JP2014218611A - Cellulose-based resin composition and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cellulose-based resin composition having excellent optical properties, and a film formed from the resin composition.SOLUTION: A cellulose-based resin composition is prepared by blending (A) 100 pts.mass of a cellulose-based resin with: (B) 1-30 pts.mass of one or more selected from the group consisting of the following polyester compounds except cellulose ester, i.e., (b-1) polyester compounds comprising polyhydric alcohol and polycarboxylic acid, (b-2) polyester compounds comprising polyhydric alcohol and monocarboxylic acid, and (b-3) polyester compounds comprising polycarboxylic acid and monoalcohol; and (C) 0.1-30 pts.mass of a β-diketone compound.

Description

  The present invention relates to a cellulose resin composition having excellent optical properties and a film formed by molding the resin composition.

  In recent years, resin films such as cellulose acylate, polycarbonate, polyacrylate, and polyolefin have been mainly used for optical compensation films for liquid crystal display devices. Among them, cellulose acylate films are widely used because they are excellent in bonding properties to polyvinyl alcohol used for polarizers, have high transparency, and have appropriate strength.

  However, the cellulose acylate film easily passes moisture, and as a result, problems such as deterioration of the polarizer have occurred. Therefore, conventionally, plasticizers such as triphenyl phosphate have been used as additives having a plasticizing effect and moisture permeation resistance on the film.

  In addition, with the thinning of liquid crystal displays, studies are being made to further reduce the thickness of the optical compensation film. Under such circumstances, triphenyl phosphate is not sufficiently compatible with the resin, and thus bleed may occur due to the influence of heat and humidity in the film production process. Furthermore, since triphenyl phosphate is a low molecular weight compound, it has high volatility and has a problem due to contamination of the film production apparatus.

  Moreover, since the retardation (birefringence) essential for the optical compensation film is not sufficient as it is, the cellulose ester film has been studied variously to impart retardation to the cellulose ester film. Furthermore, in recent years, a larger retardation has been demanded for further widening the viewing angle and thinning of liquid crystal televisions.

  In order to increase the retardation of the resin film, a method of adding a retardation increasing agent is known. However, the conventional retardation increasing agent needs to be added in a large amount, and problems such as bleeding occur. It was difficult. In addition, a method for reducing the total acyl group substitution degree of cellulose has been proposed, but there has been a problem that hygroscopicity is increased.

Under such circumstances, in recent years, a method for adding a specific retardation increasing agent has been proposed for practical use. For example, in Patent Document 1, optical properties, moisture permeation resistance, and the like are improved by using an ester compound of a diol and a specific aromatic dicarboxylic acid compound.
For example, Patent Document 2 proposes a film having a high UV-cutting ability in which dibenzoylmethane is added to a cellulose ester film.

JP 2010-138379 A JP 2003-177235 A

  However, the cellulose ester film composed of a diol and a specific aromatic dicarboxylic acid in Patent Document 1 is insufficient to have a high retardation value associated with the thinning of the liquid crystal structure.

  On the other hand, Patent Document 2 in which a film with improved UV-cutting ability by addition of dibenzoylmethane has been proposed does not describe the effect of improving optical characteristics at all, and it is not possible to use this for a stretched optical compensation film. Not even suggested.

  Then, the objective of this invention is providing the film formed by shape | molding the cellulose resin composition which has the outstanding optical characteristic, and this resin composition.

In order to solve the above problems, the cellulose resin composition of the present invention is:
(A) For 100 parts by mass of cellulosic resin,
(B) 1 or more to 1 to 30 parts by mass selected from the group consisting of the following polyester compounds excluding cellulose ester,
(B-1) a polyester compound comprising a polyhydric alcohol and a polycarboxylic acid,
(B-2) a polyester compound comprising a polyhydric alcohol and a monocarboxylic acid,
(B-3) A polyester compound composed of a polyvalent carboxylic acid and a monoalcohol, and (C) 0.1 to 30 parts by mass of a β-diketone compound are blended.

  In the cellulose resin composition of the present invention, the component (B-1) of the polyester compound (b-1) is 30% by mass or more, the polyester compound (b-2) is 30% by mass or more, or (b-3). It is preferable that the polyester compound is 30% by mass or more.

（式（１）中、ｌは平均重合度を表す数で、１〜３０であり、Ａは炭素原子数１〜１８のアルキレン基または炭素原子数６〜１８の芳香族基を、Ｇは炭素原子数２〜１２のアルキレン基または炭素原子数４〜１２のエーテル結合を有するアルキレン基を、Ｅは水素原子または炭素原子数２〜１０の脂肪族アシル基または炭素原子数７〜１３の芳香族アシル基を表す。）、
（ｂ−２）のポリエステル化合物が次式（２）、

（式（２）中、Ｒ^１は脂肪族基を有してもよい炭素原子数６〜２０の芳香族基であり、Ｒ^２はｍ価の炭素原子数２〜２０の脂肪族基であり、ｍは２〜１０の数を表す。）、及び
（ｂ−３）のポリエステル化合物が次式（３）、

