JP2015025039A - Cellulose-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition including a cellulose-based resin that has excellent optical characteristics.SOLUTION: The cellulose-based resin composition is produced by blending, based on 100 pts.mass of (A) a cellulose-based resin, 1-30 pts.mass of (B) one or more kinds selected from the group consisting of polyester compounds other than cellulose ester as follows: (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; and (b-3) a polyester compound comprising a polycarboxylic acid and a monoalcohol and 0.1-50 pts.mass of (C) one or more kinds of compounds represented by any of the general formulae (c-1) to (c-9).

Description

  The present invention is characterized in that 0.1 to 30 parts by mass of any one or more of a specific carboxylic acid ester compound and a specific compound is blended with respect to 100 parts by mass of a cellulose resin. The present invention relates to a resin composition 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 have excellent adhesiveness to polyvinyl alcohol used for polarizers, high transparency, and appropriate strength.
However, the cellulose acylate film easily passes moisture, and as a result, problems such as deterioration of the polarizer have occurred. Therefore, a film to which a plasticizer such as triphenyl phosphate is added has been conventionally used as an additive having a plasticizing effect and moisture permeation resistance.

  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 requires a large amount of addition and causes problems such as bleeding, so that it has been difficult to put into practical use so far. Met. 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, there is no description of the optical property improvement effect for the film with improved UV cut ability by addition of dibenzoylmethane in Patent Document 2, and it is not even suggested to use this for a stretched optical compensation film. .
Then, the objective of this invention is providing the resin composition excellent in the optical characteristic by mix | blending with a cellulose resin.

  The cellulose resin composition of the present invention has (B) 1 to 30 parts by mass selected from the group consisting of the following polyester compounds that are not cellulose esters, with respect to 100 parts by mass of (A) cellulose resin. -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 comprising a polyhydric carboxylic acid and a monoalcohol, and (C) One or more compounds represented by any one of the following general formulas (c-1) to (c-9) are blended in an amount of 0.1 to 50 parts by mass.

(In the formula, n ¹ and n ² each independently represent 1 or 2, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or Represents a substituted or unsubstituted aryl group, and when n ³ = 0, the groups represented by R ³ and R ⁴ are linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded. May be.)

(Wherein, X ^{1 to} X ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. A group, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, wherein R ^{01 to} R ⁰⁴ are each independently a hydrogen atom, R ¹¹ represents an alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted ketone diarylene group. Or a substituted or unsubstituted oxydiarylene group.)

（式中、Ｘ^２１〜Ｘ^２５はそれぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、置換または無置換の炭素数１〜２０のアルキル基、置換または無置換の炭素数６〜２０のアリール基、置換または無置換の１〜２０のアルコキシ基、置換または無置換の炭素数６〜２０のアリールオキシ基、置換または無置換の炭素数７〜２０のアリールアルキル基、置換または無置換の炭素数５〜１２のシクロアルキル基、置換または無置換の炭素数２〜１０のアルカノイルオキシ基、置換または無置換の炭素数２〜１０のアルコキシカルボニル基を表し、Ｘ^２２〜Ｘ^２５で表される基のうち隣り合う２個の基が連結してそれぞれが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い。Ｘ^２６〜Ｘ^３０はそれぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、置換または無置換の炭素数１〜２０のアルキル基、置換または無置換の炭素数６〜２０のアリール基、置換または無置換の１〜２０のアルコキシ基、置換または無置換の炭素数６〜２０のアリールオキシ基、置換または無置換の炭素数７〜２０のアリールアルキル基、置換または無置換の炭素数５〜１２のシクロアルキル基、置換または無置換の炭素数２〜１０のアルカノイルオキシ基、置換または無置換の炭素数２〜１０のアルコキシカルボニル基を表し、Ｘ^２６〜Ｘ^３０で表される基のうち隣り合う２個の基が連結してそれぞれが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い。但し、Ｘ^２６〜Ｘ^３０の全てが水素原子となることはない。） Wherein X ^{11 to} X ²⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and represented by X ^{11 to} X ²⁰ Two adjacent groups among the groups may be linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded.

