JP6121811B2 - Retardation raising agent - Google Patents

Description

  The present invention relates to a retardation increasing agent used for an optical film, a cellulose resin composition containing the same, and a film obtained from the cellulose resin composition.

  Until now, resin films such as cellulose acylate, polycarbonate, and polyolefin have been mainly used for optical compensation films for liquid crystal display devices. Among them, cellulose acylate films are widely used because of their excellent bonding properties to polyvinyl alcohol used for polarizers.

  However, since the retardation (birefringence) essential for the optical compensation film is not sufficient if the cellulose ester film is used as it is, various studies for imparting retardation to the cellulose ester film have been made. 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 bleed out. 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, Patent Document 1 proposes a retardation plate made of a cellulose ester film containing a retardation improver made of a specific aromatic compound. Patent Document 2 proposes a cinnamic acid derivative compound having a photoreactive group as a retardation increasing agent. Furthermore, Patent Document 3 proposes a retardation increasing agent based on a combination of a specific polycyclic aromatic compound and a sugar ester compound.

Japanese Patent No. 4605908 JP 2007-25203 A International Publication No. WO2007 / 125564

  However, since the cellulose ester film containing the retardation increasing agent composed of a specific aromatic compound in Patent Document 1 has insufficient compatibility, the effect of improving optical properties has been insufficient. In addition, when the cinnamic acid derivative compound having a photoreactive group in Patent Document 2 is used as a retardation increasing agent, a light irradiation reaction with a non-liquid crystalline polymer is required, which increases the number of processes and incidental facilities. It is disadvantageous in terms of cost due to necessity. For this reason, the technique which does not have a special installation and improves retardation is desired. In Patent Document 3, a sugar ester compound is mentioned as a retardation increasing agent, and cinnamic acid is described as an example of an acid, but there is no specific description of a compound using cinnamic acid. Moreover, by using a sugar ester as a retardation increasing agent, the retardation is lowered as compared with the case where it is not added.

Accordingly, an object of the present invention is to provide a retardation increasing agent that is excellent in compatibility and can impart a large retardation.
Another object of the present invention is to provide a cellulose resin composition containing the retardation increasing agent.
Furthermore, the other object of this invention is to provide the film which has the outstanding optical characteristic obtained from this cellulose resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by using a specific compound as a retardation increasing agent, and have completed the present invention.

（式中、Ｒ^１〜Ｒ^５は水素原子を表し、また、Ｒ^６はｎ１価の芳香族基、若しくは芳香族基で置換されたｎ１価の脂肪族基を表す。）

（式中、Ｒ^１１〜Ｒ^１７は水素原子、ハロゲン原子、ヒドロキシル基、置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有し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、置換基を有し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、シアノ基、ニトロ基、１級又は２級のアミノ基、置換基を有してもよいアミド基を表し、Ｒ^１１〜Ｒ^１５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。また、Ｒ^１８はｎ２価の脂肪族基またはｎ２価の芳香族基、若しくは芳香族基で置換されたｎ２価の脂肪族基を表す。） That is, the retardation increasing agent of the present invention is characterized by comprising at least one of the compounds represented by the following general formulas (1) and (2).

(Wherein R ^{1 to} R ⁵ represent a hydrogen atom, and R ⁶ represents an n1-valent aromatic group or an n1-valent aliphatic group substituted with an aromatic group.)

(Wherein R ^{11 to} R ¹⁷ are a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. 10 alkoxy groups, aryloxy groups having 6 to 20 carbon atoms that may have substituents, arylalkyl groups having 7 to 20 carbon atoms that may have substituents, and substituents Good C5-C12 cycloalkyl group, C2-C10 alkanoyloxy group which may have a substituent, C2-C20 alkoxyalkyleneoxy group which may have a substituent , An optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms, and an optionally substituted carbon A with 3 to 21 atoms Kill carbonyl oxyalkylene group, a cyano group, a nitro group, a primary or secondary amino groups, represent an amido group which may have a substituent group, 2 adjacent Among the groups represented by R ¹¹ to R ¹⁵ R ¹⁸ may form a 5-membered ring or a 6-membered ring together with carbon atoms to which each group is bonded, and R ¹⁸ is an n2-valent aliphatic group, an n2-valent aromatic group, or an aromatic group. Represents an n2-valent aliphatic group substituted with a group.)