（式（３）中、Ｒ^３は芳香族基を有してもよい炭素原子数１〜２０の脂肪族基であり、Ｒ^４はｎ価の炭素原子数６〜２０の芳香族基であり、ｎは２〜４の数を表す。）
で表されるものが夫々好ましい。 Moreover, as for the cellulose resin composition of this invention, the polyester compound of (b-1) is a following formula (1) among a component (B),

(In the formula (1), l is a number representing an average degree of polymerization and is 1 to 30, A is an alkylene group having 1 to 18 carbon atoms or an aromatic group having 6 to 18 carbon atoms, and G is carbon. An alkylene group having 2 to 12 atoms or an alkylene group having an ether bond having 4 to 12 carbon atoms, E is a hydrogen atom, an aliphatic acyl group having 2 to 10 carbon atoms, or an aromatic group having 7 to 13 carbon atoms Represents an acyl group),
The polyester compound of (b-2) is represented by the following formula (2),

(In Formula (2), R ¹ is an aromatic group having 6 to 20 carbon atoms which may have an aliphatic group, and R ² is an m-valent aliphatic group having 2 to 20 carbon atoms. , M represents a number of 2 to 10), and the polyester compound of (b-3) is represented by the following formula (3),

(In Formula (3), R ³ is an aliphatic group having 1 to 20 carbon atoms which may have an aromatic group, and R ⁴ is an n-valent aromatic group having 6 to 20 carbon atoms. , N represents a number from 2 to 4.
Are preferably represented.

（式（４）中、Ｒ^５〜Ｒ^１６は、各々独立して、水素原子、アミノ基、アミド基、ニトロ基、シアノ基、ヒドロキシル基、ハロゲン原子、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数１〜１０のアルコキシ基、置換基を有していてもよい炭素原子数６〜２０のアリール基、置換基を有していてもよい炭素原子数６〜２０のアリールオキシ基、置換基を有していてもよい炭素原子数７〜２０のアリールアルキル基、置換基を有していてもよい炭素原子数７〜２０のアリールカルボニル基、置換基を有していてもよい炭素原子数５〜１２のシクロアルキル基、置換基を有していてもよい炭素原子数２〜１０のアルカノイルオキシ基、置換基を有していてもよい炭素原子数３〜２１のアルキルカルボニルオキシアルキレンオキシ基、置換基を有していてもよい炭素原子数２〜１０のアルコキシカルボニル基、置換基を有していてもよい炭素原子数２〜１０のアルキルカルボニル基、置換基を有していてもよい炭素原子数２〜２０のアルコキシアルキレンオキシ基、置換基を有していてもよい炭素原子数３〜２１のアルコキシカルボニルアルキレンオキシ基を表し、また、隣り合う２個の基が連結してそれぞれ結合する炭素原子とともに５員環または６員環を形成していてもよく、この５員環、６員環は置換基を有していてもよい。） In the cellulose resin composition of the present invention, the component (C) is preferably a β-diketone compound represented by the following formula (4).

(In Formula (4), R ^{5 to} R ¹⁶ are each independently a hydrogen atom, an amino group, an amide group, a nitro group, a cyano group, a hydroxyl group, a halogen atom, or an optionally substituted carbon. An alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent; An aryloxy group having 6 to 20 carbon atoms which may have, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, and 7 carbon atoms which may have a substituent An arylcarbonyl group of -20, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, an alkanoyloxy group having 2 to 10 carbon atoms which may have a substituent, and a substituent; Alkyl having 3 to 21 carbon atoms which may have A carbonyloxyalkyleneoxy group, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted alkylcarbonyl group having 2 to 10 carbon atoms, and a substituent. Represents an alkoxyalkyleneoxy group having 2 to 20 carbon atoms which may be substituted, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent, and two adjacent groups are A 5-membered ring or a 6-membered ring may be formed together with carbon atoms that are bonded to each other, and this 5-membered ring or 6-membered ring may have a substituent.

  In the cellulose resin composition of the present invention, the cellulose resin is preferably cellulose acylate.

  The film of the present invention is formed by molding the cellulose resin composition of the present invention.

  The film of the present invention is preferably a stretched optical compensation film formed by stretching.

In the present invention, being excellent in optical properties means that a large retardation is imparted, and this retardation can generally be grasped by a retardation value (Rth) in the thickness direction of the film.
Rth is a value defined by the following formula.
Rth = {(nx + ny) / 2−nz} × d
[In the formula, nx is the refractive index in the direction where the refractive index in the film plane is the largest, ny is the refractive index in the film plane in the direction perpendicular to nx, nz is the refractive index in the thickness direction of the film, and d is the refractive index of the film Represents thickness (nm). ]
This retardation value Rth can be measured, for example, using an automatic birefringence meter such as KOBRA-WR (manufactured by Oji Scientific Instruments) or RETS-100 (manufactured by Otsuka Electronics Co., Ltd.).

  The resin composition of the present invention has excellent optical properties, that is, has a large retardation, and is suitably used as a retardation film for a liquid crystal display device, particularly a VA liquid crystal display device using a VA mode liquid crystal cell. The

Hereinafter, the present invention will be described in detail.
(A) Cellulose-based resin The (A) cellulose-based resin used in the present invention may be any type, but is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Examples of the lower fatty acid ester of cellulose include cellulose acetate, cellulose propionate, and cellulose butyrate. Examples include mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in Japanese Patent No. -45804, Japanese Patent Laid-Open No. 8-231761, and US Pat. No. 2,319. .