(Wherein X ^{21 to} X ²⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and represented by X ^{22 to} X ²⁵ good .X ²⁶ to X ³⁰ may form a 5- or 6-membered ring together with the carbon atom to which each concatenated two adjacent groups are bonded among groups are each independently, Elementary atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted 1 to 20 alkoxy group, substituted Or an unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted carbon Represents an alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and two adjacent groups among the groups represented by X ^{26 to} X ³⁰ are linked to each other. A 5-membered ring or a 6-membered ring may be formed together with the carbon atoms to be bonded, provided that not all of X ^{26 to} X ³⁰ are hydrogen atoms.

(In the formula, X ^{31 to} X ³⁵ and R ²² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 3 carbon atoms, 10 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl groups having 7 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 12 carbon atoms, A substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon A C3-C21 alkoxycarbonylalkyleneoxy group, a substituted or unsubstituted C3-C21 alkylcarbonyloxyalkyleneoxy group , A cyano group, a nitro group, a primary or secondary amino group, a substituted or an unsubstituted amide group, respectively coupled by connecting the two adjacent groups among the groups represented by X ³¹ to X ³⁵ A 5-membered ring or a 6-membered ring may be formed together with carbon atoms to be represented, and R ²¹ represents an n ⁴ -valent aromatic group or an n ⁴ -valent aliphatic group substituted with an aromatic group. )

(In the formula, X ^{41 to} X ⁴⁵ , R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon, An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted cyclohexane having 5 to 12 carbon atoms; An alkyl group, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted Substituted C3-C21 alkoxycarbonylalkyleneoxy group, substituted or unsubstituted C3-C21 alkylcarbonyloxyalkylene Represents a nonoxy group, a cyano group, a nitro group, a primary or secondary amino group, a substituted or unsubstituted amide group, and two adjacent groups among the groups represented by R ^{41 to} R ⁴⁵ are linked. each may form a 5- or 6-membered ring together with the carbon atom bonded. Further, R ³³ is substituted with n ⁵ divalent aliphatic group or n ⁵ divalent aromatic group, or an aromatic group It represents a n ⁵ divalent aliphatic group.

(In the formula, R ^{41 to} R ⁴⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, a substituted or unsubstituted group. An alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms Oxy group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms, substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, substituted or unsubstituted An alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 3 to 21 carbon atoms. Job aryloxycarbonyl alkyleneoxy group, a substituted or unsubstituted alkylcarbonyloxy alkyleneoxy group having a carbon number of 3 to 21, n ⁶ represents an integer of 0 or 1, of the groups represented by R ⁴¹ to R ⁴⁶ Two adjacent groups may be connected to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded, and this 5-membered or 6-membered ring may have a substituent. Examples of the divalent organic group represented by R ⁴⁷ include alkylene, cycloalkylene, arylene, and a combination thereof, each of which may be substituted or unsubstituted.

(In the formula, each of R ⁵¹ and R ⁵² independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon number. Represents a 7-20 arylalkyl group, R ⁵³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 2 to 10 carbon atoms, substituted Or an unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 20 carbon atoms, and Q is a hydrogen atom, a halogen atom, a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms. Alkyl groups, substituted or unsubstituted alkylcarbonyl groups having 2 to 10 carbon atoms, substituted or unsubstituted arylalkyl groups having 7 to 20 carbon atoms, substituted or unsubstituted 7 to 7 carbon atoms 0 arylcarbonyl group, or represents an alkylene group having 1 to 10 carbon atoms, when R ⁵³ or Q is a hydrogen atom, always the other represents those non-hydrogen atoms, and R ⁵³ and Q are linked carbon A ring group having a number of 3 to 30 may be formed, n ⁷ is an integer of 1 or 2, and when Q is not an alkylene group, n ⁷ represents 1 and when Q is an alkylene group, n ⁷ represents 2, and the substituent is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amide group, an amino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. Alkoxy group, alkanoyloxy group having 1 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, alkoxyalkyleneoxy group having 2 to 20 carbon atoms, alkoxycarbonylalkyl having 3 to 21 carbon atoms Represents a lenoxy group, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof, the alkyl group, the alkanoyloxy group, the alkoxycarbonyl group, the above The alkoxyalkyleneoxy group, the above alkoxycarbonylalkyleneoxy group, and the alkyl group in the arylalkyl group, or the above alkylene group have an oxygen atom, an ester group, a carbonyl group, or a substituted or unsubstituted carbon number of 6 to 20 carbon atoms. One or more of the aryl groups may be interrupted.)

