cellulose acylate solution, treatment such as solution concentration and filtration may be performed, and these are similarly disclosed in the technical report of the Japan Society of Invention (Publication No. 2001-1745, March 15, 2001). It is described in detail on page 25. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

  As a method and equipment for producing the cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose acylate film can be used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for silver halide photographic light-sensitive materials and functional protective films for electronic displays, in addition to the solution casting film forming apparatus, an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. In many cases, a coating device is added to the surface processing of the film. Each of these manufacturing processes is described in detail on pages 25 to 30 of the Japan Society of Invention Public Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). Including), metal support, drying, peeling, stretching, etc.

In the present invention, the film produced by the melt film forming method or the solution film forming method is further subjected to a stretching treatment.
Stretching may be performed on-line during the film forming process, or may be performed off-line after winding up once after film formation is completed. That is, in the case of melt film formation, the stretching may be performed without completion of cooling during film formation, or may be performed after completion of cooling.
The stretching is preferably performed at Tg to (Tg + 50 ° C.), more preferably (Tg) to (Tg + 40 ° C.), and particularly preferably (Tg) to (Tg + 30 ° C.). A preferable draw ratio is 0.1% to 300%, more preferably 10% to 200%, and particularly preferably 30% to 100%. These stretching operations may be performed in one stage or in multiple stages. The draw ratio here is determined using the following equation.
Stretch ratio (%) = 100 × {(Length after stretching) − (Length before stretching)} / Length before stretching

Such stretching is performed by longitudinal stretching, lateral stretching, and combinations thereof. Longitudinal stretching includes (1) roll stretching (using two or more pairs of nip rolls with increased peripheral speed on the exit side, stretching in the longitudinal direction, also referred to as free end stretching), and (2) fixed end stretching (both ends of the film Gripping, conveying this gradually in the longitudinal direction and stretching in the longitudinal direction), etc. can be used. Further, for the transverse stretching, tenter stretching (stretching by stretching both sides of the film with a chuck and stretching it in the transverse direction (perpendicular to the longitudinal direction)) can be used. These longitudinal stretching and lateral stretching may be performed alone (uniaxial stretching) or in combination (biaxial stretching). In the case of biaxial stretching, it may be carried out in the longitudinal and transverse sequential manners (sequential stretching) or simultaneously (simultaneous stretching).
The stretching speed of longitudinal stretching and lateral stretching is preferably 10% / min to 10000% / min, more preferably 20% / min to 1000% / min, particularly preferably 30% / min to 800% / min. In the case of multistage stretching, the average value of the stretching speed of each stage is indicated.

Following such stretching, it is also preferable to relax by 0% to 10% in the longitudinal or lateral direction. Furthermore, it is also preferable to heat-fix at 150-250 degreeC for 1 second-3 minutes following extending | stretching.
The film thickness after stretching in this manner is preferably 10 to 300 μm, more preferably 20 μm to 200 μm, and particularly preferably 30 μm to 100 μm.

  The angle θ formed by the film forming direction (longitudinal direction) and the slow axis of Re of the film is preferably closer to 0 °, + 90 °, or −90 °. That is, in the case of longitudinal stretching, the closer to 0 °, the better, preferably 0 ± 3 °, more preferably 0 ± 2 °, and particularly preferably 0 ± 1 °. In the case of transverse stretching, 90 ± 3 ° or −90 ± 3 ° is preferable, 90 ± 2 ° or −90 ± 2 ° is more preferable, and 90 ± 1 ° or −90 ± 1 ° is particularly preferable.

When Re occurs due to the tension applied in the longitudinal direction of the film between casting and peeling, Re can be brought close to 0 by stretching in the width direction with a tenter. In this case, a preferable draw ratio is 0.1% to 20%, more preferably 0.5% to 10%, and particularly preferably 1% to 5%.
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 containing a residual solvent, and the stretching can be preferably performed at a residual solvent amount of 2 to 30% by mass.

  The thickness of the cellulose acylate film obtained after drying varies depending on the purpose of use, is preferably in the range of 5 to 500 μm, more preferably in the range of 20 to 300 μm, and in the range of 30 to 150 μm. Is more preferable. 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 cellulose acylate film of the present invention may be formed into a long shape. For example, the width is 0.5 to 3 m (preferably 0.6 to 2.5 m, more preferably 0.8 to 2.2 m), and the length is 100 to 10,000 m per roll (preferably 500 to 7000 m, more preferably 1000). ˜6000 m), and can be produced as a long film. 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.

