JP6054233B2 - Resin composition and optical film using the same - Google Patents

Description

  The present invention relates to a resin composition and an optical film using the same, and more specifically, a cellulose-based resin composition, in particular, a liquid crystal display device by adding a specific β-diketone compound to a cellulose ester. The present invention relates to a cellulose ester resin composition that is suitable as an optical film. Examples of such an optical film include a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film, and those in which these are laminated.

  In the liquid crystal display device, polarizing films are arranged on both sides of the liquid crystal cell depending on the display method. Various optical elements are used to improve display quality. For example, a retardation film for preventing coloring, a viewing angle widening film for improving a viewing angle of a liquid crystal display, and a contrast of a liquid crystal display. A brightness enhancement film or the like for increasing the brightness is used. These films are collectively called optical films.

  As the optical film, resin films such as cellulose acylate, polycarbonate, and polyolefin are used, and among them, cellulose acylate film is widely used because of its excellent bonding property to polyvinyl alcohol used in polarizers. It is used.

  However, since the cellulose acylate film as it is does not have sufficient retardation (birefringence) necessary for an optical film, various studies have been made to impart retardation to the cellulose acylate film. In particular, in recent years, a liquid crystal display device having a larger retardation has been demanded in order to further widen the viewing angle and reduce the film thickness.

  In order to increase the retardation of the optical film, a method of adding a retardation increasing agent is known. However, when a conventional retardation increasing agent is added in a large amount, problems such as bleed out occur, and it has been difficult to put it to practical use. Further, although a method for reducing the total acyl group substitution degree of cellulose has been proposed, there are problems such as an increase in hygroscopicity, and it has been difficult to put it to practical use.

  Under such circumstances, in recent years, various retardation increasing agents have been proposed. For example, Patent Document 1 proposes a retardation plate made of a cellulose ester film using a specific aromatic compound as a retardation increasing agent. Patent Document 2 proposes a cellulose ester film using a polycyclic aromatic compound having a phenolic hydroxyl group as a retardation increasing agent. On the other hand, Patent Document 3 proposes a UV filter element using dibenzoylmethane as an ultraviolet absorber rather than as a retardation increasing agent.

International Publication No. 2000/55657 Pamphlet JP 2010-222433 A JP 2003-177235 A

  However, since the specific aromatic compound in Patent Document 1 has insufficient compatibility with the cellulose ester resin, the effect of improving optical characteristics has been insufficient. Further, the polycyclic aromatic compound having a phenolic hydroxyl group in Patent Document 2 is also insufficient in compatibility with the cellulose ester resin, and thus the effect of improving optical properties is insufficient.

  On the other hand, the UV filter element described in Patent Document 3 is a technology relating to UV absorption to the last, and Patent Document 3 does not describe the effect of improving optical characteristics by adding a dibenzoylmethane compound. In addition, to the β-diketone compound described in Patent Document 3, by adding a certain amount in order to obtain a desired retardation value, the wavelength dispersibility becomes a forward wavelength dispersibility, and an oblique direction is obtained. There has been a problem that a so-called color shift (color unevenness) occurs in which the color changes.

In the present invention, “wavelength dispersibility” refers to the degree of variation in the polarization state (phase difference between the fast axis and the slow axis due to birefringence) in the light of each wavelength. "In-plane retardation (Ro ¹ ) for a light beam having a specific wavelength and in-plane retardation (Ro ² ) for a light beam having a longer wavelength than the specific wavelength are both positive, and Ro ¹ / Ro ² The property having a value exceeding 1.0 is referred to as “reverse wavelength dispersion”.

  Then, the objective of this invention is providing the optical film which consists of a cellulose resin which was excellent in the optical characteristic and the color nonuniformity was suppressed.

  As a result of intensive investigations to solve the above problems, the present inventors have achieved the above object by using a resin composition obtained by blending a specific β-diketone compound with a cellulose resin. As a result, the present invention has been completed.