(In formula (c-9), R ⁸¹ and R ⁸² each independently represents a hydrogen atom or a methyl group, and n ¹¹ represents an integer of 1 to 5.)

The cellulose resin composition of the present invention is characterized in that the component (B) contains 30% by mass or more of (b-1).
The cellulose resin composition of the present invention is characterized in that the component (B) contains 30% by mass or more of (b-2).
The cellulose resin composition of the present invention is characterized in that the component (B) contains 30% by mass or more of (b-3).

  The cellulose resin composition of the present invention is characterized in that the component (B) is a polyester compound represented by the formula (b-1).

(In the formula (b-1), ^{n 8} is a number representing the average degree of polymerization, represents a number that is between 1 to 30, A is an aromatic having 6 to 18 carbon alkylene group or a C 1 to 18 carbon atoms G represents an alkylene group having 2 to 12 carbon atoms, E represents a hydrogen atom, an aliphatic acyl group having 2 to 10 carbon atoms, or an aromatic acyl group having 7 to 13 carbon atoms.)

  The cellulose resin composition of the present invention is characterized in that the component (B) is a polyester compound represented by the formula (b-2).

(In the formula (b-2), R ⁶¹ is an aromatic group having 6 to 20 carbon atoms which may have an aliphatic group, and R ⁶² is an n ^9- valent aliphatic group having 2 to 20 carbon atoms. And n ⁹ represents a number of 2 to 10.)

  The cellulose resin composition of the present invention is characterized in that the component (B) is a polyester compound represented by the formula (b-3).

(In the formula (b-3), R ⁷¹ is an aliphatic group having 1 to 20 carbon atoms which may have an aromatic group, and R ⁷² is an n ^10- valent aromatic group having 6 to 20 carbon atoms. N ¹⁰ represents a number of 2 to 4.)

  The cellulose resin composition of the present invention is characterized in that the cellulose resin is cellulose acylate.

Moreover, this invention is a film formed by shape | molding the said cellulose resin composition.
In addition, the present invention is a stretched optical compensation film characterized in that the film is stretched.

  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.
The cellulose-based resin (A) 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, cellulose butyrate, and the like. Mention may be made of 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. 2,319,052. it can.

(B-1) Polyester compound consisting of polyhydric alcohol and polycarboxylic acid (b-1) Polyester compound consisting of polyhydric alcohol and monocarboxylic acid (B-3) A polyester compound comprising a polyvalent carboxylic acid and a monoalcohol is used. 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.

  The compound represented by (C) used in the present invention can be synthesized by an arbitrary condensation reaction. For example, the compound of (c-3) is an aldol condensation reaction of a benzaldehyde compound and an acetophenone compound under a base catalyst. The compounds of (c-5) and (c-6) can be obtained from an alcohol, amine, hydrazine and the like corresponding to an acid halogen compound, and the compound of (c-8) is a base It can be synthesized by the reaction of a dibenzoylmethane derivative and an alkyl halide in the presence. However, the method for synthesizing the compound by the above method is not limited at all.

  In the general formula (b-1), examples of the C1-C18 alkylene group 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 A group in which any one hydrogen atom is removed.

In the general formula (b-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 (b-1), examples of the 2 to 12 alkylene group represented by G include the corresponding group and an alkylene group having an ether bond, such as a corresponding glycol, for example, ethylene. Examples include glycol, diethylene glycol, and triethylene 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, 2-ethyl -1, alkylene glycols such as 1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol, and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol and hexaethylene glycol In addition, a small percentage of glycerin and trimethylo Propane, trimethylol ethane, dipentaerythritol, polyalcohols 3 or more valences such as pentaerythritol 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 (b-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. Can be mentioned.
In the general formula (b-1), examples of the aromatic acyl group having 7 to 13 carbon atoms include benzoyl which may have a substituent, substituted or unsubstituted cinnamoyl and the like.
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.