(B) Polyester compound excluding cellulose ester (B) Polyester compound excluding cellulose ester used in the present invention is (b-1) a polyester compound composed of a polyhydric alcohol and a polycarboxylic acid, and (b-2) a polyvalent compound. It is at least one selected from the group consisting of a polyester compound consisting of an alcohol and a monocarboxylic acid, and (b-3) a polyester compound consisting of a polyvalent carboxylic acid and a monoalcohol. Polyester composed of a polyhydric alcohol and a polycarboxylic acid means that a polyhydric alcohol and a polycarboxylic acid may be esterified with an esterification catalyst such as an acid catalyst, a titanium compound, a tin compound or a zirconium compound. It may be esterified by reacting an acid chloride corresponding to a polyhydric alcohol, or a transesterification reaction of a phenyl ester of a polycarboxylic acid and a polyhydric alcohol in the presence of a transesterification catalyst. Is not particularly limited.

Moreover, it is preferable to refine | purify by a various method as needed, and to reduce an acid value and a catalyst residue so that stability and optical characteristics of a cellulose resin composition may not be impaired.
However, the method for synthesizing the compound by the above method is not limited at all.

（式（１）中、ｌは平均重合度を表す数で、１〜３０であり、Ａは炭素原子数１〜１８のアルキレン基または炭素原子数６〜１８の芳香族基を、Ｇは炭素原子数２〜１２のアルキレン基または炭素原子数４〜１２のエーテル結合を有するアルキレン基を、Ｅは水素原子または炭素原子数２〜１０の脂肪族アシル基または炭素原子数７〜１３の芳香族アシル基を表す。）で表されるものであることが好ましい。 Among the components (B), the polyester compound (b-1) is represented by the following formula (1),

(In the formula (1), l is a number representing an average degree of polymerization and is 1 to 30, A is an alkylene group having 1 to 18 carbon atoms or an aromatic group having 6 to 18 carbon atoms, and G is carbon. An alkylene group having 2 to 12 atoms or an alkylene group having an ether bond having 4 to 12 carbon atoms, E is a hydrogen atom, an aliphatic acyl group having 2 to 10 carbon atoms, or an aromatic group having 7 to 13 carbon atoms Represents an acyl group).

  In the general formula (1), examples of the alkylene group having 1 to 18 carbon atoms represented by A include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-amyl, 1,2-dimethylpropyl, n-hexyl, 1,2-dimethylbutyl, 1-isopropylpropyl, 1,3-dimethylbutyl, n-heptyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-methylhexyl, 2-ethylhexyl, 2-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoun Sil, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecyl, isoheptadecyl, n-octadecyl, isooctadecyl And the like are groups in which any one hydrogen atom is removed.

In the general formula (1), examples of the aromatic group having 6 to 18 carbon atoms include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, and the like.
A contained in the polyester may be a single or a mixture of two or more as long as it is an alkylene group or an aromatic group.

In the general formula (1), examples of the alkylene group having 2 to 12 carbon atoms or the ether group having 4 to 12 carbon atoms represented by G include corresponding glycols such as ethylene glycol. , Diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3 -Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Alkylene glycols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol , Oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, etc., in addition, a small proportion of glycerin, trimethylolpropane, trimethylolethane, dipentaerythritol, pentaerythritol, etc. A trihydric or higher polyhydric alcohol can be used.
G contained in the polyester may be a single or a mixture of two or more as long as it is an alkylene group or an alkylene group having an ether bond.

In the general formula (1), examples of the aliphatic acyl group having 2 to 10 carbon atoms represented by E include acetyl, propanoyl (propionic acid), butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl and decanoyl. It is done.
In the general formula (1), examples of the aromatic acyl group having 7 to 13 carbon atoms represented by E include benzoyl which may have a substituent, cinnamoyl which may have a substituent, and the like. Can be mentioned.
E contained in the polyester may be a single atom or a mixture of two or more, as long as it is a hydrogen atom, the above-mentioned aliphatic acyl group and aromatic acyl group.

（式（２）中、Ｒ^１は脂肪族基を有してもよい炭素原子数６〜２０の芳香族基であり、Ｒ^２はｍ価の炭素原子数２〜２０の脂肪族基であり、ｍは２〜１０の数を表す。）で表されるものであることが好ましい。 Among the components (B), the polyester compound (b-2) has the following formula (2),

(In Formula (2), R ¹ is an aromatic group having 6 to 20 carbon atoms which may have an aliphatic group, and R ² is an m-valent aliphatic group having 2 to 20 carbon atoms. , M represents a number of 2 to 10).

In the general formula (2), R ¹ is an aromatic group which may have an aliphatic group, and examples of the corresponding monocarboxylic acid include benzoic acid, toluic acid, anisic acid, phenylacetic acid, and cinnamic acid. And the like, and tert-butylbenzoic acid having an alkyl group introduced at an arbitrary position of the benzene ring of benzoic acid, and trimethoxybenzoic acid having an alkoxy group introduced. Moreover, aromatic monocarboxylic acid which has two or more benzene rings, such as biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid, or derivatives thereof are mentioned.