（式中、Ｒ^４〜Ｒ^１３は、各々独立して、水素原子、直鎖若しくは分岐を有する炭素原子数１〜１０のアルキル基、または、炭素原子数１〜１０のアルコキシ基を表し、Ｒ^３およびＲ^１４は、各々独立して、水素原子、直鎖若しくは分岐を有する炭素原子数１〜１０のアルキル基、炭素原子数７〜２０のアリールアルキル基、または、炭素原子数７〜２０のアリールカルボニル基を表すが、Ｒ^３またはＲ^１４が水素原子である場合、必ず他方は水素原子ではないものを表す。）

（式中、Ｒ^１５〜Ｒ^３４は、各々独立して、水素原子、直鎖若しくは分岐を有する炭素原子数１〜１０のアルキル基、または、炭素原子数１〜１０のアルコキシ基を表し、Ｒ^３５は、炭素原子数１〜１０のアルキレン基を表し、Ｒ^３およびＲ^３’は、水素原子を表し、上記アルキレン基は、炭素原子数６〜２０のアリール基で単数または複数中断されていてもよい。）

That is, the resin composition of the present invention is a β-diketone compound represented by the following general formula (2) or (3) with respect to 100 parts by mass of the cellulose resin (however, excluding the following compound (2-1)). However, 0.5-30 mass parts is mix | blended.

(Wherein R ^{4 to} R ¹³ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ³ and R ¹⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. Represents an arylcarbonyl group, and when R ³ or R ¹⁴ is a hydrogen atom, the other is not necessarily a hydrogen atom.)

(Wherein R ^{15 to} R ³⁴ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; ³⁵ represents an alkylene group having 1 to 10 carbon atoms, R ³ and R ^{3 ′} represent a hydrogen atom, and the alkylene group is interrupted by one or more aryl groups having 6 to 20 carbon atoms. May be good.)

  The optical film of the present invention is formed by using the resin composition of the present invention. In the optical film of the present invention, cellulose acylate can be suitably used as the cellulose resin. The optical film of the present invention is particularly suitable as a film for a liquid crystal display device.

Here, excellent optical characteristics in the present invention means that a large retardation is imparted, and this retardation is generally the in-plane retardation value (Ro) of the film, and It can be grasped by the retardation value (Rth) in the thickness direction. Ro and Rth are values defined by the following equations, respectively. These retardation values Ro and Rth can be measured using, for example, an automatic birefringence meter such as KOBRA-WR (manufactured by Oji Scientific Instruments) or RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). .
Ro = (Nx−Ny) × d
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 (μm).)

  The optical film obtained by the resin composition of the present invention is excellent in optical characteristics, that is, has a large retardation. Therefore, a liquid crystal display device, particularly a VA liquid crystal display using a VA mode liquid crystal cell. It can be suitably used as a retardation film for an apparatus.

Hereinafter, the present invention will be described in detail.
The cellulose resin used in the present invention may be any type, but a low fatty acid ester of cellulose is preferable. The low fatty acid in the low fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Examples of the low fatty acid ester of cellulose include cellulose acetate, cellulose propionate, and cellulose butyrate. 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, JP-A-8-2311761, US Pat. No. 2,319,052, etc. Can do.

In the β-diketone compound used in the present invention, examples of the unsubstituted or substituted alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) include, for example, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, Examples include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like. The alkyl group may be interrupted by one or more of an oxygen atom, an ester group, a carbonyl group, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, such as a halogen atom, a hydroxyl group, or a nitro group. , A cyano group, an amino group, an amide group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, and the number of carbon atoms 2-10 alkoxycarbonyl group, C2-C20 alkoxyalkyleneoxy group, C3-C21 alkoxycarbonylalkyleneoxy group, C7-C20 arylalkyl group, C6-C20 May be substituted with an aryl group or a combination thereof.

Examples of the unsubstituted or substituted arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² include benzyl, phenethyl, 2-phenylpropan-2-yl, styryl, cinnamyl, Examples include diphenylmethyl and triphenylmethyl. The alkyl group in the arylalkyl group may be interrupted by one or more of an oxygen atom, an ester group, a carbonyl group, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, a halogen atom , Hydroxyl group, nitro group, cyano group, amino group, amide group, linear or branched alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkanoyloxy having 1 to 10 carbon atoms Group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkoxyalkyleneoxy group having 2 to 20 carbon atoms, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon The aryl group having 6 to 20 atoms or a combination thereof may be substituted.