In the general formula (b-2), R ⁶¹ 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, Cinnamic acid and the like can be mentioned, 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 can be mentioned.
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 (b-2), R ⁶² is an n ^9- valent aliphatic group, and the aliphatic group may be a chain, a ring, an ether bond, or interrupted by an aromatic ring. As the corresponding polyhydric alcohol, for example, 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-tri Lumpur, pinacol, sorbitol, pentaerythritol, dipentaerythritol, trimethylolpropane, trimethylolethane, xylitol, glucose, 1,4-phenylene methanol, and the like. Among these, trimethylolpropane, dipentaerythritol, mannitol, and glucose are preferable.

In the general formula (b-3), R ⁷¹ 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 -Methylhexyl, 2-ethylhexyl, 2-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, Examples include chlorhexyl and benzyl.

In the general formula (b-3), R ⁷² is an n ^10- valent aromatic group, and examples of the corresponding aromatic polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimethyl Mellitic acid, trimesic acid, pyromellitic acid, merit acid, naphthalenedicarboxylic acid and the like can be mentioned.

In the general formula (c-2), X ^{1 to} X ¹⁰ , in the general formula (c-3), X ^{11 to} X ²⁰ , in the general formula (c-4), X ^{21 to} X ³⁰ , the general In the formula (c-5), X ^{31 to} X ³⁵ and R ²² , in the general formula (c-6), X ^{41 to} X ⁴⁵ and R ³¹ , R ³² , in the general formula (c-7), R ^{41 to} R ⁴⁶ and the halogen atom represented by R ⁵³ in the general formula (c-8) include fluorine, chlorine, bromine, iodine and the like.

In the general formula (c-2), X ^{1 to} X ¹⁰ , in the general formula (c-5), X ^{31 to} X ³⁵ and R ²² , and in the general formula (c-6), X ^{41 to} X ⁴⁵ And R ³¹ , R ³² , the general formula (c-7), R ^{41 to} R ⁴⁶ , and the general formula (c-8), the substituted or unsubstituted C 1-10 represented by R ⁵³ Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl. , nonyl, isononyl, decyl, and the like, also, in general formula ^{(c-1), R 1} ~R 4, wherein in the general formula ^{(c-3), X 11} ~X 20, the one Wherein ^{(c-4), X 21} ~X 30, wherein in the general formula ^(c-8), as a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms represented by R ^{51, R 52,} said In addition to an alkyl group, dodecyl, icosyl and the like can be mentioned.

Further, in general formula ^{(c-2), X 1} ~X 10, in general formula ^{(c-5), X 31} ~X 35, R 22, in general formula ^{(c-6), X 41} ~ X ⁴⁵ , R ³¹ , R ³² , the general formula (c-7), R ^{41 to} R ⁴⁶ , and the general formula (c-8), the substituted or unsubstituted carbon represented by R ^{51 to} R ⁵³ Examples of the alkoxy group of 1 to 10 include those corresponding to an alkyl group, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, And neopentyloxy, 1,2-dimethyl-propoxy, hexyloxy, cyclohexyloxy, heptyloxy, octoxy, nonyloxy, decanoxy, etc. In general formula ^{(c-3), X 11} ~X 20, wherein in the general formula ^(c-4), as a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms represented by X 21 ^{to X 30} is In addition to the above alkoxy group, an alkoxy group corresponding to the above alkyl group and the like can be mentioned.

In the general formula (C), examples of the substituted or unsubstituted aryl group include phenyl, naphthyl, tolyl, benzyl, trityl, and styryl.
In the general formula (C), examples of the substituted or unsubstituted aryloxy group include those corresponding to the aryl group, and examples thereof include phenoxy and naphthoxy.
In the general formula (C), examples of the substituted or unsubstituted arylalkyl group include benzyl, phenethyl, 2-phenylpropan-2-yl, styryl, cinnamyl, diphenylmethyl, triphenylmethyl and the like. .
In the general formula (C), examples of the substituted or unsubstituted arylcarbonyl group include benzoyl and the like, and examples thereof include an arylcarbonyl group having a substituent corresponding to the alkyl group and the alkoxy group.
In the general formula (C), examples of the substituted or unsubstituted cycloalkyl group include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl, and the like.
In the general formula (C), examples of the substituted or unsubstituted alkanoyloxy group include alkanoyloxy groups corresponding to the alkyl groups.
In the general formula (C), the substituted or unsubstituted alkylcarbonyloxyalkyleneoxy group includes an alkylcarbonyloxyalkyleneoxy group corresponding to the alkyl group.
In the general formula (C), examples of the substituted or unsubstituted alkoxycarbonyl group include an alkoxycarbonyl group corresponding to the alkoxy group.
In the general formula (C), examples of the substituted or unsubstituted alkoxyalkyleneoxy group include alkoxyalkyleneoxy groups corresponding to the alkoxy groups and alkyl groups.
In the general formula (C), examples of the substituted or unsubstituted alkoxycarbonylalkyleneoxy group include alkoxycarbonylalkyleneoxy groups corresponding to the alkoxy groups and alkyl groups.
In the general formula (C), examples of the substituted or unsubstituted ketone diarylene group include a ketone diphenylene group.
In the general formula (C), examples of the substituted or unsubstituted oxydiarylene group include an oxydiphenylene group.