In the general formula (2), R ² is an m-valent aliphatic group, and the aliphatic group may be chain-like, cyclic, ether-bonded, interrupted by an aromatic ring, and correspondingly Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, adonitol, arabitol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol , Mannitol, 3-methylpentane-1,3,5-triol, Examples include nachol, sorbitol, pentaerythritol, dipentaerythritol, trimethylolpropane, trimethylolethane, xylitol, glucose, 1,4-phenylenedimethanol and the like. Among these, trimethylolpropane, dipentaerythritol, mannitol, and glucose are preferable.

（式（３）中、Ｒ^３は芳香族基を有してもよい炭素原子数１〜２０の脂肪族基であり、Ｒ^４はｎ価の炭素原子数６〜２０の芳香族基であり、ｎは２〜４の数を表す。）で表されるものであることが好ましい。 Among the components (B), the polyester compound (b-3) is represented by the following formula (3),

(In Formula (3), R ³ is an aliphatic group having 1 to 20 carbon atoms which may have an aromatic group, and R ⁴ is an n-valent aromatic group having 6 to 20 carbon atoms. , N represents a number of 2 to 4).

In the general formula (3), R ³ is an aliphatic group which may have an aromatic group, and the aliphatic group may be linear or cyclic, and is methyl, ethyl, n-propyl, isopropyl, n-butyl. , Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-amyl, 1,2-dimethylpropyl, n-hexyl, 1,2-dimethylbutyl, 1-isopropylpropyl, 1,3- Dimethylbutyl, n-heptyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-methyl Hexyl, 2-ethylhexyl, 2-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclohexyl Xyl, benzyl and the like.

In the general formula (3), R ⁴ is an n-valent aromatic group, and examples of the corresponding aromatic polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, Examples include trimesic acid, pyromellitic acid, merit acid, naphthalenedicarboxylic acid and the like.

  The polyester compound which consists of a (b-1) polyhydric alcohol and polyhydric carboxylic acid represented by the said General formula (1) used by this invention below is illustrated, However, This invention is limited by this is not. In addition, the inside of () of a mixture shows molar ratio. Moreover, these polyester compounds may be used independently or may use 2 or more types as a mixture.

Compound No. 1: Polyethylene alcohol component G as ethylene glycol (50) and 1,2-propylene glycol (50), polyhydric carboxylic acid component A as succinic acid (50) and terephthalic acid (50), terminal E is acetyl 1 = 5 polyester compound comprising a group.
Compound No. 2: 1,2-propylene glycol as the polyhydric alcohol component G, 2,6-naphthalenedicarboxylic acid as the polyhydric carboxylic acid component A, and l = 2 polyester compound composed of hydrogen at the terminal E.
Compound No. 3: Polyester compound of 1 = 10 in which ethylene glycol is used as the polyhydric alcohol component G, adipic acid is used as the polyhydric carboxylic acid component A, and the terminal E is an acetyl group.
Compound No. 4: Polyester compound of 1 = 5, in which 1,2-propylene glycol is used as the polyhydric alcohol component G, and terephthalic acid is used as the polycarboxylic acid component A, and the terminal E is a toluyl group.

化合物Ｎｏ．７

化合物Ｎｏ．８

化合物Ｎｏ．９

The polyester compound which consists of a (b-2) polyhydric alcohol and monocarboxylic acid represented by the said General formula (2) used by this invention below is illustrated, However, This invention is not limited by this Absent. Moreover, these polyester compounds may be used independently or may use 2 or more types as a mixture.
Compound No. 5 Compound No. 5 6

Compound No. 7

Compound No. 8

Compound No. 9

化合物Ｎｏ．１１

化合物Ｎｏ．１２

Examples of the polyester compound composed of a polyester compound composed of (b-3) a polycarboxylic acid and a monoalcohol represented by the general formula (3) used in the present invention are shown below, but the present invention is limited thereby. Is not to be done. Moreover, these polyester compounds may be used independently or may use 2 or more types as a mixture.
Compound No. 10

Compound No. 11

Compound No. 12

  In the cellulose resin composition of the present invention, the component (B-1) of the polyester compound (b-1) is 30% by mass or more, the polyester compound (b-2) is 30% by mass or more, or (b-3). It is preferable that the polyester compound is 30% by mass or more.

  Moreover, the usage-amount of the polyester compound of a component (B) is 1-30 mass parts with respect to 100 mass parts of cellulose resins, Preferably it is 1-20 mass parts. When the amount used is less than 1 part by mass, the effect is not sufficiently exhibited. On the other hand, when the amount exceeds 30 parts by mass, bleeding occurs, which is not preferable.

(C) β-diketone compound The (C) β-diketone compound used in the present invention can be synthesized by any condensation reaction. For example, an acetophenone derivative and a benzoate derivative under a basic catalyst such as sodium methoxide. Can be synthesized by a Claisen condensation reaction.
However, the method for synthesizing the compound by the above method is not limited at all.