Furthermore, examples of the unsubstituted or substituted aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² include phenyl, naphthyl, phenanthrene, and anthracenyl. The aryl group is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an amide group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a carbon atom. An alkanoyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkoxyalkyleneoxy group having 2 to 20 carbon atoms, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms, and 7 to 7 carbon atoms It may be substituted with a 20 arylalkyl group, an aryl group having 6 to 20 carbon atoms, or a combination thereof.

In the general formula (1), examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ³ and A include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second Examples include butyl, tertiary butyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like. The alkyl group may be interrupted by one or more of an oxygen atom, an ester group, a carbonyl group, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, such as a halogen atom, a hydroxyl group, or a nitro group. , A cyano group, an amino group, an amide group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, and the number of carbon atoms 2-10 alkoxycarbonyl group, C2-C20 alkoxyalkyleneoxy group, C3-C21 alkoxycarbonylalkyleneoxy group, C7-C20 arylalkyl group, C6-C20 May be substituted with an aryl group or a combination thereof.

In the general formula (1), examples of the alkylcarbonyl group having 2 to 10 carbon atoms represented by R ³ and A include acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3- Examples include methylbutanoyl, octanoyl, decanoyl, dodecanoyl and the like. The alkyl group in the alkylcarbonyl group is a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an amide group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. An alkoxy group, an alkanoyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkoxyalkyleneoxy group having 2 to 20 carbon atoms, an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms, It may be substituted with an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof.

In the general formula (1), the aryl alkyl group having 7 to 20 carbon atoms represented by R ³ and A, same can be mentioned an aryl alkyl group as described above.

In the general formula (1), examples of the arylcarbonyl group having 7 to 20 carbon atoms represented by R ³ and A include those linked to the aryl group by a carbonyl group.

  In the general formula (1), examples of the alkylene group having 1 to 10 carbon atoms represented by A include methylene, ethylene, propylene, propane-2,2-diyl, butylene, isobutylene, hexylene, heptylene and the like. Can be mentioned. The alkylene group may be interrupted by one or more of an oxygen atom, an ester group, a carbonyl group, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, such as a halogen atom, a hydroxyl group, or a nitro group. , A cyano group, an amino group, an amide group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, and the number of carbon atoms 2-10 alkoxycarbonyl group, C2-C20 alkoxyalkyleneoxy group, C3-C21 alkoxycarbonylalkyleneoxy group, C7-C20 arylalkyl group, C6-C20 May be substituted with an aryl group or a combination thereof.

で表される。また、上記アルコキシカルボニルアルキレンオキシ基は、具体的には、次式、

で表される。 Examples of the substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, C 1-10 alkyl groups such as nonyl, isononyl, decyl; alkoxy groups having 1-10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy; methanoyloxy, ethanoyloxy, propa An alkanoyloxy group having 1 to 10 carbon atoms such as noyloxy; an alkoxycarbonyl group having 2 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl; methoxymethyleneoxy, ethoxymethyleneoxy and methoxyethylene An alkoxyalkyleneoxy group having 2 to 20 carbon atoms such as xy; an alkoxycarbonylalkyleneoxy group having 3 to 21 carbon atoms such as methoxycarbonylethyleneoxy, ethoxycarbonylmethyleneoxy, methoxycarbonylethyleneoxy; benzyl, phenethyl, 2- Arylalkyl groups having 7 to 20 carbon atoms such as phenylpropan-2-yl, styryl, cinnamyl, diphenylmethyl and triphenylmethyl; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl, phenanthrene and anthracenyl; chloro Halogen atoms such as bromo and fluoro; hydroxyl groups and the like. The alkoxyalkyleneoxy group is specifically represented by the following formula:

It is represented by Further, the alkoxycarbonylalkyleneoxy group specifically has the following formula:

It is represented by

In the general formula (1), the cyclic group having 3 to 30 carbon atoms formed by connecting R ³ and A may be a monocyclic ring, a polycyclic ring, a condensed ring or an aggregate ring, and is an aromatic cyclic group. The saturated aliphatic cyclic group can be used without distinction, and part or all of the hydrogen atoms of the cyclic group are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. May be. Examples of the cyclic group having 3 to 30 carbon atoms include phenyl, naphthyl, anthracene, biphenyl, triphenyl, 2-methylphenyl (o-tolyl, cresyl), 3-methylphenyl (m-tolyl), 4- Methylphenyl (p-tolyl), 4-hydroxyphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl (xylyl), 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, , 4-ditertiarybutylphenyl, 2,5-ditertiarybutylphenyl, 2,6-ditertiarybutylphenyl, 2,4-ditertiarypentylphenyl, 2,5-ditertiaryamylphenyl, , 5-ditertiary octylphenyl, 2,4-dicumylphenyl, cyclohexylphenyl, 2,4,5-trimethylphenyl (mesityl), 3,4,5-trimethoxyphenyl, cyclopropyl, cyclobutyl, cyclohexyl, cyclo And heptyl.

