KR101841854B1

KR101841854B1 - Cellulose acylate film, polarizer, and liquid-crystal display device

Info

Publication number: KR101841854B1
Application number: KR1020167002315A
Authority: KR
Inventors: 다카시 세라; 히로카즈 사토
Original assignee: 코니카 미놀타 가부시키가이샤
Priority date: 2013-08-12
Filing date: 2014-08-01
Publication date: 2018-03-23
Also published as: TW201520039A; TWI537129B; CN105473653A; CN105473653B; WO2015022867A1; KR20160027053A; JPWO2015022867A1; JP6428621B2

Abstract

Disclosure of the Invention Problems to be Solved by the Invention A problem to be solved by the present invention is to provide a filter for preventing the fluctuation of phase difference relative to humidity from volatilization and scattering in a production line, , And to provide a cellulose acylate film having both stability of retardation against humidity fluctuation and continuous production suitability. The cellulose acylate film of the present invention comprises a cellulose acylate and a nitrogen-containing heterocyclic compound having a molecular weight within a range of from 100 to 800 and having a melting point in the range of -60 to 120 占 폚, And an organic ester having a 1% mass reduction temperature Td1 within a range of 100 to 350 占 폚.

Description

TECHNICAL FIELD [0001] The present invention relates to a cellulose acylate film, a polarizing plate, and a liquid crystal display device using the cellulose acylate film,

The present invention relates to a cellulose acylate film, a polarizing plate and a liquid crystal display device. More specifically, even when the humidity of the environment fluctuates, even when the compound contains a compound that suppresses the fluctuation of the retardation and the compound volatilizes and disperses in the production line, the non-product is efficiently collected to improve the clogging of the filter To a cellulose acylate film having both stability of retardation against humidity fluctuation and continuous production suitability.

With the commercialization of liquid crystal displays, panel makers are demanding efficiency and cost reduction in every scene. During such movements, in recent years, as the packaging has been simplified, moisture is invaded by exposure to a high-humidity environment during panel transportation, phase difference fluctuation of the retardation film constituting the panel occurs, It is a problem that color unevenness occurs on the screen.

Particularly, in the retardation film containing cellulose acylate as a main component, the fluctuation of the retardation with respect to moisture is larger than that of the retardation film comprising cycloolefin or polycarbonate as a main component. To solve this problem, many studies have been made from the past.

In the past examination, as a compound for suppressing the fluctuation of the retardation due to humidity fluctuation, 20% by mass or more of a polyester compound was added to increase the hydrophobicity of the film (see, for example, Patent Documents 1 to 3). (See, for example, Patent Documents 4 and 5) and the like for enhancing the interaction with cellulose molecules, and the like. However, it is possible to reduce the magnitude of the fluctuation of the phase difference to a sufficient level In addition to the lack thereof, there was a problem in durability in the aged.

The inventors of the present invention have conducted extensive studies to solve this problem. As a result, it has been found that by using a specific nitrogen-containing heterocyclic compound, the durability can be maintained while the fluctuation of the retardation due to the humidity fluctuation can be improved. Has a low molecular weight and a high melting point and is liable to scatter in a production line and is adhered in a large volume in a cotton-like manner in the production line, thereby causing problems such as contamination of the wall surface or clogging of the filter to shorten the filter life Thus, a new problem has arisen that the continuous production suitability is lower than that of a product not containing the conventional compound.

Japanese Patent Application Laid-Open No. 2002-027103 Japanese Patent Application Laid-Open No. 2012-063748 Japanese Patent Application Laid-Open Publication No. 2012-042938 Japanese Patent Application Laid-Open No. 2011-227508 Japanese Patent Laid-Open Publication No. 2012-082235

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above problems, and a problem to be solved is that a compound that suppresses the fluctuation of the phase difference with respect to humidity is volatilized and scattered in the production line, Or the occurrence of clogging of the filter is improved to provide a cellulose acylate film having both stability of retardation against humidity fluctuation and continuous production suitability. Further, it is intended to provide a highly durable polarizing plate and liquid crystal display device having the cellulose acylate film.