（式（４）中、Ｒ^５〜Ｒ^１６は、各々独立して、水素原子、アミノ基、アミド基、ニトロ基、シアノ基、ヒドロキシル基、ハロゲン原子、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数１〜１０のアルコキシ基、置換基を有していてもよい炭素原子数６〜２０のアリール基、置換基を有していてもよい炭素原子数６〜２０のアリールオキシ基、置換基を有していてもよい炭素原子数７〜２０のアリールアルキル基、置換基を有していてもよい炭素原子数７〜２０のアリールカルボニル基、置換基を有していてもよい炭素原子数５〜１２のシクロアルキル基、置換基を有していてもよい炭素原子数２〜１０のアルカノイルオキシ基、置換基を有していてもよい炭素原子数３〜２１のアルキルカルボニルオキシアルキレンオキシ基、置換基を有していてもよい炭素原子数２〜１０のアルコキシカルボニル基、置換基を有していてもよい炭素原子数２〜１０のアルキルカルボニル基、置換基を有していてもよい炭素原子数２〜２０のアルコキシアルキレンオキシ基、置換基を有していてもよい炭素原子数３〜２１のアルコキシカルボニルアルキレンオキシ基を表し、また、隣り合う２個の基が連結してそれぞれ結合する炭素原子とともに５員環または６員環を形成していてもよく、この５員環、６員環は置換基を有していてもよい。） A β-diketone compound represented by the following formula (4) is preferable.

(In Formula (4), R ^{5 to} R ¹⁶ are each independently a hydrogen atom, an amino group, an amide group, a nitro group, a cyano group, a hydroxyl group, a halogen atom, or an optionally substituted carbon. An alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent; An aryloxy group having 6 to 20 carbon atoms which may have, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, and 7 carbon atoms which may have a substituent An arylcarbonyl group of -20, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, an alkanoyloxy group having 2 to 10 carbon atoms which may have a substituent, and a substituent; Alkyl having 3 to 21 carbon atoms which may have A carbonyloxyalkyleneoxy group, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted alkylcarbonyl group having 2 to 10 carbon atoms, and a substituent. Represents an alkoxyalkyleneoxy group having 2 to 20 carbon atoms which may be substituted, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent, and two adjacent groups are A 5-membered ring or a 6-membered ring may be formed together with carbon atoms that are bonded to each other, and this 5-membered ring or 6-membered ring may have a substituent.

In the general formula (4), examples of the halogen atom represented by R ^{5 to} R ¹⁶ include fluorine, chlorine, bromine, and iodine.
In the general formula (4), examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R ^{5 to} R ¹⁶ include methyl, ethyl, propyl, isopropyl, butyl, Examples include isobutyl, sec-butyl, tert-butyl, pentyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like.

  In addition, examples of the alkoxy group having 1 to 10 carbon atoms which may have a substituent include those corresponding to an alkyl group. For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- Examples include butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, 1,2-dimethyl-propoxy, hexyloxy, cyclohexyloxy, heptyloxy, octoxy, nonyloxy, decanoxy and the like.

Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent include phenyl, naphthyl, tolyl, benzyl, trityl, and styryl.
Examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent include those corresponding to the aryl group, and examples thereof include phenoxy and naphthoxy.

  Examples of the optionally substituted arylalkyl group having 7 to 20 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, styryl, cinnamyl, diphenylmethyl, triphenylmethyl and the like. Is mentioned.

  Examples of the arylcarbonyl group having 7 to 20 carbon atoms which may have a substituent include benzoyl and the like, and an arylcarbonyl group having a substituent corresponding to the alkyl group or alkoxy group is Can be mentioned.

  Examples of the cycloalkyl group having 5 to 12 carbon atoms which may have a substituent include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like.

  Examples of the alkanoyloxy group having 2 to 10 carbon atoms which may have a substituent include alkanoyloxy groups corresponding to the alkyl groups.

  Examples of the alkylcarbonyloxyalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent include an alkylcarbonyloxyalkyleneoxy group corresponding to the alkyl group.

Examples of the alkylcarbonyl group having 2 to 10 carbon atoms that may have a substituent include an alkylcarbonyl group corresponding to the alkyl group.
Moreover, the C2-C10 alkoxycarbonyl group which may have a substituent includes an alkoxycarbonyl group corresponding to the alkoxy group.

  Examples of the alkoxyalkyleneoxy group having 2 to 20 carbon atoms which may have a substituent include alkoxyalkyleneoxy groups corresponding to the above alkoxy groups and alkyl groups.

  Examples of the alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent include alkoxycarbonylalkyleneoxy groups corresponding to the alkoxy groups and alkyl groups.

  Examples of the 5-membered ring when two adjacent groups are linked to form a 5-membered ring or 6-membered ring with the carbon atoms to which they are bonded include a cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole And a ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiophene ring, a furan ring, and a pyrrole ring. Examples of the 6-membered ring include a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring, a benzene ring, a pyridine ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrazine ring, a pyrone ring, and a pyrrolidine ring. The 5-membered ring and 6-membered ring may have the above-described substituent.

化合物ＢＤ−３ 化合物ＢＤ−４

化合物ＢＤ−５

化合物ＢＤ−６

化合物ＢＤ−７

化合物ＢＤ−８

The (C) β-diketone compound used in the present invention is exemplified below, but the present invention is not limited thereto.
Compound BD-1 Compound BD-2

Compound BD-3 Compound BD-4

Compound BD-5

Compound BD-6

Compound BD-7

Compound BD-8

  The amount of the β-diketone compound used is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the cellulose resin. When the amount used is less than 0.1 parts by mass, the effect is not sufficiently exhibited. On the other hand, when the amount exceeds 30 parts by mass, bleeding occurs, which is not preferable.