  Examples of the alkyl group having 1 to 10 carbon atoms that replaces the hydrogen atom of the cyclic group include the same ones as the alkyl group.

Examples of the alkoxy group having 1 to 10 carbon atoms that replaces the hydrogen atom of the cyclic group include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyl List oxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, etc. can be, any -CH 2 in such alkoxy groups _- is an oxygen atom, it may be interrupted by a carbonyl group or an ester group, a part or all of the hydrogen atoms may be substituted by a halogen atom

Examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms represented by R ^{4 to} R ¹³ in the general formula (2) include the same alkyl groups as those described above.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^{4 to} R ¹³ in the general formula (2) include the same alkoxy groups as those described above.

Examples of the alkanoyloxy group having 1 to 10 carbon atoms represented by R ^{4 to} R ¹³ in the general formula (2) include the same alkanoyloxy groups as those described above.

As the alkoxycarbonyl group of the general formula (2) R ⁴ ~R ¹³ 2 to 10 carbon atoms represented by in may be the same as those described above alkoxycarbonyl group.

Moreover, the same thing as said alkoxy alkyleneoxy group is mentioned as a C2-C20 alkoxy alkylene oxy group represented by R < ⁴ > -R < ¹³ > in the said General formula (2).

Further, alkoxycarbonyl alkyleneoxy group having a carbon number 3 to 21 represented by R ⁴ to R ¹³ in the general formula (2) include the same alkoxycarbonyl alkylene group above.

The aryl alkyl group having 7 to 20 carbon atoms represented by R ⁴ to R ¹³ in the general formula (2) include the same above arylalkyl groups.

The aryl group having 6 to 20 carbon atoms represented by ^R 4 ^{to R 13} in the general formula (2) include the same as the aryl group.

The alkyl group having 1 to 10 carbon atoms represented by R ³ and R ¹⁴ in the general formula (2) include the same as the above alkyl group.

The alkyl group of the general formula (2) R ³ and 2 to 10 carbon atoms represented by R ¹⁴ in may be the same as those described above alkylcarbonyl group.

Moreover, as a C7-C20 arylalkyl group represented by R < ³ > and R < ¹⁴ > in the said General formula (2), the same thing as the said arylalkyl group is mentioned.

Examples of the arylcarbonyl group having 7 to 20 carbon atoms represented by R ³ and R ¹⁴ in the general formula (2) include the same arylcarbonyl groups as those described above.

Examples of the cyclic group having 3 to 30 carbon atoms formed by connecting R ³ and R ¹⁴ in the general formula (2) include the same as the cyclic group.

  In the present invention, examples of the β-diketone compound represented by the general formula (2) include the following compounds. However, the present invention is not limited by the following compounds.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ^{15 to} R ³⁴ in the general formula (3) include the same alkyl groups as those described above.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^{15 to} R ³⁴ in the general formula (3) include the same ones as the above alkoxy group.

Examples of the alkanoyloxy group having 1 to 10 carbon atoms represented by R ^{15 to} R ³⁴ in the general formula (3) include the same alkanoyloxy groups.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms represented by R ^{15 to} R ³⁴ in the general formula (3) include the same ones as the above alkoxycarbonyl group.

Formula (3) represented by R ¹⁵ to R ³⁴ in, as the alkoxy alkyleneoxy group having 2 to 20 carbon atoms include the same above alkoxy alkyleneoxy group.

Formula (3) represented by R ¹⁵ to R ³⁴ in, alkoxycarbonyl alkylene group of carbon atoms 3 to 21 include the same above alkoxycarbonyloxy alkyleneoxy group.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{15 to} R ³⁴ in the general formula (3) include the same arylalkyl groups as those described above.