  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 be substituted or unsubstituted as described above.

  Although the polyester compound which consists of (b-1) polyhydric alcohol and polyhydric carboxylic acid represented by general formula (B) used by this invention below is illustrated, this invention is not limited by this. Absent. The inside of () of a mixture shows molar ratio. These polyester compounds may be used alone or in combination of two or more.

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 N ⁸ = 5 polyester compound comprising a group.
Compound No. 2: Polyester compound of n ⁸ = 2 comprising 1,2-propylene glycol as the polyhydric alcohol component G, 2,6-naphthalenedicarboxylic acid as the polyhydric carboxylic acid component A, and terminal E consisting of hydrogen.
Compound No. 3: Polyester compound of n ⁸ = 10 in which ethylene glycol is used as the polyhydric alcohol component G, and adipic acid is used as the polycarboxylic acid component A, and the terminal E is an acetyl group.
Compound No. 4: Polyester compound of n ⁸ = 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.

  Although the polyester compound which consists of a (b-2) polyhydric alcohol and monocarboxylic acid represented by general formula (B) used by this invention below is illustrated, this invention is not limited by this. . These polyester compounds may be used alone or in combination of two or more.

  The polyester compound which consists of the polyester compound which consists of a (b-3) polyhydric carboxylic acid and monoalcohol represented by the general formula (B) used by this invention below is illustrated, but this invention is limited by this. It is not something. These polyester compounds may be used alone or in combination of two or more.

Although the compound represented by (C) used by this invention below is illustrated, this invention is not limited by this.
In addition, the compound of (c-9) -1 is a mixture of compounds having different numbers of n ¹¹ (wherein n ¹¹ represents a number of 1 to 5).

また、これらポリエステル化合物の使用量は、セルロース系樹脂１００質量部に対し、１〜３０質量部、好ましくは１〜２０質量部である。この使用量が１質量部未満ではその効果が十分に発揮されず、一方、３０質量部を超えて使用した場合には、ブリードを生じるため、好ましくない。
これらポリエステル化合物は単独で用いても二種類以上を混合物として用いても良い。

Moreover, the usage-amount of these polyester compounds 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.
These polyester compounds may be used alone or in combination of two or more.

  Moreover, the usage-amount of the compound represented by these (C) is 0.1-50 mass parts with respect to 100 mass parts of cellulose resins, Preferably it is 1-20 mass parts. If the amount used is less than 0.1 parts by mass, the effect is not sufficiently exhibited. On the other hand, if the amount exceeds 50 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.
The cellulose resin composition of the present invention may further contain various additives such as phosphorus, phenol or sulfur antioxidants, ultraviolet absorbers, hindered amine light stabilizers and the like.

  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, bird Uril trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, 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 (Octylfe ) Bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)] 1,6-hexanediol diphosphite, tetratridecyl4,4'-butylidenebis Tributyl-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, tetrakis (2,4-ditert-butyl Phenyl) biphenylphosphonite 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- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol And bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

  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 -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-tert-butyl) -5-methylphenyl) -5-chlorobenzotriazole 2- (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) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol esters of carboxyphenyl) benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3 -Triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxy) 2- (2-hydroxyphenyl) -1,3,5-triazines such as ethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; phenyl salicylate, resorcinol mono Benzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-eth Substituted oxanilides such as xy-4′-dodecyloxanilide; cyano such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Acrylates, 2- (2-hydroxy-4- (2- (2-ethylhexanoyloxy) ethyloxy) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris (2- Hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4- (2-octanoyloxyethyl) phenyl) -1,3 5-triazine, tetrakis (α-cyano-β, β-diphenylacryloyloxymethyl) methane and the like can be mentioned.