  The above-mentioned stretched cellulose acylate film may be used alone, or may be used in combination with a polarizing plate, and a liquid crystal layer, a layer with a controlled refractive index (low reflection layer) or a hard coat on them. A layer may be provided and used.

[Optical properties of cellulose acylate film]
In the present specification, Re (λ) and Rth (λ) represent in-plane retardation (nm) and retardation in the thickness direction (nm) at wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light of wavelength λ nm is incident from each of the inclined directions in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (11) and (12).

Note:
In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents a film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.

Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Examples include polystyrene (1.59).
By inputting the assumed value of the average refractive index and the film thickness, nx, ny, and nz can be calculated by KOBRA 21ADH.

なお、上記式中、Ｒｅ１０％（５９０）及びＲｅ８０％（５９０）はそれぞれ、２５℃１０％ＲＨにおける波長５９０ｎｍの光に対するＲｅ及び２５℃８０％ＲＨにおける波長５９０ｎｍの光に対するＲｅである。ΔＲｅ／Ｒｅが小さいほど、Ｒｅの湿度依存性が小さいと言える。上記範囲程度のΔＲｅ／Ｒｅであれば、通常の環境湿度によっては、例えば画像表示装置の部材として利用した場合に、その表示特性に影響を与えるほどのＲｅの変動はほとんどないと言えるであろう。 Re and Rth of the cellulose acylate film of the present invention can be adjusted by the substitution degree distributions at the 2-position, 3-position and 6-position of the substituent A, the draw ratio, and the type of ultraviolet absorber used together. In the present invention, since the substitution degree of the substituent A includes cellulose acylate satisfying the above formulas (I) and (II), and an ultraviolet absorber, the absolute value of Re is increased by performing the stretching treatment. , Rth can be reduced in absolute value. Specifically, in the cellulose acylate film of the present invention, Re is about 120 to 400 nm, Rth is about −40 to 30 nm, and Nz value is about 0.5 (specifically, 0.25 to 0.65). It can become the film which shows the characteristic of. However, the optical properties of the cellulose acylate film of the present invention are not limited to this range.
In addition, since the cellulose acylate film of the present invention uses the cellulose acylate satisfying the above formulas (I) and (II) and the ultraviolet absorber, it satisfies the above optical characteristics and has a low humidity dependency of Re. Become a film. Specifically, ΔRe / Re, which is an index of the humidity dependency of Re calculated by the following equation, can be about 0.01 to 0.13.

In the above formula, Re 10% (590) and Re 80% (590) are Re for light having a wavelength of 590 nm at 25 ° C. and 10% RH, and Re for light having a wavelength of 590 nm at 25 ° C. and 80% RH, respectively. It can be said that the smaller the ΔRe / Re, the smaller the humidity dependency of Re. If ΔRe / Re is in the above range, it can be said that there is almost no fluctuation in Re that affects the display characteristics when used as a member of an image display device, depending on normal environmental humidity. .

  Further, the variation in the Re (590) value in the width direction of the film is preferably ± 5 nm, and more preferably ± 3 nm. Further, the variation in the Rth (590) value in the width direction is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in the Re value and the Rth value in the length direction is also within the range of the variation in the width direction.

  An example of the film formed by stretching the cellulose acylate film of the present invention is a film having an in-plane slow axis in a direction perpendicular to the stretching direction. The direction of the in-plane slow axis after stretching is affected by the values of DS of cellulose acylate and DSA2 + DSA3-DSA6 used for the production of the cellulose acylate film. Specifically, the DS of cellulose acylate is high. When DSA2 + DSA3-DSA6 is large (that is, DSA6 is small), when the produced cellulose acylate film is stretched, the in-plane slow axis of the stretched film tends to be perpendicular to the stretching direction. Therefore, when the cellulose acylate film of the present invention is stretched, the in-plane slow axis of the stretched film will be in a direction perpendicular to the stretching direction. However, it is not limited to this aspect. The direction of the slow axis in the plane of the film can be detected by KOBRA 21ADH.