  In the present invention, other plasticizers can be arbitrarily used. Examples of the plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like; dioctyl adipate, diisononyl adipate, diisodecyl Adipate plasticizers such as adipate and di (butyldiglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxy) Ethyl) phosphate, octyl diphenyl phosphate, etc. Plasticizers; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1, 5-hexanediol, 1,6-hexanediol, neopentyl glycol and the like, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Polyester plasticizer using phthalic acid, isophthalic acid, terephthalic acid, etc., and using monohydric alcohol or monocarboxylic acid (acetic acid, aromatic acid, etc.) as a stopper if necessary; Tetrahydrophthalic acid plasticizer, Azelain Acid plasticizer, sebacic acid plasticizer, stearic acid Agent, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer, polyhydric alcohol aromatic acid ester plasticizer (trimethylolpropane tribenzoate, etc.) Etc.

In addition, various additives such as phosphorus, phenol or sulfur antioxidants, ultraviolet absorbers, hindered amine light stabilizers and the like can be further blended in the present invention.
Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, Trila Uril trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4 '-Isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-diamilphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (Octylphenyl) bi [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl, 4,4'-butylidenebis (2-tert-butyl- 5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol · 2,4,6-tritert-butylphenol monophosphite, and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4,6-di) Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-to Methylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4) -Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3 -Tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [ β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2 2-methacryloyloxyethoxyethoxy) benzophenone, 2-hydroxybenzophenones such as 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tertiary) Butyl-5-methylphenyl) -5-chlorobenzotriazole, -(2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy -3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxy) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of phenyl) benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5 Triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxyethoxy) 2- (2-hydroxyphenyl) -1,3,5-triazines such as phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy Substituted oxanilides such as cis-4'-dodecyloxanilide; cyano such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Examples include acrylates.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro- -Morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine Polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 -Yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl) -4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- ( 2,2,6,6-tetramethyl-4-piperidyl) amino-s-to Riazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine -6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxy] Carbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  In addition, the present invention further includes other additives as necessary, for example, fillers, colorants, crosslinking agents, antistatic agents, plate-out preventing agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents. Agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents and the like can be blended.

Next, although the manufacturing method of the film of this invention is demonstrated, it is not limited by the following methods.
The production of the present invention is performed by applying and drying a dope solution in which cellulose ester is dissolved in a solvent. Various additives can be mixed in the dope liquid as necessary. The concentration of the cellulose ester in the dope is preferably higher because the drying load after casting on the support can be reduced. However, if the concentration of the cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. As a density | concentration which makes these compatible, 10-30 mass% is preferable, More preferably, it is 15-25 mass%.

  Although the solvent used for preparation of the dope liquid concerning this invention may be individual or it may use together, it is preferable from the point of production efficiency to mix and use the good solvent and poor solvent of a cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 30 to 2% by mass for the poor solvent. With the good solvent and the poor solvent used in the present invention, those that dissolve the cellulose ester used alone are defined as good solvents, and those that swell or cannot dissolve alone are defined as poor solvents. Therefore, depending on the average degree of acetylation of cellulose, the good solvent and the poor solvent change. For example, acetone becomes a good solvent for cellulose esters having an average degree of acetylation of 55%, and poor for cellulose esters having an average degree of acetylation of 60%. It becomes a solvent. Thus, the good solvent and the poor solvent are not uniquely determined in all cases. In the case of the preferred cellulose ester in the present invention, examples of the good solvent include organic halogen compounds such as methylene chloride, dioxolanes, acetone, and methyl acetate. On the other hand, examples of the poor solvent include methanol, ethanol, n-butanol, cyclohexane, and cyclohexanone.

  As a method for dissolving the cellulose ester in preparing the dope solution, a general method can be used, but heating is performed at a temperature not lower than the boiling point at normal pressure of the solvent and in a range where the solvent does not boil under pressure. In addition, the method of dissolving with stirring is preferable because it can prevent the generation of massive undissolved material called gel or mamako. Further, a method in which cellulose ester is mixed with a poor solvent and wetted or swollen, and then mixed with a good solvent and dissolved is also preferably used. Furthermore, a known cooling dissolution method may be used. When the cooling dissolution method is used, methyl acetate or acetone can be used as a good solvent. The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature after the addition of the solvent is preferably a temperature that is not less than the boiling point of the solvent used at normal pressure and does not boil from the viewpoint of the solubility of the cellulose ester. If the heating temperature is too high, the required pressure increases and productivity decreases. The range of preferable heating temperature is 45-120 degreeC, 60-110 degreeC is more preferable, and 70-105 degreeC is still more preferable. The pressure is adjusted so that the solvent does not boil at the set temperature. After heating, the obtained cellulose ester solution is filtered using an appropriate filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove unnecessary substances and the like, but if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium in the range of 0.001 to 0.008 mm is more preferable, and a filter medium in the range of 0.003 to 0.006 mm is still more preferable. The material of the filter medium is not particularly limited, and a normal filter medium can be used. For example, a filter medium made of plastic such as polypropylene and Teflon (registered trademark) or a metal filter medium such as stainless steel does not lose fibers. ,preferable.