In order to solve the above-mentioned problems, the inventors of the present invention have found that, in a process of examining the cause of the above-mentioned problems, the present inventors have found that when a cellulose acylate and a nitrogen-containing heterocyclic compound having a molecular weight within a range of 100 to 800, And a cellulose acylate film containing an organic ester having a melting point within a range of -60 to 120 占 폚 and having a 1% mass reduction temperature Td1 within a range of 100 to 350 占 폚. Can be solved.

That is, the above object of the present invention is solved by the following means.

1. A cellulose acylate composition comprising a cellulose acylate and a compound having a structure represented by the following general formula (1) within a molecular weight range of 100 to 800 and having a melting point in the range of -60 to 120 占 폚, Wherein the 1% mass reduction temperature Td1 of the cellulose acylate film is within a range of 100 to 350 占 폚.

T ₁ and T ₂ represent a linking group represented by the following general formula (1-2): L ₁ (A ₁₎ , A ₂ and B represent an alkyl group, a cycloalkyl group, an aromatic hydrocarbon ring or an aromatic heterocycle. To L ₄ each represent a single bond or a divalent linking group, and n represents an integer of 0 to 5)

(Wherein * represents the bonding position with L ₁ , L ₂ , L ₃ or L ₄ in the general formula (1), R ⁵ represents a hydrogen atom or a non-aromatic substituent)

2. The cellulose acylate film according to claim 1, wherein the compound having a structure represented by the general formula (1) is at least one selected from the group consisting of a pyrazole ring, a triazole ring, and a compound having an imidazole ring .

3. The cellulose acylate film according to claim 2, wherein the compound having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (3).

(Wherein A represents a pyrazole ring, Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon ring or aromatic heterocycle, and may have a substituent, and R ₁ represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, an alkyloxycarbonyl group , Or an aryloxycarbonyl group, q represents an integer of 1 to 2. n and m represent an integer of 1 to 3.)

4. The cellulose acylate film according to claim 1, wherein the organic ester is at least one selected from sugar esters, polycondensation esters, and polyhydric alcohol esters.

5. The cellulose acylate film according to claim 1, wherein the cellulose acylate film contains a compound having a structure represented by the general formula (1) in an amount of 0.5 to 10 mass%, and the organic ester is contained in an amount of 0.5 to 20 mass% The cellulose acylate film according to claim 1, wherein the cellulose acylate film is a cellulose acylate film.

6. The cellulose acylate film according to claim 1, wherein the cellulose acylate has a total acyl group degree of substitution in the range of 2.0 to 2.7, or cellulose acetate propionate.

(7) a retardation value Ro in an in-plane direction represented by the following formula (i) in a measurement at an optical wavelength of 590 nm under an environment of 23 占 폚 and 55% RH and within the range of 40 to 70 nm; Wherein the retardation value Rt in the thickness direction represented by the following formula is within a range of 100 to 300 nm.

Formula (i): Ro = (n x -n y) × d

Formula (ii): Rt = {( n x + n y) / 2-n z} × d

[In the formulas (i) and (ii), n _x represents the refractive index in the direction x at which the refractive index becomes maximum in the in-plane direction of the film. n _y represents the refractive index in the direction y perpendicular to the direction x in the in-plane direction of the film. and n _z represents the refractive index in the thickness direction z of the film. and d represents the thickness (nm) of the film.

8. A polarizing plate characterized in that the cellulose acylate film according to any one of claims 1 to 7 is bonded to a polarizer using a water-soluble or active energy ray-curable adhesive.

9. A polarizer according to any one of claims 1 to 8, wherein a polyester film or an acrylic film is bonded to the polarizer using a water-shed or active-energy ray-curable adhesive on the surface of the polarizer opposite to the surface to which the cellulose acylate film is bonded The polarizer according to item 8.