The retardation increasing agent of the present invention preferably has 1 to 4 carbon atoms in the aliphatic group moiety in the aliphatic group substituted with the aromatic group represented by R ⁶ in the general formula (1). The aromatic group represented by R ⁶ in the general formula (1) is preferably an aromatic group having 6 to 12 carbon atoms.

  In the retardation increasing agent of the present invention, n2 in the general formula (2) is preferably 1.

  The cellulose resin composition of the present invention is characterized in that 0.1 to 30 parts by mass of the retardation increasing agent is blended with 100 parts by mass of the cellulose resin.

  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 above cellulose-based resin composition.

In the present invention, being excellent in optical properties means that a large retardation is imparted, and this retardation can be generally 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). ]
These retardation values and Rth can be measured using an automatic birefringence meter such as KOBRA-WR (manufactured by Oji Scientific Instruments) or RETS-100 (manufactured by Otsuka Electronics Co., Ltd.).

  According to the present invention, it 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.

Hereinafter, the present invention will be described in detail.
<Cellulosic resin>
The cellulose 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, for example, cellulose acetate, cellulose propionate, cellulose butyrate, JP-A-10-45804, JP-A-8-231761, and U.S. Pat. No. 2,319,052. Examples thereof include mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in the literature.

<Retardation raising agent>
In the general formulas (1) and (2), examples of the halogen atom that R ^{1 to} R ⁵ , R ^7, and R ^{11 to} R ¹⁷ can include fluorine, chlorine, bromine, iodine, and the like.

In the general formulas (1) and (2), the alkyl group having 1 to 10 carbon atoms that may have a substituent that R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ may have, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-amyl, 1,2-dimethylpropyl, n-hexyl, 1,3 -Dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3- Methylbutyl, n-octyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propylhexyl, n- Cycloalkenyl, isononyl, n- decyl, isodecyl, and the like.

In the general formula (1) and ^(2), examples of the alkoxy group R ¹ to R 5, ^{R 7} and ^R 11 ^{to R 17} are carbon atoms which may have a substituent which may take from 1 to 10 Are those corresponding to the above alkyl groups, specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyl. Examples include oxy, neopentyloxy, 1,2-dimethyl-propoxy, n-hexyloxy, cyclohexyloxy, 1,3-dimethylbutoxy, 1-isopropylpropoxy and the like.

In the general formulas (1) and (2), examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent which R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ can take. Examples thereof include those corresponding to the above aryl groups, and specific examples include phenoxy, naphthoxy and the like.

In the general formulas (1) and (2), examples of the arylalkyl group having 7 to 20 carbon atoms which may have a substituent which R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ can take. Examples thereof include benzyl, phenethyl, 2-phenylpropan-2-yl, styryl, cinnamyl, diphenylmethyl, triphenylmethyl and the like.

In the general formula (1) and ^(2), cycloalkyl groups of R ¹ to R 5, ^{R 7} and ^R 11 ^{to R 17} may 5 to 12 carbon atoms which may have a substituent which may take examples Examples thereof include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like.

In the general formulas (1) and (2), examples of the alkanoyloxy group having 2 to 10 carbon atoms which may have a substituent which R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ can take. As, there may be mentioned an alkanoyloxy group corresponding to the alkyl group.

In the general formulas (1) and (2), R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ may have a substituent which may have a substituent of an alkoxyalkyleneoxy group having 2 to 20 carbon atoms. Examples include an alkoxyalkyleneoxy group corresponding to the alkyl group.

In the general formulas (1) and (2), examples of the alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent that R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ can take. As for, the alkoxycarbonyl group corresponding to the said alkyl group is mentioned.

In the general formulas (1) and (2), an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms which may have a substituent that R ^{1 to} R ⁵ , R ⁷ and R ^{11 to} R ¹⁷ can take. Examples of these include alkoxycarbonylalkyleneoxy groups corresponding to the alkyl groups.

In general formula (1) and in ^(2), R ¹ to R 5, ^{R 7} and ^R 11 ^{to R 17} are carbon atoms which may have a substituent which may take 3-21 alkylcarbonyloxy alkyleneoxy Examples of the group include an alkylcarbonyloxyalkyleneoxy group corresponding to the alkyl group.