The dope solution can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at a normal pressure and in a range where the solvent does not boil is a differential pressure before and after the filter medium. An increase in (hereinafter sometimes referred to as filtration pressure) is small and preferable. The temperature of preferable filtration is 45-120 degreeC, 45-70 degreeC is more preferable, and 45-55 degreeC is still more preferable. A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 × 10 ⁶ Pa or less, more preferably 1.2 × 10 ⁶ Pa or less, and further preferably 1.0 × 10 ⁶ Pa or less.

  The support used in the casting (casting) step is preferably a support obtained by mirror-finishing endless belt-shaped or drum-shaped stainless steel. The temperature of the support in the casting step is preferably from 0 ° C. to a temperature lower than the boiling point of the solvent. The higher the temperature, the faster the drying speed. However, if the temperature is too high, foaming may occur and flatness may deteriorate. A preferable support body temperature is 0-50 degreeC, and 5-30 degreeC is still more preferable. The method for controlling the temperature of the support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of bringing a hot water bat into contact with the support. Among these methods, the method using a hot water bat is preferable because heat transfer is efficiently performed and the time during which the temperature of the support becomes constant is shortened. When using warm air, it is necessary to use wind at a temperature higher than the target temperature. In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling from the support is preferably 10 to 120% by mass, more preferably 20 to 40% by mass or 60 to 120% by mass. Especially preferably, it is 20-30 mass% or 70-115 mass%.

In the present invention, the residual solvent amount is defined by the following formula.
Residual solvent amount = [(film mass before heat treatment−film mass after heat treatment) / (film mass after heat treatment)] × 100 (%)
The heat treatment for measuring the residual solvent amount means heating the film at 115 ° C. for 1 hour. Moreover, in the drying process of a cellulose-ester film, it is preferable to dry further the film peeled from the support body, and to make residual solvent amount 3 mass% or less, and 0.5 mass% or less is more preferable. In the film drying process, generally, a roll suspending method or a tenter method can be adopted in which the film is dried while being conveyed.

  While the amount of residual solvent immediately after peeling from the support is large, it is preferable to carry out width holding or stretching by a tenter method because the effect of improving dimensional stability is more exhibited. The means for drying the film is not particularly limited, and can be performed with hot air, infrared rays, a heating roll, microwaves, or the like. In terms of simplicity, it is preferable to use hot air. In this case, the drying temperature is preferably increased stepwise in the range of 40 to 150 ° C., and more preferably 50 to 140 ° C. in order to improve dimensional stability.

  The stretched optical compensation film is preferably thin because the liquid crystal display can be easily thinned. However, if the stretched optical compensation film is too thin, the moisture permeability increases and the tear strength and the like are insufficient. As a film thickness of the cellulose ester film which makes these compatible, 10-150 micrometers is preferable and 20-100 micrometers is more preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples. The unit of the blending amount in the table is part by mass.

  100 parts by weight of cellulose triacetate (degree of acetylation 61%, degree of polymerization 260) and the additives listed in Tables 1 to 10 below are parts by weight listed in the same table, 400 parts by weight of methylene chloride, 100 parts by weight of methyl alcohol, The mixture was uniformly dissolved with stirring to prepare various dope solutions for evaluation of volatility and film production. Next, the obtained dope solution was cast on a glass plate to a thickness of about 80 μm, dried at room temperature for 16 hours, dried at 50 ° C. for 1 hour, further dried at 120 ° C. for 1 hour, and various evaluations A film was obtained. The film thicknesses of the obtained films were all about 80 μm.

<Retardation measurement method>
About the obtained film, retardation (Rth) in the thickness direction at a wavelength of 590 nm under an environment of 25 ° C. and a relative humidity of 60% using an automatic birefringence meter RETS-100 (manufactured by Otsuka Electronics Co., Ltd.) according to the following formula. It was measured.
Rth = {(nx + ny) / 2−nz} × d
[In the formula, nx is the refractive index in the direction where the refractive index in the film plane is the largest, ny is the refractive index in the film plane in the direction perpendicular to nx, nz is the refractive index in the thickness direction of the film, and d is the refractive index of the film Represents thickness (nm). ]

<Evaluation method of volatility>
About the prepared dope solutions, the solvent was distilled off on conditions of 140 degreeC and 10 kPa. The solvent distilled off was analyzed with a gas chromatograph and evaluated according to the following criteria.
A: A polyester compound was not detected.
X: A polyester compound or triphenyl phosphate was detected.
(Gas chromatograph analysis conditions)
Device: GC-17A (manufactured by Shimadzu Corporation)
Column: BPX-5 (manufactured by SGE)
Inlet temperature: 300 ° C
Detector temperature: 300 ° C
Temperature rising program: 100 ° C. → 15 ° C./min.

The obtained evaluation results are shown in Tables 1 to 8 below.
<Method for evaluating moisture permeability>
The film obtained by the above method was measured for moisture permeability according to the method described in JIS Z 0208. The measurement conditions are 40 ° C. and relative humidity 90%.
The obtained evaluation results are shown in Tables 9 to 10 below.