10. A liquid crystal display device comprising the cellulose acylate film according to any one of claims 1 to 7.

11. A liquid crystal display device comprising the polarizing plate according to claim 8.

By the above-mentioned means of the present invention, the compound which suppresses the fluctuation of the retardation with respect to humidity is volatilized and scattered in the production line, and adhered in a large volume in the form of a cotton, thereby causing contamination of the wall surface or clogging of the filter It is possible to provide a cellulose acylate film having both stability of retardation against humidity fluctuation and continuous production suitability. Further, it is possible to provide a highly durable polarizing plate and liquid crystal display device having the cellulose acylate film.

The mechanism and mechanism for manifesting the effects of the present invention are not clarified, but are estimated as follows.

According to the study by the present inventors, by using a specific nitrogen-containing heterocyclic compound in the cellulose acylate film, it is possible to reduce the variation of the retardation with respect to humidity. On the other hand, since these compounds are low in molecular weight and have a high melting point, they easily scatter in the production line, and they are adhered to the filter in the air conditioner in a large volume in a cocoon shape, thereby contaminating the wall surface or clogging the filter, And the like.

As a result of examining the relationship between the molecular weight and the non-acid amount of the nitrogen-containing heterocyclic compound and the effect of suppressing the fluctuation of the retardation with respect to humidity, the compound having a molecular weight smaller than 100 has a large molecular weight, And is not useful as a humidity fluctuation inhibitor or a retardation enhancer. Further, it was found that a compound having a molecular weight of more than 800 did not cause clogging of the filter due to a low occurrence of scattered water, but it was not useful because it could not secure the performance as a humidity fluctuation inhibitor or retardation increasing agent or transparency of the film Respectively. Therefore, in order to expect performance as a humidity fluctuation inhibitor or a retardation enhancer, it is preferable that the molecular weight is within a range of 100 to 800, but a compound having a molecular weight within this range tends to scatter in the production line and needs to be improved.

According to the present invention, there is provided a cellulose acylate film comprising a nitrogen-containing heterocyclic compound and an organic ester having a melting point in the range of -60 to 120 占 폚 and having a 1% mass reduction temperature Td1 in the range of 100 to 350 占 폚 The nitrogen-containing heterocyclic compound is scattered and the organic ester is also scattered, and the non-product is cooled in the production line to be liquefied and adhered to the filter as a highly viscous deposit. Therefore, It is presumed that the scattering of the filter can be reduced and the service life of the filter can be increased since it is possible to capture the non-product of the surface of the filter easily on the filter and reduce the volume of the product by its viscosity.

That is, the organic ester having a melting point and a 1% mass reduction temperature Td1 within a specific range has volatility, easiness of liquefaction when the volatiles are cooled, and suitable viscosity, so that the non-product of the nitrogen- It is presumed that it can be captured on the filter.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a dope preparing step, a softening step and a drying step of a preferable solution casting film-forming method of the cellulose acylate film of the present invention.
Fig. 2 is a schematic view of a system for evaluating filter life (clogging) due to non-product. Fig.

The cellulose acylate film of the present invention comprises cellulose acylate and a compound having a structure represented by the above general formula (1) within a molecular weight range of 100 to 800 and having a melting point within a range of -60 to 120 占 폚 And a 1% mass reduction temperature by differential thermal or thermogravimetric measurement is in the range of 100 to 350 占 폚. This feature is a technical feature that is common to the invention according to claims 1 to 11.

As an embodiment of the present invention, it is preferable that from the viewpoint of manifesting the effect of the present invention, the compound having the structure represented by the general formula (1) is at least one selected from a compound having a pyrazole ring, a triazole ring, Is preferably a species and is a compound having a structure represented by the above general formula (3), as the packaging is simplified, moisture is invaded by exposure to a high humidity environment at the time of panel transportation, It is preferable that the retardation fluctuation hardly occurs and also the durability in a long time is high.

The organic ester is preferably at least one selected from a sugar ester, a polycondensation ester, and a polyhydric alcohol ester, and the cellulose acylate film preferably contains a compound having a structure represented by the general formula (1) Mass%, and the organic ester is contained in the range of 0.5 to 20 mass% is liquefied and adhered to the filter when cooled in the production line, Structure, it is preferable because the volume of filter collected can be made small.