Examples of the aryl group having 6 to 20 carbon atoms and represented by R ^{15 to} R ³⁴ in the general formula (3) include the same aryl groups as those described above.

Examples of the alkylene group having 1 to 10 carbon atoms represented by R ³⁵ in the general formula (3) include the same alkylene groups as those described above.

  In the present invention, examples of the β-diketone compound represented by the general formula (3) include the following compounds. However, the present invention is not limited by the following compounds.

  The amount of the β-diketone compound used is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the cellulose resin. If the amount used is less than 0.5 parts by mass, the effect is not sufficiently exhibited. On the other hand, if the amount used exceeds 30 parts by mass, bleeding may occur or physical properties of the optical film may be reduced. Therefore, it is not preferable.

Although it does not specifically limit as a manufacturing method of the (beta) -diketone compound based on this invention, For example, it can manufacture according to Reaction formula shown to the following [Chemical Formula 1] or [Chemical Formula 2]. Incidentally, ^R 4 ^{to R 13} in chemical formula 1] has the same meaning as ^R 4 ^{to R 13} in the general formula (2), ^R 15 ^{to R 35} in the chemical formula 2], the general formula ( 3) it has the same meaning as ^R 15 ^{to R 35} of, X in the chemical formula 1] and [Formula 2] represents a halogen atom.

[Chemical formula 1]

[Chemical formula 2]

  Here, as the base (BASE) used in the above reaction, metal oxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as lithium hydride and sodium hydride; carbonates such as potassium carbonate, sodium Examples thereof include metal alkoxides such as methoxide and potassium tert-butoxide. The amount of the base used is preferably added in equimolar amounts or more with respect to the halogen atom in the halogen compound to be added.

  The solvent (solv.) Used in the above reaction includes toluene, xylene, N, N-dimethylformamide (DMF), 1,3-dimethylimidazolidinone (DMI), THF, triethylamine, dimethylacetamide (DMAc). ), Chloroform, dichloromethane, pyridine, dimethyl sulfoxide (DMSO) and the like. Although the usage-amount of the said solvent can be made into arbitrary amounts, Preferably, it can use suitably in the range of 10-500 mass parts with respect to 100 mass parts of (beta) -diketone compounds.

  In addition, the optical film of the present invention further includes various additives such as modifiers (including plasticizers), phenolic, phosphorous, thioether antioxidants, ultraviolet absorbers, hindered amine light stabilizers, A flame retardant etc. can be mix | blended.

  Examples of the modifier (including a plasticizer) include dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl. Phthalate esters such as phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, triphenyl phosphate, biphenylyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate , Tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) ) Phosphate esters such as phosphate, octyl diphenyl phosphate, glycolic acid esters such as triacetin, tributyrin, butyl phthalyl butyl glycolate, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, pentaerythritol tetraacetate, etc. Compounds.

  Other examples of the plasticizer include the following. For example, adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate, 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, etc., and dibasic acids such as oxalic acid, malonic acid, succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., if necessary, monohydric alcohol, monocarboxylic acid (acetic acid, aromatic acid, etc.) Made using stopper Plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers such as tributyl acetylcitrate, trimellitic acid plasticizers, pyromellitic acid plasticizers, biphenylene polycarboxylic acid plasticizers And aromatic acid ester plasticizers such as trimethylolpropane tribenzoate.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4 Hydroxyphenyl) propionamide, 2,2′-oxamido-bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3 ′, 5 ′ -Di-t-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-t-butylphenol), 3,5-bis (1,1-dimethylethyl) -4- Hydroxy-benzenepropanoic acid and ester of C13-15 alkyl, 2,5-di-t-amylhydroquinone, hindered phenol polymer (trade name AO.OH998, manufactured by Adeka Palmalol), 2,2′-methylenebis [ 6- (1-methylcyclohexyl) -p-cresol], 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-me Rubenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butylbenz [d, f] [1,3,2] -dioxaphosphobin, Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7 -Bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone and o-xylene reaction product, 2,6-di-t-butyl-4- (4,6-bis ( Ok Tilthio) -1,3,5-triazin-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3 -Bis- (4′-hydroxy-3′-t-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol Stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-t- Butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], , 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-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (2, 6-di-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 1,1 , 3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ] Methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [2- ( -T-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β -(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide, palmityl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-ditert 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as tributyl-4-hydroxyphenyl) propionic acid amide I can get lost.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyloctylphenyl phosphite, diphenyltridecyl Phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) ) Phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonyl fe) Phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, Di (Tori Syl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl Tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4 , 4'-n-Butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, tetrakis (2, 4-di-t-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanyl-3-ylidene) tris (2-1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis 4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8, 10-tetrakis-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2, 4,8,10-tetraoxa-3,9-diphosphasspiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2ethyl-1,3-propanediolphos Phyto, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-t-butylphenol Sufaito, and the like.

  Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-t-butyl. Phenyl) sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol), distearyl- Disulfide is mentioned.

  Examples of the ultraviolet absorber include a benzotriazole compound, a triazine compound, a benzoate compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, an oxanilide compound, and other ultraviolet absorbers, but is compatible with a cellulose resin. Are preferable.

  Examples of the benzotriazole compound include 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-ditert-butyl-C7-9 mixed alkoxycarbonylethylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′- Methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) fur Nor), 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2 -Hydroxy-3-secondarybutyl-5-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) benzotriazole, 3- (2H-benzotriazoyl) -5-tert-butyl-4-hydroxy-benzenepropanoic acid octyl ester, 2- [2-hydroxy-3- (3,4, 5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-carboxyl) Yl) benzotriazole compounds such as polyethylene glycol esters of benzotriazole.

  Examples of the triazine compound include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) -phenol, 2,4. -Bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctylphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 1,6-hexadiamine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) ) And 2,4-dichloro-6- (4-morpholinyl) -1,3,5-triazine, 2- (4,6-bis- (2,4-dimethylphenyl) -1,3,5 -Triazin-2-yl) -5-octylo Ii) -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[(2-hydroxy-3) -(2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- [2-hydroxy- 3-dodecyloxypropyl] oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4-[(2-hydroxy-3- Tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Examples of the benzoate compound include resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, and 2,4-ditert-butylamylphenyl-3,5. -Di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like.

  Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-benzoyloxy-2-hydroxybenzophenone, methylene [Bis (hydroxymethoxyphenylene)] bis (phenyl) ketone, 1,4-bis (4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, poly-4- (2-acryloxyethoxy) -2- Hydroxybenzophenone, 2- Droxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, diisodium-2,2′-dihydroxy-4,4′-dimethoxy-5,5′- Examples include dibenzoic acid benzophenone 2-hydroxy-4-tert-butyl-4 ′-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), and the like.

  Examples of the cyanoacrylate compound include 1,3-bis [(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis-{[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] methyl} -propane, ethyl-2-cyano-3,3-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, (2-ethylhexyl) ) -2-cyano-3,3-diphenyl acrylate and the like.

  Examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate.

  Examples of the oxanilide compound include 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide and the like.

  Examples of other UV absorbers include N- (4-ethoxycarbonylphenyl) -N′-methyl-N′-phenylformamidine, N- (ethoxycarbonylphenyl) -N′-ethyl-N′-ethyl- N′-phenylformamidine, tetraethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, [(4-methoxy-phenyl) -methylene] -dimethyl ester, 4,4′-hexamethylenebis ( 1,1-dimethylsemicarbazide) and the like.

  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, and 2,2,6. , 6-Tetramethyl-4-piperidylbenzoate, bis (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) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-pi Lysyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-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 / 2,4-dichloro-6-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, -Tetramethyl-4-piperidyl) amino) -s-triazin-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-triazin-6-yl] aminoundecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis {4- (1-octyloxy-2,2,6,6-tetramethyl Le) piperidyl} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVINNOR 371 manufactured by Ciba Specialty Chemicals.

  Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate), (1-methylethylidene) ) Di-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, ADK STAB FP-500 (manufactured by ADEKA), ADK STAB FP-600 (ADEKA) ), Adekastab FP-800 (manufactured by ADEKA), etc., aromatic phosphoric acid esters, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl and phenylphosphonic acid (1-butenyl) phosphonic acid esters, di Phosphinic acid esters such as phenyl phenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing flame retardants such as phosphorus-containing vinylbenzyl compounds and red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis Pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene Ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, Examples thereof include pentabromobenzyl acrylate and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, and flame retardant aids such as polyhydric alcohols and hydrotalcite.