  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-piperidyloxycarbonyl) 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-piperidyloxycarbonyl] ) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine- - yl) such as carbonate.

  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 mass of cellulose triacetate (degree of acetylation 61%, degree of polymerization 260) and the additives shown in Tables 1 to 9 below in the amounts (%) shown in the same table, 400 parts by mass of methylene chloride and 100 of methyl alcohol The mixture was uniformly dissolved in a mixed solvent consisting of parts by mass to prepare various dope solutions for evaluation of volatility and film formation. Next, the obtained dope solution was cast on a glass plate so as to have 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.

  It was confirmed that the obtained film was excellent in practicality.

Claims (10)

(A) For 100 parts by mass of cellulosic resin,
(B) 1 to 30 parts by mass selected from the group consisting of the following polyester compounds that are not cellulose esters,
(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 resin composition obtained by blending 0.1 to 50 parts by mass of one or more compounds represented by any one of the following general formulas (c-1) to (c-9).

(In the formula, n ¹ and n ² each independently represent 1 or 2, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or Represents a substituted or unsubstituted aryl group, and when n ³ = 0, the groups represented by R ³ and R ⁴ are linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded. May be.)

(Wherein, X ^{1 to} X ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. A group, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, wherein R ^{01 to} R ⁰⁴ are each independently a hydrogen atom, R ¹¹ represents an alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted ketone diarylene group. Or a substituted or unsubstituted oxydiarylene group.)

Wherein X ^{11 to} X ²⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and represented by X ^{11 to} X ²⁰ Two adjacent groups among the groups may be linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded.

(Wherein X ^{21 to} X ²⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and represented by X ^{22 to} X ²⁵ good .X ²⁶ to X ³⁰ may form a 5- or 6-membered ring together with the carbon atom to which each concatenated two adjacent groups are bonded among groups are each independently, Elementary atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted 1 to 20 alkoxy group, substituted Or an unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms, a substituted or unsubstituted carbon Represents an alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, and two adjacent groups among the groups represented by X ^{26 to} X ³⁰ are linked to each other. A 5-membered ring or a 6-membered ring may be formed together with the carbon atoms to be bonded, provided that not all of X ^{26 to} X ³⁰ are hydrogen atoms.

(In the formula, X ^{31 to} X ³⁵ and R ²² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 3 carbon atoms, 10 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl groups having 7 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 12 carbon atoms, A substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon A C3-C21 alkoxycarbonylalkyleneoxy group, a substituted or unsubstituted C3-C21 alkylcarbonyloxyalkyleneoxy group , A cyano group, a nitro group, a primary or secondary amino group, a substituted or an unsubstituted amide group, respectively coupled by connecting the two adjacent groups among the groups represented by X ³¹ to X ³⁵ A 5-membered ring or a 6-membered ring may be formed together with carbon atoms to be represented, and R ²¹ represents an n ⁴ -valent aromatic group or an n ⁴ -valent aliphatic group substituted with an aromatic group. )

(In the formula, X ^{41 to} X ⁴⁵ , R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon, An alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted cyclohexane having 5 to 12 carbon atoms; An alkyl group, a substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, substituted or unsubstituted Substituted C3-C21 alkoxycarbonylalkyleneoxy group, substituted or unsubstituted C3-C21 alkylcarbonyloxyalkylene Represents a nonoxy group, a cyano group, a nitro group, a primary or secondary amino group, a substituted or unsubstituted amide group, and two adjacent groups among the groups represented by R ^{41 to} R ⁴⁵ are linked. each may form a 5- or 6-membered ring together with the carbon atom bonded. Further, R ³³ is substituted with n ⁵ divalent aliphatic group or n ⁵ divalent aromatic group, or an aromatic group n represents a ^pentavalent aliphatic group.)