The cellulose acylate having a total acyl group substitution degree within the range of 2.0 to 2.7 is preferably used as the cellulose acylate resin used as the retardation film for widening the viewing angle. The retardation value of the retardation film is preferably in the range of 40 to 70 nm in the retardation value in the in-plane direction in the measurement at an optical wavelength of 590 nm under an environment of 23 占 폚 and 55% RH and the retardation value It is preferable that Rt is in the range of 100 to 300 nm.

The cellulose acylate film of the present invention is preferably bonded to a polarizer using a water-soluble or active-energy ray-curable adhesive because it is possible to provide a polarizing plate having small fluctuation in retardation due to humidity fluctuations in the environment, A polarizing plate is bonded to a polarizing film by using a polyester film or an acrylic film on a surface opposite to the surface to which the cellulose acylate film is bonded with a water-soluble or active energy ray-curable adhesive, .

The cellulose acylate film and the polarizing plate of the present invention are suitably provided in a liquid crystal display device.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, " to " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

<< Outline of Cellulose Acylate Film of the Present Invention >>

The cellulose acylate film of the present invention comprises cellulose acylate and a nitrogen-containing heterocyclic compound having a molecular weight in the range of 100 to 800, and a compound having a structure represented by the general formula (1) And the 1% mass reduction temperature Td1 by differential thermal and thermogravimetric measurement is in the range of 100 to 350 占 폚. By such a constitution, the compound having the structure represented by the general formula (1) for suppressing the fluctuation of the phase difference with respect to humidity is volatilized and scattered in the production line, and adhered to a large volume in a cotton- , It is possible to provide a cellulose acylate film having improved stability of retardation against humidity fluctuation and continuous production suitability by improving the clogging of the air conditioning filter.

The present invention relates to the use of an organic ester having a melting point within a range of -60 to 120 占 폚 and having Td1 within a range of 100 to 350 占 폚 together with a compound having a structure represented by the general formula (1) Since the compound having the structure represented by the formula (1) is scattered and the organic ester thereof is scattered and the product is liquefied when it is cooled in the production line and attached to the air conditioning filter, Of the compound having a structure represented by formula (I) is easily trapped on the filter, and the volume of the fly ash is reduced by viscosity, so that the clogging of the filter can be reduced and the filter life can be prolonged. A cellulose acylate film having high stability of phase difference to fluctuation and high continuous production suitability is realized.

&Lt; Configuration of Cellulose Acylate Film of the Present Invention &

The cellulose acylate constituting the cellulose acylate film of the present invention is preferably cellulose acetate having a total acyl group degree of substitution in the range of 2.0 to 2.7, or cellulose acetate propionate.

Examples of the raw material cellulose include cotton linters, wood pulp (hardwood pulp, softwood pulp), and cellulose acylates obtained from any raw material cellulose may be used. Details of these raw materials of the cellulose are described in, for example, Marusawa, Uda, "Plastic material lecture (17) Fiber-based resin", Nikkan High School Shinko Borax (published in 1970) (Pages 7 to 8) can be used.

The cellulose acylate is a cellulose acylate having a total acyl group substitution degree in the range of 2.0 to 2.7. The cellulose acylate has a nitrogen-containing heterocyclic compound or an organic ester (for example, And is preferable from the viewpoint of excellent compatibility because hydrogen bonds easily. From the viewpoint of improving the flexibility and stretchability at the time of film formation and further improving the uniformity of the film thickness, the total acyl group substitution degree of the cellulose acylate is preferably from 2.1 to 2.5.

The cellulose acylate according to the present invention is preferably at least one selected from cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate and cellulose butyrate. Among them, more preferable cellulose acylate Acylates are cellulose acetate, cellulose acetate propionate.

The substitution degree of the acetyl group or the substitution degree of the other acyl group can be obtained by the method defined in ASTM-D817-96.

The weight average molecular weight (Mw) of the cellulose acylate according to the present invention is preferably 75000 or more, more preferably 75000 to 300000, even more preferably 100000 to 240000, and particularly preferably 160000 to 240000 desirable. When the weight average molecular weight (Mw) of the cellulose acylate resin is 75000 or more, the effect of improving the magnetic film forming property and adhesion of the cellulose acylate layer itself is exhibited. In the present invention, two or more kinds of cellulose acylate resins may be mixed and used.