Equilibrium moisture content:
The moisture content was measured by the Karl Fischer method using a cellulose acylate film sample of 7 mm × 35 mm of the present invention with a moisture meter and a sample drying apparatus (Aqua Counter AQ-200, LE-20S, both Hiranuma Sangyo Co., Ltd.). taking measurement. It is calculated by dividing the amount of water (g) by the sample mass (g).

  The equilibrium water content of the cellulose acylate film of the present invention is preferably 0 to 10% at 25 ° C. and 80% RH. It is more preferably 0.1 to 7%, and particularly preferably 0.3 to 5%. An equilibrium water content of 10% or more is not preferable because the dependence of retardation on humidity changes is great when used as a support for an optical compensation film, and the optical compensation performance decreases.

Hayes:
The cellulose acylate film of the present invention preferably has a value measured using, for example, a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) of 0.1 to 0.8. It is more preferably 1 or more and 0.7 or less, and particularly preferably 0.1 or more and 0.60 or less. By controlling the haze within the above range, a high-contrast image can be obtained when incorporated in a liquid crystal display device as an optical compensation film.

Photoelastic coefficient:
The cellulose acylate film of the present invention is preferably used as a polarizing plate protective film or a retardation plate. When used as a polarizing plate protective film or a retardation plate, the birefringence (Re, Rth) may change due to the stress due to expansion and contraction due to moisture absorption. The change in birefringence due to such stress can be measured as a photoelastic coefficient, and the range is preferably 5 × 10 ⁻⁷ (cm ² / kgf) to 30 × 10 ⁻⁷ (cm ² / kgf), and 6 × 10 ⁻⁷ (cm ² / kgf) to 25 × 10 ⁻⁷ (cm ² / kgf) is more preferable, and 7 × 10 ⁻⁷ (cm ² / kgf) to 20 × 10 ⁻⁷ (cm ² / kgf) It is particularly preferred.

Glass-transition temperature:
The glass transition temperature of the cellulose acylate film can be measured by the method described in JIS standard K7121. In this specification, the glass transition temperature (Tg) represents a value measured by the method described in JIS standard K7121.
The glass transition temperature of the cellulose acylate film of the present invention is preferably from 80 ° C. to 300 ° C., more preferably from 100 ° C. to 250 ° C. The glass transition temperature can be lowered by including a low molecular compound such as a plasticizer or a solvent.

surface treatment:
The cellulose acylate film that has not been stretched or has been stretched is optionally subjected to surface treatment to achieve improved adhesion between the cellulose acylate film and each functional layer (for example, the undercoat layer and the back layer). Can do. For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used.

[Phase difference film]
The cellulose acylate film of the present invention can be used as a retardation film.
In addition, the cellulose acylate film of the present invention has a functional layer described in detail on pages 32 to 45 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). Are preferably combined. Among these, application of a polarizing film (formation of a polarizing plate), application of an optical compensation layer made of a liquid crystal composition (optical compensation film), and application of an antireflection layer (antireflection film) are preferred.
[Optical compensation film]
The cellulose acylate film of the present invention can be used for optical compensation of a liquid crystal display device. When the cellulose acylate film of the present invention satisfies the optical properties necessary for optical compensation, it can be used as it is as an optical compensation film. Further, in order to satisfy the optical characteristics necessary for optical compensation, one or more other layers, for example, an optically anisotropic layer formed by curing a liquid crystal composition, or a layer made of another birefringent polymer film, After being laminated, it can also be used as an optical compensation film.

[Antireflection film]
The present invention also relates to an antireflection film having the cellulose acylate film of the present invention and an antireflection layer. The antireflection film can be manufactured based on a normal manufacturing method, and can be manufactured by referring to, for example, JP-A-2006-241433.

[Polarizer]
The present invention also relates to a polarizing plate comprising a polarizing film and two protective films sandwiching the polarizing film, wherein at least one of the two protective films is a cellulose acylate film of the present invention. Related. The cellulose acylate film may be bonded to a polarizing film as a part of an optical compensation film having an optically anisotropic layer and as a part of an antireflection film having an antireflection layer. Also when it has another layer, it is preferable that the surface of the cellulose acylate film of the present invention is bonded to the surface of the polarizing film. For example, it can manufacture with reference to Unexamined-Japanese-Patent No. 2006-241433.

[Image display device]
The present invention also relates to an image display device including at least one cellulose acylate film of the present invention. The cellulose acylate film of the present invention is used in a display device as a retardation film or an optical compensation film, or as a part of a polarizing plate, an optical compensation film, an antireflection film, or the like.