(In the formula, R ^{41 to} R ⁴⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, a substituted or unsubstituted group. An alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms Oxy group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms, substituted or unsubstituted alkanoyloxy group having 2 to 10 carbon atoms, substituted or unsubstituted An alkoxyalkyleneoxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 3 to 21 carbon atoms. Job aryloxycarbonyl alkyleneoxy group, a substituted or unsubstituted alkylcarbonyloxy alkyleneoxy group having a carbon number of 3 to 21, n ⁶ represents an integer of 0 or 1, of the groups represented by R ⁴¹ to R ⁴⁶ Two adjacent groups may be connected to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded, and this 5-membered or 6-membered ring may have a substituent. Examples of the divalent organic group represented by R ⁴⁷ include alkylene, cycloalkylene, arylene, and a combination thereof, each of which may be substituted or unsubstituted.

(In the formula, each of R ⁵¹ and R ⁵² independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon number. Represents a 7-20 arylalkyl group, R ⁵³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 2 to 10 carbon atoms, substituted Or an unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 20 carbon atoms, and Q is a hydrogen atom, a halogen atom, a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms. Alkyl groups, substituted or unsubstituted alkylcarbonyl groups having 2 to 10 carbon atoms, substituted or unsubstituted arylalkyl groups having 7 to 20 carbon atoms, substituted or unsubstituted 7 to 7 carbon atoms 0 arylcarbonyl group, or represents an alkylene group having 1 to 10 carbon atoms, when R ⁵³ or Q is a hydrogen atom, always the other represents those non-hydrogen atoms, and R ⁵³ and Q are linked carbon A ring group having a number of 3 to 30 may be formed, n ⁷ is an integer of 1 or 2, and when Q is not an alkylene group, n ⁷ represents 1 and when Q is an alkylene group, n ⁷ represents 2, and the substituent is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amide group, an amino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. Alkoxy group, alkanoyloxy group having 1 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, alkoxyalkyleneoxy group having 2 to 20 carbon atoms, alkoxycarbonylalkyl having 3 to 21 carbon atoms Represents a lenoxy group, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof, the alkyl group, the alkanoyloxy group, the alkoxycarbonyl group, the above The alkoxyalkyleneoxy group, the above alkoxycarbonylalkyleneoxy group, and the alkyl group in the arylalkyl group, or the above alkylene group have an oxygen atom, an ester group, a carbonyl group, or a substituted or unsubstituted carbon number of 6 to 20 carbon atoms. One or more of the aryl groups may be interrupted.)

(In formula (c-9), R ⁸¹ and R ⁸² each independently represents a hydrogen atom or a methyl group, and n ¹¹ represents an integer of 1 to 5.)   The cellulose resin composition of Claim 1 in which a component (B) contains 30 mass% or more of (b-1).   The cellulose resin composition of Claim 1 in which a component (B) contains 30 mass% or more of (b-2).   The cellulose resin composition of Claim 1 in which a component (B) contains 30 mass% or more of (b-3). The cellulose resin composition according to any one of claims 1 to 4, wherein the component (B) is a polyester compound represented by the formula (b-1).

(In the formula (b-1), ^{n 8} is a number representing the average degree of polymerization, represents a number that is between 1 to 30, A is an aromatic having 6 to 18 carbon alkylene group or a C 1 to 18 carbon atoms G represents an alkylene group having 2 to 12 carbon atoms, E represents a hydrogen atom, an aliphatic acyl group having 2 to 10 carbon atoms, or an aromatic acyl group having 7 to 13 carbon atoms.) The cellulose resin composition according to any one of claims 1 to 4, wherein the component (B) is a polyester compound represented by the formula (b-2).

(In the formula (b-2), R ⁶¹ is an aromatic group having 6 to 20 carbon atoms which may have an aliphatic group, and R ⁶² is an n ^9- valent aliphatic group having 2 to 20 carbon atoms. And n ⁹ represents a number of 2 to 10.) The cellulose resin composition according to any one of claims 1 to 4, wherein the component (B) is a polyester compound represented by the formula (b-3).

(In the formula (b-3), R ⁷¹ is an aliphatic group having 1 to 20 carbon atoms which may have an aromatic group, and R ⁷² is an n ^10- valent aromatic group having 6 to 20 carbon atoms. N ¹⁰ represents a number of 2 to 4.)   The resin composition according to any one of claims 1 to 7, wherein the cellulosic resin is cellulose acylate. A film formed by molding the resin composition according to claim 1.   A stretched optical compensation film, wherein the film according to claim 8 or 9 is stretched.