The average molecular weight (Mn, Mw) of the cellulose acylate can be measured by gel permeation chromatography under the following measurement conditions.

Solvent: methylene chloride

Column: Shodex K806, K805, and K803G (manufactured by Showa Denko K.K., were connected and used)

Column temperature: 25 ° C

Sample concentration: 0.1 mass%

Detector: RI Model 504 (manufactured by GL Science)

Pump: L6000 (manufactured by Hitachi Seisakusho Co., Ltd.)

Flow rate: 1.0 ml / min

Calibration curve: Standard polystyrene STK standard A calibration curve with 13 samples within the range of Mw = 500 to 2800000 (polystyrene manufactured by Tosoh Corporation) was used. The 13 samples are preferably used at substantially equal intervals.

<Nitrogen-containing heterocyclic compound>

The compound having the structure represented by the general formula (1) according to the present invention is a nitrogen-containing heterocyclic compound having a molecular weight within the range of 100 to 800, and is a compound represented by the following general formula (1). The compound having the structure represented by the following general formula (1) can be used together with cellulose acylate to suppress the occurrence of fluctuations in the retardation due to the humidity fluctuation of the environment when the polarizing plate is used for a liquid crystal display, The occurrence of unevenness can be suppressed. It can also function as a phase difference increasing agent.

The molecular weight is within a range of 250 to 450, which is a preferable range from the viewpoint of the effect of suppressing the fluctuation of the retardation due to humidity fluctuation and the occurrence of non-product.

&Lt; Compound having a structure represented by general formula (1) >

In the above general formula (1), A ₁ , A ₂ and B each independently represent an alkyl group (such as a methyl group, ethyl group, n-propyl group, isopropyl group, A cyclohexyl group, a cyclopentyl group, a 4-n-dodecylhexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocycle. Of these, an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferable, and a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is particularly preferable.

There is no limitation on the structure of the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, but examples thereof include a benzene ring, a pyrole ring, a pyrazole ring, an imidazole ring, a 1,2,3- Oxadiazole ring, isooxadiazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, isothiadiazole ring and the like can be given. have.

The 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle represented by A ₁ , A ₂ and B may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine An iodine atom and the like), an alkyl group (a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group and a 2-ethylhexyl group), a cycloalkyl group (a cyclohexyl group, (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group and the like), an alkynyl group (2-pyrrolyl group, 2-furyl group, 2-thienyl group, pyrrolyl group, imide group, etc.), an aromatic hydrocarbon ring group (phenyl group, p-tolyl group or naphthyl group) A thiazolyl group, a benzoimidazolyl group, a benzooxazolyl group, a 2-benzothiazolyl group, a pyrazolinone group, a pyridyl group, a pyridinyl group, a 2-pyrimidinyl group, A thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, A hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (methoxy group, ethoxy group, ethoxy group, ethoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-tert-butylphenoxy group and the like), an isopropoxy group, -Nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like), acyloxy group (formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy An amino group (an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group etc.), an acylamino group (formylamino group, acetylamino group, (Methylamino) ethylamino group, a propylamino group, a propylamino group, a propylamino group, a propylamino group, a propylamino group, a propylamino group, Methylphenylsulfonylamino group, etc.), a mercapto group, an alkylthio group (such as a methylthio group, an ethylthio group, an n-hexadecylthio group), an arylthio group (such as a phenylthio group, a p- Phenylthio group, etc.), a sulfamoyl group (N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetyl sulfamoyl group, (Carbamoyl group, N-methylcarbamoyl group, carbamoyl group, carbamoyl group, carbamoyl group, carbamoyl group, carbamoyl group, A N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, an N- (methylsulfonyl) carbamoyl group and the like.

In the general formula (1), A ₁ , A ₂ and B represent a benzene ring, a pyrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4- Is preferable because a cellulose acylate film excellent in variation in optical characteristics and excellent in durability is obtained.