<Liquid crystal display device>
The cellulose acylate film of the present invention can be incorporated into a liquid crystal display device as a retardation film, or as a polarizing plate, an optical compensation film or an antireflection film using the cellulose acylate film. Examples of the liquid crystal display device include TN type, IPS type, FLC type, AFLC type, OCB type, STN type, ECB type, VA type and HAN type display devices, preferably IPS type. In addition, the cellulose acylate film of the present invention can be used for any of transmissive, reflective, and transflective liquid crystal display devices.

  When the cellulose acylate film of the present invention is used in an IPS mode liquid crystal display device, it is preferable to dispose one sheet between the liquid crystal cell and the display surface side polarizing plate or the backlight side polarizing plate. Further, it may function as a protective film for the display surface side polarizing plate or the backlight side polarizing plate, and may be incorporated in a liquid crystal display device as one member of the polarizing plate and disposed between the liquid crystal cell and the polarizing film. By disposing one cellulose acylate film of the present invention at the above position, the display characteristics of an IPS mode liquid crystal display device can be improved, and in particular, the color shift can be reduced in an oblique direction during black display. In the embodiment used for optical compensation of the IPS mode liquid crystal display device, the Rth of the cellulose acylate film of the present invention is preferably −40 nm to 30 nm, and Re is preferably 120 nm to 400 nm. The Nz value is preferably about 0.5, and specifically, the Nz value is preferably 0.25 to 0.65. In this embodiment, the cellulose acylate film of the present invention is preferably disposed with its in-plane slow axis parallel or perpendicular to the absorption axis of the display surface side polarizing film (or backlight side polarizing film).

  In this aspect, it is preferable that no retardation layer other than the cellulose acylate film exists between the display surface side polarizing film and the backlight side polarizing film and the liquid crystal cell. Therefore, for example, the display surface side polarizing plate or the backlight side polarizing plate has a protective film for a polarizing film other than the cellulose acylate film, and the protective film includes the liquid crystal cell and the display surface side polarizing film or the backlight side. When the protective film is disposed between the polarizing film and the protective film, it is preferable to use an isotropic polymer film in which both Re and Rth are almost zero. A cellulose acylate film described in, for example, 2006-030937 is preferably used.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Synthesis Example 1: Synthesis of Exemplary Compound A-1)
100 g of acetylcellulose having a substitution degree of 1.76 and 1000 mL of pyridine were weighed into a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel and stirred at room temperature. To this, 60 mL of benzoyl chloride was slowly added dropwise, and after the addition, the mixture was further stirred at 60 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, and the reaction solution was poured into 10 L of methanol with vigorous stirring, whereby a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of methanol three times. The obtained white solid was dried at 60 ° C. overnight and then vacuum-dried at 90 ° C. for 6 hours to obtain 115 g of the objective exemplified compound A-1 as a white powder. The average degree of polymerization was 119.

(Synthesis Example 2: Synthesis of Comparative Compound B-1)
109 g of the target B-1 was obtained as a white powder in the same manner as in the production of the exemplified compound A-1, except that 60 mL of benzoyl chloride was changed to 40 mL. The average degree of polymerization was 110.

(Synthesis Example 3: Synthesis of Comparative Compound B-2)
The compound was synthesized by the method described in JP-A-2006-328298. In a 5 L three-necked flask equipped with a mechanical stirrer, 100 g of cellulose and 100 mL of water were weighed and stirred overnight, and the water was filtered under reduced pressure. 400 mL of methanol (Wako Pure Chemical Industries, Ltd.) was added to the resulting slurry, and the mixture was stirred at room temperature for 1 hour and then filtered under reduced pressure twice. Furthermore, 400 mL of dimethylacetamide (Wako Pure Chemical Industries, Ltd.) was added to the resulting slurry, and the mixture was stirred at room temperature for 1 hour and filtered under reduced pressure three times to obtain activated cellulose. In a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 1000 mL of dimethylacetamide and lithium chloride (Wako Pure Chemical Industries) were weighed and dissolved at 80 ° C. After cooling to 40 ° C., activated cellulose was added and stirred for 1 hour. Cooled to room temperature, 93 g of acetic acid (Wako Pure Chemical), 38 g of benzoic acid (Wako Pure Chemical), 380 g of dicyclohexylcarbodiimide (Wako Pure Chemical), 130 g of 4-dimethylaminopyridine (Wako Pure Chemical), dimethylaminopyridium p -130 g of toluene sulfonate (Tokyo Kasei) was added and stirred for 24 hours. After the reaction, the mixture was allowed to cool to room temperature, and the reaction solution was poured into 5 L of water with vigorous stirring, whereby a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of methanol three times. The obtained white solid was dried at 60 ° C. overnight and then vacuum dried at 90 ° C. for 6 hours to obtain 90 g of the intended comparative compound B-2 as a white powder. The average degree of polymerization was 250.