  In addition, the optical film of the present invention may further include other additives such as a filler, a colorant, a crosslinking agent, an antistatic agent, a plate-out preventing agent, a surface treatment agent, a lubricant, a flame retardant, if necessary. Fluorescent agents, fungicides, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents and the like can be blended.

  The resin composition of the present invention can be used without being limited to the processing method. Examples of the processing method include processing methods such as solution casting, melt casting, calendaring, roll processing, extrusion molding, melt rolling, pressure molding, and powder molding.

  By molding the resin composition of the present invention, it can be used as a molded article having optical anisotropy. This molded body is, for example, a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarizing element, dichroic polarizing plate, liquid crystal alignment film, antireflection film, selective reflection film, viewing angle compensation film It can be used as an optical film.

  In addition, the optical film of the present invention selectively displays specific light (for example, visible light, near infrared light) in addition to a film for a display (liquid crystal display device) including a retardation film, a brightness enhancement film, a pattern retarder film, and the like. And a selective reflection film having a function of reflecting light. It can also be used for information recording materials such as optical lenses such as liquid crystal lenses and microlenses, PDLC electronic paper, and digital paper.

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

  The optical film of the present invention is produced, for example, 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%.

  The solvent used for the preparation of the dope solution according to the present invention may be a single solvent or a mixture of two or more solvents, but it is preferable in terms of production efficiency to use a good solvent and a poor solvent of 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, good solvents and poor solvents are not uniquely determined in all cases. In the case of cellulose triacetate which is a preferred cellulose ester 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, And methyl acetate. 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 ester when preparing the dope solution, a general method can be used, but the temperature is within the range where the solvent does not boil under pressure under the normal pressure of the solvent. The method of heating with stirring and 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 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 not less than the boiling point of the solvent used at normal pressure and in a range where the solvent 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 the productivity deteriorates. The range of preferable heating temperature is 45-120 degreeC, 60-110 degreeC is more preferable, and 70-105 degreeC is further 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 can be used without any particular limitation. For example, a plastic filter medium such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel are preferable because fibers do not fall off.

The dope solution can be filtered by a normal method, but the method of filtering while heating at a temperature that is higher than the boiling point of the solvent under normal pressure and in a range where the solvent does not boil is applied before and after the filter medium. The increase in the differential pressure (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 further more preferable. A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 × 10 ⁶ Pa or less, and more 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 or the 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 the cellulose ester film, the film peeled off from the support is further dried, and the residual solvent amount is preferably 3% by mass or less, more preferably 0.5% by mass or less. 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.

  It is preferable to maintain or stretch the width by a tenter method while the amount of residual solvent immediately after peeling from the support is large, since 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 optical film is preferable because it makes it easier to reduce the thickness of the display device. However, if it is too thin, the moisture permeability increases and the tear strength is insufficient. As a film thickness of the optical film which makes these compatible, 10-150 micrometers is preferable and 20-100 micrometers is more preferable.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by the following examples.

  Cellulose acylate (acetyl group substitution degree 2.00, butyryl group substitution degree 0.70, polymerization degree 220) is 100 parts by mass, and the additives shown in Table 1 below are parts by mass shown in the same table, and methylene chloride is 400 parts by mass. Various dope solutions were prepared by uniformly dissolving with stirring in a mixed solvent consisting of 100 parts by mass of methyl alcohol and 100 parts by mass of methyl alcohol. Next, the obtained dope solution was cast on a glass plate to a thickness of about 0.1 mm, dried at room temperature for 16 hours, then dried at 50 ° C. for 1 hour, and further at 120 ° C. for 1 hour. Dried. Thereafter, uniaxial stretching was performed at 170 ° C. at a stretching speed of 15 mm / min using a stretching apparatus EX10-B1 (manufactured by Toyo Seiki Co., Ltd.) to obtain various evaluation films. The film thicknesses of the obtained films were all about 80 μm, and the draw ratio was 1.25 medium.

  The following evaluation was performed using the obtained film. These results are shown in Table 1 below. In addition, the number of the compound in a table | surface represents the number of said corresponding (beta) -diketone compound.