In the above general formula (1), T ₁ and T ₂ each independently represent a pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring. Among them, a pyrazole ring, a triazole ring or an imidazole ring is particularly preferable because a resin composition having excellent durability and a particularly excellent effect of suppressing fluctuation of retardation against humidity fluctuation can be obtained, and pyrazole ring is particularly preferable. The pyrazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring or imidazole ring represented by T ₁ and T ₂ may be a tautomer. Specific structures of pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring are shown below.

In the formulas, * represents the bonding position with L ₁ , L ₂ , L ₃ or L ₄ in the general formula (1). R ⁵ represents a hydrogen atom or a non-aromatic substituent. As the non-aromatic substituent represented by R ⁵ , the same group as the non-aromatic substituent in the substituent group that A ₁ in the general formula (1) may have may be mentioned. When the substituent represented by R ⁵ is a substituent having an aromatic group, A ₁ and T ₁ or B and T ₁ are liable to be twisted, and A ₁ , B and T ₁ can not form an interaction with the cellulose acylate , It is difficult to suppress the fluctuation of the optical characteristics. In order to enhance the fluctuation-suppressing effect of the optical properties, R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom.

In the general formula (1), T ₁ and T ₂ may have a substituent, and examples of the substituent include the same groups as the substituent which A ₁ and A ₂ in the general formula (1) may have .

In the general formula (1), L ₁ , L ₂ , L ₃ and L ₄ each independently represent a single bond or a divalent linking group, and may be a 5-membered or 6-membered Of an aromatic hydrocarbon ring or an aromatic heterocycle. The term " intervening two or less atoms " means the minimum number of atoms existing between substituents connected to atoms constituting a linking group. The divalent linking group having two or less connected atoms is not particularly limited and includes a group consisting of an alkylene group, an alkenylene group, an alkynylene group, O, (C = O), NR, S, (O = S = O) Or a combination of two of them. R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include an alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group and 2-ethylhexyl group, a cycloalkyl group (cyclohexyl group, (2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-thienyl group and the like), an aromatic hydrocarbon ring group , 2-benzothiazolyl group, 2-pyridyl group and the like), cyano group and the like. The divalent linking group represented by L ₁ , L ₂ , L ₃ and L ₄ may have a substituent. The substituent is not particularly limited. For example, when A ₁ and A ₂ in the general formula (1) And the same group as the substituent which may be contained.

In the general formula (1), L ₁ , L ₂ , L _3, and L ₄ are each a group having a higher planarity of a compound having a structure represented by the general formula (1) (C = O) -O, O- (C = O), (C = O) -NR or NR- (C = O) More preferably a single bond.

In the general formula (1), n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of A ₂ , T ₂ , L ₃ , and L ₄ in the general formula (1) may be the same or different. The larger n is, the stronger the interaction effect between the compound having the structure represented by the general formula (1) and the resin adsorbing water, the better the effect of suppressing the fluctuation of the optical properties, and the smaller the value of n is, &Lt; / RTI > Therefore, n is preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

&Lt; Compound having a structure represented by general formula (2) >

The compound having the structure represented by the general formula (1) is preferably a compound having the structure represented by the general formula (2).

(Wherein _{A 1, A 2, T 1} , T 2, L 1, L 2, L 3 and L ₄ are, A _1, in each of the above-mentioned general formula _{(1) A 2, T 1} , T 2, L _1, is L _2, L ₃ and L ₄ with consent. a ₃ and T _3, respectively a ₁ and represents the same groups as T ₁ in the formula (1). L ₅ and L ₆ are the general Represents the same group as L ₁ in the formula (1), and m represents an integer of 0 to 4.)

m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, since m is smaller in compatibility with cellulose acylate.

&Lt; Compound having a structure represented by general formula (1.1) >

The compound having a structure represented by the general formula (1) is preferably a triazole compound having a structure represented by the following general formula (1.1).

(Wherein A _1, B, L ₁ and L ₂ is, A ₁ represents the same groups as B, L ₁ and L ₂ in the general formula (1). K is an integer of 1-4. T ₁ represents a 1,2,4-triazole ring.)