In the general formulas (1) and (2), two adjacent groups among the groups represented by R ^{1 to} R ⁵ and R ^{11 to} R ¹⁵ are linked together with the carbon atom to which each is bonded to form a 5-membered ring. Alternatively, a 6-membered ring may be formed.
Examples of the 5-membered ring include a cyclopentene ring, a cyclopentadiene ring, an imidazole ring, a thiazole 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 the 6-membered ring may have a substituent.

In the general formulas (1) and (2), examples of the aliphatic n2-valent organic group represented by R ¹⁸ include methane, ethane, propane, butane, 2-methylpropane, pentane, 2,2- N hydrogen atoms from alkanes such as dimethylpropane, 2-methylbutane, hexane, heptane, octane, 2-ethylhexane, 2,2,4-trimethylpentane, nonane and decane, and alkenes such as ethylene, propylene and butene. Excluded groups are mentioned. The position of the hydrogen atom to be removed is not particularly limited, and may be any of primary, secondary, and tertiary. These n-valent aliphatic organic groups may have a substituent such as a hydroxy group or a halogen atom, and may have a bond such as an ether bond, a thioether bond, an ester bond, or an amide bond. Examples of the aromatic n1 and n2 organic groups represented by R ⁶ and R ¹⁸ include aromatic compounds such as naphthalene, anthracene, biphenyl, and terphenyl, and aliphatic substitution such as toluene, xylene, and ethylbenzene. And a group obtained by removing n1 and n2 hydrogen atoms from an aromatic compound having a group. The position of the hydrogen atom to be removed is not particularly limited, and may be from an aromatic group or an aliphatic group. These n1 and n2 valent aromatic organic groups may have a substituent such as a hydroxy group or a halogen atom in an aromatic group or an aliphatic group, and a bond such as an ether bond, a thioether bond, an ester bond or an amide bond. You may have. Furthermore, examples of the n1 and n2 valent aliphatic group substituted with an aromatic group represented by R ⁶ and R ¹⁸ include the above aromatic groups and aliphatic groups.

  In general formula (1), n1 is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of availability. For the same reason, in the general formula (2), n2 is preferably 1 to 20, and more preferably 1 to 10.

これら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よい。 Specific examples of the retardation increasing agent used in the present invention are shown below, but the present invention is not limited thereto.

These compounds may be used alone or in combination of two or more.

  Moreover, the usage-amount of these compounds is 0.1-30 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 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.

  A plasticizer can be arbitrarily used in the cellulose resin composition of the present invention. 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- Examples include 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 -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 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 required, for example, fillers, colorants, crosslinking agents, antistatic agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, A glaze, disinfectant, metal deactivator, release agent, pigment, processing aid, antioxidant, light stabilizer, foaming agent, and the like can be blended.

  As a method for synthesizing the compound in the present invention, it can be synthesized by an arbitrary condensation reaction, and for example, it can be obtained from an alcohol, amine, hydrazine or the like corresponding to an acid halogen compound. However, the method for synthesizing the compound by the above method is not limited at all.

  Next, although the manufacturing method of the film of this invention is demonstrated, it is not limited by the following methods.

  The film production method of the present invention is performed by applying and drying a dope solution in which a cellulose resin is dissolved in a solvent. Various additives can be mixed in the dope liquid as necessary. The concentration of cellulosic resin in the dope solution is preferably higher because the drying load after casting on the support can be reduced. However, if the concentration of cellulosic resin is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-30 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used for the preparation of the dope liquid according to the present invention may be used alone or in combination of two or more. However, it is possible to use a mixture of a good solvent and a poor solvent of cellulose resin in terms of production efficiency. preferable. 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. Regarding the good solvent and the poor solvent used in the present invention, those that dissolve the cellulose resin used alone are defined as good solvents, and those that only swell or cannot be dissolved alone are defined as poor solvents. Therefore, depending on the average degree of acetylation of the cellulose resin, the good solvent and the poor solvent change. For example, acetone becomes a good solvent in a cellulose resin having an average degree of acetylation of 55%, and cellulose having an average degree of acetylation of 60%. It becomes a poor solvent in the system resin. Thus, the good solvent and the poor solvent are not uniquely determined in all cases. In the case of cellulose triacetate which is a preferred cellulose resin in the present invention, examples of the good solvent include organic halogen compounds such as methylene chloride and dioxolanes. In the case of cellulose acetate propionate, methylene chloride, Acetone, methyl acetate and the like can be mentioned. On the other hand, in these cases, examples of the poor solvent include methanol, ethanol, n-butanol, cyclohexane, and cyclohexanone.