[Example 1: Production of cellulose acylate film]
Cellulose acylate films shown in the following table were prepared by the following methods.
As the UV absorber, UV1-1, UV2-1, UV3-5, or UV4-1 and trityl alcohol were used, respectively.
1) Preparation of Cellulose Acylate Solution The following raw materials were put into a mixing tank, stirred while heating and dissolved to prepare a solution having a cellulose acylate solution.
Cellulose acylate (described in the following table) 85 parts by mass UV absorber (described in the following table) 15 parts by mass Methylene chloride 400 parts by mass

2) Preparation of Cellulose Acylate Film Sample A film obtained by casting 500 parts by mass of a cellulose acylate solution composition using a band casting machine at a glass transition temperature + 30 ° C. at a draw ratio shown in the following table. Each of the cellulose acylate films shown in the following table was produced by uniaxial stretching at the fixed end. Hereinafter, all the thicknesses of the produced films are 80 μm unless otherwise specified.

3) Evaluation of cellulose acylate film sample For evaluation of the film sample, a part (120 mm × 120 mm) of each film sample obtained above was prepared, and the retardation value was “KOBRA 21ADH” (Oji Scientific Instruments ( Re and Rth with respect to light having a wavelength of 550 nm were measured. The results are shown in the table below.

From the results shown in the above table, the cellulose acylate films (SA-1 to 4) of the examples of the present invention have a large absolute value of Re, a small absolute value of Rth, and humidity dependency of Re (ΔRe / It can be seen that Re) is small.
DSA2 + DSA3 + DSA6 value is within the scope of the present invention, but DSA2 + DSA3-DSA6 is outside the scope of the present invention, that is, the film of the comparative example (SB) prepared using cellulose acylate that does not satisfy the formula (I). -1) was highly dependent on the humidity of the retardation.
DSA2 + DSA3-DSA6 and DSA2 + DSA3 + DSA6 values are outside the scope of the present invention, that is, the comparative film (SB-2) produced using cellulose acylate does not satisfy the above formulas (I) and (II). The absolute value of Rth was large, and the humidity dependency of retardation was increased.
Moreover, the absolute value of Re was small in the film (SB-3) of the comparative example which has not performed the extending | stretching process.
The comparative film (SB-4) containing no ultraviolet absorber had a large absolute value of Rth.

[Reference example]
A film (SC-1) was produced in the same manner as the film (SA-1) of Example except that the ultraviolet absorber UV1-1 was replaced with trityl alcohol.
The Rth of this film (SC-1) was -136 nm, and Re was 261 nm. That is, it has been found that when trityl alcohol is used as an ultraviolet absorber, an effect of reducing Rth is hardly obtained as compared with an additive-free one.
Further, ΔRe / Re was 0.1, and the humidity dependency of Re was more significant than in the above examples, and was also more significant than that of the additive-free one.

[Example 2: Production of IPS mode liquid crystal display device]
1) Saponification of film SA-1, SA-2, SA-3 and SB-2, SB-3, SB-4 films prepared in Examples and Comparative Examples, Fujitac TF80UL (manufactured by FUJIFILM Corporation: (Tack A ”) was immersed in a 1.5 mol / L aqueous sodium hydroxide solution (saponification solution) adjusted to 55 ° C. for 2 minutes, and then the film was washed with water, and then added to a 0.05 mol / L sulfuric acid aqueous solution. After soaking for 2 seconds, it was further passed through a washing bath. Then, draining with an air knife was repeated three times, and after dropping the water, the film was retained in a drying zone at 70 ° C. for 15 seconds and dried to produce a saponified film.