(Retardation value)
The obtained film was subjected to in-plane retardation (Ro) at a wavelength of 590 nm under an environment of 25 ° C. and 60% RH using an automatic birefringence meter RETS-100 (manufactured by Otsuka Electronics Co., Ltd.) according to the following formula. It was measured.
Ro = (Nx−Ny) × d
(In the formula, Nx represents the refractive index in the direction where the refractive index within the film surface is the largest, Ny represents the refractive index within the film surface in the direction perpendicular to Nx, and d represents the thickness (nm) of the film.)

(Wavelength dispersion)
In the central part of the width direction of the film, an automatic birefringence meter RETS-100 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure retardation at wavelengths of 450 nm and 630 nm in an environment of 25 ° C. and 60% RH. The wavelength dispersion was determined by substituting into the following equation. In the present invention, this value is preferably 1.00 or less.
Wavelength dispersion = Ro (450 nm) / Ro (630 nm)

(Yellowness (YI))
About the obtained film, yellowness (YI) was measured according to ASTM D 1925 using a spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd .; MSC-IS-2DH).

(Evaluation of bleed resistance)
The obtained film was cut into a size of 30 mm × 40 mm and left in a high temperature and high humidity of 85 ° C. and 90% relative humidity for 120 hours. Thereafter, the film surface was visually observed and evaluated as x when the bleed material was confirmed and evaluated as ◯ when the bleed material could not be confirmed.

(Volatile)
30 mg of each additive compound was weighed and used as a measurement sample. Using Rigaku Thermoplus 2 / (TG-DTA series), 140 ° C. from room temperature under a nitrogen atmosphere (flow rate: 200 ml / min), measurement sample: 5 mg, and heating rate: 20 ° C./min. The temperature was raised to ° C and maintained at 140 ° C for 60 minutes. Measure the weight reduction amount of the measurement sample at this time, x if the weight is reduced by 2% or more, △ if it is reduced within the range of 1-2%, if the weight reduction is less than 1% As ◯, the volatility of the measurement sample was evaluated.

＊１）コントロール：β−ジケトン化合物未配合，
比較化合物１：１，３−ジフェニル−プロパン−１，３−ジオン，
比較化合物２：１−（４−第三ブチルフェニル）−３−（４−メトキシフェニル）−プロパン−１，３−ジオン，
比較化合物３：１，３−ビス（４−メトキシフェニル）−プロパン−１，３−ジオン

* 1) Control: β-diketone compound not included,
Comparative compound 1: 1,3-diphenyl-propane-1,3-dione,
Comparative compound 2: 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione,
Comparative compound 3: 1,3-bis (4-methoxyphenyl) -propane-1,3-dione

  From Comparative Examples 2 to 4 in Table 1 above, the optical film using the conventional β-diketone compound has a high retardation value but a wavelength dispersibility higher than 1 and a color tone, and a bleed product is confirmed. There was a case. On the other hand, it was confirmed that the optical films of the respective examples showed reverse dispersibility in wavelength dispersion, excellent color tone, and suppressed bleeding.

Further, when the optical film of the present invention was mounted on a liquid crystal display device in an environment of 23 ° C. and 55%, the liquid crystal display was displayed in black, and color unevenness was confirmed from the front and an oblique 45 ° angle. It was confirmed that there was no.
From the above, it was confirmed that the optical film of the present invention is an optical material suitably used in a liquid crystal display device.

Claims (4)

0.5 to 30 parts by mass of β-diketone compound represented by the following general formula (2) or (3) ( excluding the following compound (2-1)) is added to 100 parts by mass of the cellulose resin. A resin composition characterized by being made.

(Wherein R ^{4 to} R ¹³ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ³ and R ¹⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 7 to 20 carbon atoms. Represents an arylcarbonyl group, and when R ³ or R ¹⁴ is a hydrogen atom, the other is not necessarily a hydrogen atom.)

(Wherein R ^{15 to} R ³⁴ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; ³⁵ represents an alkylene group having 1 to 10 carbon atoms, R ³ and R ^{3 ′} represent a hydrogen atom, and the alkylene group is interrupted by one or more aryl groups having 6 to 20 carbon atoms. May be good.)

An optical film formed by using the resin composition according to claim 1 . The optical film according to claim 2 , wherein the cellulose resin is cellulose acylate. The optical film according to claim 2 or 3, which is a film for a liquid crystal display device.