The triazole compound having a structure represented by the general formula (1.1) is preferably a triazole compound having a structure represented by the following general formula (1.2).

(Z represents a structure represented by the following general formula (1.2a): q represents an integer of from 2 to 3. At least two Zs represent an ortho position or a meta position with respect to at least one Z substituted on the benzene ring, Position.)

(Wherein R ¹⁰ represents a hydrogen atom, an alkyl group or an alkoxy group, p represents an integer of 1 to 5, * represents a bonding position with a benzene ring, and T ₁ represents a 1,2,4-triazole ring.

The compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) may form a hydrate, a solvate or a salt. Further, in the present invention, the hydrate may contain an organic solvent, and the solvate may include water. That is, the "hydrate" and "solvate" include mixed solvates containing both water and an organic solvent. Salts include acid addition salts formed with inorganic or organic acids. Examples of the inorganic acid include, but are not limited to, a hydrohalic acid (hydrochloric acid, hydrobromic acid, etc.), sulfuric acid, and phosphoric acid. Examples of the organic acid include organic acids such as acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (methanesulfonic acid and the like), allylsulfonic acid (benzenesulfonic acid, 4-toluenesulfonic acid, Etc.), and the like, and the present invention is not limited to these. Of these, hydrochloride, acetate, propionate and butyrate are preferable.

Examples of salts include salts in which the acidic moiety present in the prodrug compound is replaced by a metal ion (e.g., an alkali metal salt such as sodium or potassium salt, an alkaline earth metal salt such as a calcium or magnesium salt, an ammonium salt alkali metal ion, (Aluminum ion, etc.), or a salt formed when it is adjusted with an organic base (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.) Do not. Among them, sodium salt and potassium salt are preferable.

Examples of the solvent in which the solvate is included include all common organic solvents. Specific examples of the solvent include alcohols such as methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol, esters such as ethyl acetate, hydrocarbons such as toluene, Heptane), ethers (e.g., tetrahydrofuran), nitriles (e.g., acetonitrile), ketones (acetone), and the like. Preferably, it is a solvate of an alcohol (e.g., methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol). These solvents may be either a reaction solvent used in the synthesis of the above compound, a solvent which can be used in crystal purification after synthesis, or a mixture thereof.

Further, it may contain two or more kinds of solvents at the same time, or may be a form containing water and a solvent (for example, water and an alcohol (for example, methanol, ethanol, t-butanol, etc.)).

The compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) may be added in a form not containing water, a solvent or a salt. In the composition or the cellulose acylate film, a hydrate, a solvate or a salt may be formed.

Further, the nitrogen-containing heterocyclic compound according to the present invention is more preferably a compound having a structure represented by the following general formula (3).

The aromatic hydrocarbon ring or aromatic heterocycle represented by Ar ₁ and Ar ₂ is preferably a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle represented by the general formula (1), respectively. Examples of the substituent for Ar ₁ and Ar ₂ include the same substituents as those shown for the compound having the structure represented by the above general formula (1).

Specific examples of R ₁ include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), an alkyl group (such as methyl group, ethyl group, n-propyl group, isopropyl group, Ethylhexyl group and the like), an acyl group (acetyl group, pivaloylbenzoyl group and the like), a sulfonyl group (such as a methylsulfonyl group and an ethylsulfonyl group), an alkyloxycarbonyl group (such as a methoxycarbonyl group) An aryloxycarbonyl group (e.g., phenoxycarbonyl group and the like), and the like.

q represents an integer of 1 to 2, and n and m represent an integer of 1 to 3.

Specific examples of the compound having a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle used in the present invention are illustrated below. Among them, a compound having a structure represented by the general formula (1), (2), (1.1), (1.2) or a compound represented by the general formula (3) is preferable. The 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle-containing compound usable in the present invention is not limited in any way by the following specific examples. In addition, as described above, the following specific examples may be tautomers or hydrates, solvates or salts.

delete

Next, a method of synthesizing a compound having a structure represented by the above general formula (1) will be described.