2) Production of Polarizing Film According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, a circumferential speed difference was given between two pairs of nip rolls, and the film was stretched in the longitudinal direction to produce a polarizing film having a thickness of 20 μm.

3) Bonding One of SA-1 to SA-3 and SB-2 to SB-4 saponified on one side of the polarizing film thus obtained, and tack A on the other side, respectively. The saponified surface was placed on the polarizing film side, the polarizing film was sandwiched, and a 3% aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) was bonded as an adhesive to prepare polarizing plates.

4) Mounting evaluation to IPS mode liquid crystal display device The polarizing plate produced using SA-1, SA-2, and SA-3 of each example was used as an IPS liquid crystal display device (37-inch high-definition liquid crystal television monitor ( 37Z2000), manufactured by Toshiba Corp.), the liquid crystal cell side was incorporated instead of the visual side polarizing plate, and the visibility was confirmed. It was confirmed that by using these polarizing plates, sufficient viewing angle compensation was achieved and good visibility could be secured.
On the other hand, it was incorporated into an IPS mode liquid crystal display device in the same manner as above except that it was replaced with a polarizing plate prepared using SB-2, SB-3, and SB-4 of Comparative Examples, and the visibility was confirmed. . Even when these polarizing plates were used, viewing angle compensation was insufficient, and light leakage was particularly observed when viewed from an oblique direction.

Claims (15)

At least one cellulose acylate having an acyl group containing an aromatic group (substituent A) and the degree of substitution of the substituent A satisfying the following formulas (I) and (II); and an ultraviolet absorber A cellulose acylate film comprising a composition containing at least one kind and stretched:
Formula (I) 0.30 ≦ DSA2 + DSA3-DSA6
Formula (II) 0.75 ≦ DSA2 + DSA3 + DSA6
In the formula, DSA2, DSA3, and DSA6 represent the degree of substitution of the substituent A at the 2-position, 3-position, and 6-position of cellulose acylate, respectively. The cellulose acylate film according to claim 1, wherein the cellulose acylate satisfies the following formula (III):
Formula (III) 2.5 ≦ DS ≦ 3.0
In formula (III), DS represents the total degree of substitution. The cellulose acylate film according to claim 1 or 2, wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (1):

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; at least one of R ¹¹ , R ¹² and R ¹³ has a total carbon number of 4 to Represents 20 branched or straight chain alkyl groups; R ¹¹ , R ¹² and R ¹³ are different from each other; The cellulose acylate film according to claim 1 or 2, wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (2):

In the formula, R ²¹ represents a branched or straight chain alkyl group or aryl group having 1 to 20 carbon atoms; R ²² and R ²³ each independently represents a hydrogen atom or a branched or straight chain having 1 to 20 carbon atoms. Y ² represents an electron withdrawing group; Y ² may combine with R ²¹ to form a ring. The cellulose acylate film according to claim 1 or 2, wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (3):

In the formula, Y ³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group or a phenyl group, and these alkyl group, alkenyl group and phenyl group may have a substituent; R ³ Represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group, or a substituent. Represents a phenyl group which may have a group; m and n each represent 1 or 2; The cellulose acylate film according to claim 1 or 2, wherein at least one of the ultraviolet absorbers is a compound represented by the following general formula (4):

In the formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents a hydrogen atom or COR; R represents a branched or straight chain alkyl group having 1 to 20 carbon atoms in total. Or a group containing an aromatic group. The cellulose acylate film according to any one of claims 1 to 6, wherein the cellulose acylate further has an aliphatic acyl group (substituent B). The cellulose acylate film according to claim 7, wherein the substitution degree DSB of the substituent B satisfies the following formula (IV):
Formula (IV) 0.80 ≦ DSB ≦ 2.25. The cellulose acylate film according to claim 7 or 8, wherein the substituent B is an aliphatic acyl group having 2 to 4 carbon atoms. The cellulose acylate film according to any one of claims 7 to 9, wherein the substituent B is an acetyl group. The cellulose acylate film according to claim 1, wherein the substituent A is a benzoyl group. It is a phase difference film, The cellulose acylate film of any one of Claims 1-11 characterized by the above-mentioned. An antireflection film comprising the cellulose acylate film according to claim 1 and an antireflection layer. The polarizing plate which has a polarizing film and the cellulose acylate film of any one of Claims 1-13. The image display apparatus which has at least the cellulose acylate film of any one of Claims 1-14.