  As a method for dissolving the cellulose-based resin when preparing the dope solution, a general method can be used, but under pressure, at a temperature not lower than the boiling point at the normal pressure of the solvent and in a range where the solvent does not boil. A method of heating and stirring while stirring is preferable because it can prevent the generation of massive undissolved material called gel or mamako. Further, a method in which a cellulose resin 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 addition of the solvent is preferably a temperature that is not less than the boiling point of the solvent used at normal pressure and that the solvent does not boil from the viewpoint of the solubility of the cellulose resin. 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 resin 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 resin 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. And particularly preferably 20 to 30% by mass or 70 to 115% by 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-type resin 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.

  A thinner film thickness as the stretched optical compensation film is preferable because it makes it easier to reduce the thickness of the liquid crystal display. However, if it is too thin, the moisture permeability increases and the tear strength and the like are insufficient. As a film thickness of the cellulose resin 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.
<< Examples 1 to 9, Reference Examples 1 to 4, Comparative Examples 1 to 4 >>
Cellulose triacetate (degree of acetylation 61.5%, degree of polymerization 260) is 100 parts by mass and the additives listed in Tables 1 to 3 below are parts by mass described in the same table, 400 parts by mass of dichloromethane and 100 parts by mass of methyl alcohol. Various dope solutions were prepared by uniformly dissolving in a mixed solvent consisting of 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.

<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). ]

<Volatilization evaluation method>
For the compounds shown in Tables 1 to 4 below using a calorimeter measuring device (manufactured by Rigaku), the weight loss (%) after holding at nitrogen 200 ml / min, 20 ° C./min, 140 ° C. for 60 minutes is 1. When it was less than 5%, it was evaluated as ○, and when it was 1.5% or more, it was evaluated as ×. The results are shown in Tables 1 to 4 below.

Claims (7)

A retardation increasing agent comprising at least one compound represented by the following general formulas (1) and (2).

^(Wherein, R 1 ~ ^{R 5} is table hydrogen atom, or, ^{R 6} represents a n1 divalent aliphatic group substituted with n1 valent aromatic group, or an aromatic group.)

(Wherein R ^{11 to} R ¹⁷ are a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. 10 alkoxy groups, aryloxy groups having 6 to 20 carbon atoms that may have substituents, arylalkyl groups having 7 to 20 carbon atoms that may have substituents, and substituents Good C5-C12 cycloalkyl group, C2-C10 alkanoyloxy group which may have a substituent, C2-C20 alkoxyalkyleneoxy group which may have a substituent , An optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms, and an optionally substituted carbon A with 3 to 21 atoms Kill carbonyl oxyalkylene group, a cyano group, a nitro group, a primary or secondary amino groups, represent an amido group which may have a substituent group, 2 adjacent Among the groups represented by R ¹¹ to R ¹⁵ R ¹⁸ may form a 5-membered ring or a 6-membered ring together with carbon atoms to which each group is bonded, and R ¹⁸ is an n2-valent aliphatic group, an n2-valent aromatic group, or an aromatic group. Represents an n2-valent aliphatic group substituted with a group.) The retardation increasing agent according to claim 1, wherein the number of carbon atoms in the aliphatic group moiety in the aliphatic group substituted with the aromatic group represented by R ⁶ in the general formula (1) is 1 to 4. Retardation increasing agent according to claim 1, wherein the aromatic group represented by R ⁶ is an aromatic group having 6 to 12 carbon atoms in the general formula (1).   The retardation increasing agent according to claim 1, wherein n2 in the general formula (2) is 1.   A cellulose resin composition comprising 0.1 to 30 parts by mass of the retardation increasing agent according to any one of claims 1 to 4 with respect to 100 parts by mass of the cellulose resin.   The cellulose resin composition according to claim 5, wherein the cellulose resin is cellulose acylate.   A film formed by molding the cellulose resin composition according to claim 5 or 6.