＊＊：添加剤なし

**: No additive

＊トリフェニルホスフェート

* Triphenyl phosphate

The following things became clear from the said Tables 1-8.
Compared with Comparative Example 1-2 and Comparative Example 1-4 which do not use any one of (B) polyester compound and (C) β-diketone compound according to the present invention, any example using both The retardation value was also large.
In addition, as is clear from Comparative Example 1-1, Comparative Example 1-5, and Comparative Example 1-12 to Comparative Example 1-14, the film is brittle when the (B) polyester compound is below a predetermined amount. When the test piece was cut for retardation measurement, it was cracked and the retardation could not be measured.
Further, as is clear from Comparative Examples 1-6 to 1-8, when the amount of (C) β-diketone compound was a predetermined amount or less, the retardation value was small as compared with all Examples. .
Furthermore, as is clear from Comparative Examples 1-9 to 1-11 and Comparative Examples 1-15 to 1-17, (B) the polyester compound or (C) the β-diketone compound is at a predetermined amount or more. In some cases, the film bleeds and retardation cannot be measured.

Next, Table 9 and Table 10 revealed the following.
It turned out that moisture permeability can be reduced by setting it as the composition which uses the (B) polyester compound and (C) (beta) -diketone compound which concern on this invention compared with single use of the (B) polyester compound.
Further, as apparent from Table 5, when the (C) β-diketone compound was used alone, the moisture permeability could not be measured because the film was brittle. Moreover, even if the moisture permeability as a film can be lowered due to the brittleness, if it breaks, the moisture permeability becomes easy as a result. Therefore, it is apparent that the present invention is useful in providing a cellulose film having excellent moisture permeability.

Claims (11)

(A) For 100 parts by mass of cellulosic resin,
(B) 1 or more to 1 to 30 parts by mass selected from the group consisting of the following polyester compounds excluding cellulose ester,
(B-1) Polyester compound comprising polyhydric alcohol and polycarboxylic acid (b-2) Polyester compound comprising polyhydric alcohol and monocarboxylic acid (b-3) Polyester compound comprising polyhydric carboxylic acid and monoalcohol and (C) A cellulose-based resin composition comprising 0.1 to 30 parts by mass of a β-diketone compound.   The cellulose resin composition according to claim 1, wherein the polyester compound (b-1) in the component (B) is 30% by mass or more.   The cellulose resin composition according to claim 1, wherein the polyester compound (b-2) in the component (B) is 30% by mass or more.   The cellulose-based resin composition according to claim 1, wherein the polyester compound (b-3) in the component (B) is 30% by mass or more. The cellulose resin composition according to any one of claims 1 to 4, wherein the polyester compound (b-1) is represented by the following formula (1).

(In the formula (1), l is a number representing an average degree of polymerization and is 1 to 30, A is an alkylene group having 1 to 18 carbon atoms or an aromatic group having 6 to 18 carbon atoms, and G is carbon. An alkylene group having 2 to 12 atoms or an alkylene group having an ether bond having 4 to 12 carbon atoms, E is a hydrogen atom, an aliphatic acyl group having 2 to 10 carbon atoms, or an aromatic group having 7 to 13 carbon atoms Represents an acyl group.) The cellulose resin composition according to any one of claims 1 to 4, wherein the polyester compound (b-2) is represented by the following formula (2).

(In Formula (2), R ¹ is an aromatic group having 6 to 20 carbon atoms which may have an aliphatic group, and R ² is an m-valent aliphatic group having 2 to 20 carbon atoms. M represents a number of 2 to 10.) The cellulose resin composition according to any one of claims 1 to 4, wherein the polyester compound (b-3) is represented by the following formula (3).

(In Formula (3), R ³ is an aliphatic group having 1 to 20 carbon atoms which may have an aromatic group, and R ⁴ is an n-valent aromatic group having 6 to 20 carbon atoms. , N represents a number from 2 to 4. The cellulose resin composition according to any one of claims 1 to 7, wherein the component (C) is represented by the following formula (4).

(In Formula (4), R ^{5 to} R ¹⁶ are each independently a hydrogen atom, an amino group, an amide group, a nitro group, a cyano group, a hydroxyl group, a halogen atom, or an optionally substituted carbon. An alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent; An aryloxy group having 6 to 20 carbon atoms which may have, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, and 7 carbon atoms which may have a substituent An arylcarbonyl group of -20, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, an alkanoyloxy group having 2 to 10 carbon atoms which may have a substituent, and a substituent; Alkyl having 3 to 21 carbon atoms which may have A carbonyloxyalkyleneoxy group, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted alkylcarbonyl group having 2 to 10 carbon atoms, and a substituent. Represents an alkoxyalkyleneoxy group having 2 to 20 carbon atoms which may be substituted, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent, and two adjacent groups are A 5-membered ring or a 6-membered ring may be formed together with carbon atoms that are bonded to each other, and this 5-membered ring or 6-membered ring may have a substituent.   The cellulose resin composition according to any one of claims 1 to 8, wherein the cellulose resin is cellulose acylate.   A film formed by molding the cellulose resin composition according to any one of claims 1 to 9.   The film according to claim 9 or 10, which is a stretched optical compensation film formed by stretching.