The compound having the structure represented by the general formula (1) can be synthesized by a known method. In the compound having the structure represented by the above general formula (1), the compound having a 1,2,4-triazole ring may be any raw material, but a nitrile derivative or an imino ether derivative and a hydrazide derivative may be used. A reaction method is preferable. The solvent to be used in the reaction may be any solvent as long as it is a solvent that does not react with the raw material. Examples of the solvent include esters (for example, ethyl acetate, methyl acetate and the like), amides (dimethylformamide, dimethylacetamide, (Such as ethylene glycol dimethyl ether and the like), an alcohol type (e.g. methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, ethylene glycol, ethylene glycol monomethyl ether etc.), aromatic hydrocarbon , Toluene, xylene, etc.) and water. As the solvent to be used, it is preferably an alcoholic solvent. These solvents may be mixed and used.

The amount of the solvent to be used is not particularly limited, but is preferably in the range of 0.5 to 30 times, more preferably 1.0 to 25 times, and particularly preferably 3.0 to 20 times the mass of the hydrazide derivative to be used Lt; / RTI >

When a nitrile derivative is reacted with a hydrazide derivative, it is not necessary to use a catalyst, but it is preferable to use a catalyst to accelerate the reaction. As the catalyst to be used, an acid may be used, or a base may be used. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, preferably hydrochloric acid. The acid may be diluted with water or may be added by blowing gas into the system. Examples of the base include inorganic bases such as potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate, potassium hydroxide and sodium hydroxide and organic bases such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, sodium butyrate, Diisopropylethylamine, N, N'-dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, imidazole, N-methylimidazole, pyridine, etc.) . As the inorganic base, potassium carbonate is preferable, and as the organic base, sodium methylate, sodium ethylate and sodium butyrate are preferable. The inorganic base may be added in the form of a powder, or may be added in a state of being dispersed in a solvent. The organic base may be added in a state in which it is dissolved in a solvent (for example, 28% methanol solution of sodium methylate).

The amount of the catalyst to be used is not particularly limited as far as the reaction proceeds, but is preferably in the range of 1.0 to 5.0 times the molar amount of the triazole ring to be formed, and is preferably in the range of 1.05 to 3.0 times the molar amount.

When an imino ether derivative is reacted with a hydrazide derivative, it is not necessary to use a catalyst, and the desired product can be obtained by heating in a solvent.

The method of adding the raw materials, the solvent and the catalyst used for the reaction is not particularly limited, and the catalyst may be added last, or the solvent may be added last. It is also preferable to disperse or dissolve the nitrile derivative in a solvent, add a catalyst, and then add a hydrazide derivative.

The solution temperature during the reaction may be any temperature as long as the reaction proceeds, but is preferably within the range of 0 to 150 ° C, and more preferably within the range of 20 to 140 ° C. In addition, the reaction may be carried out while removing the generated water.

Any method may be used for the treatment of the reaction solution, but when a base is used as the catalyst, a method of neutralizing the reaction solution by adding acid is preferred. As the acid to be used for neutralization, for example, hydrochloric acid, sulfuric acid, nitric acid or acetic acid may be mentioned, and acetic acid is particularly preferable. The amount of the acid to be used for neutralization is not particularly limited as long as the pH of the reaction solution is in the range of 4 to 9, but is preferably 0.1 to 3 times, more preferably 0.2 to 1.5, It is mine.

As a treatment method of the reaction solution, in the case of extraction using a suitable organic solvent, a method of washing the organic solvent with water and then concentrating is preferable. Suitable organic solvents as used herein include nonaqueous solvents such as ethyl acetate, toluene, dichloromethane and ether, or mixed solvents of the above-mentioned water-insoluble solvents and tetrahydrofuran or alcoholic solvents, preferably ethyl acetate .

In the case of crystallizing a compound having a structure represented by the general formula (1), there is no particular limitation, but a method in which water is added to the neutralized reaction solution to crystallize or a method in which a compound having the structure represented by the general formula (1) A method in which the dissolved aqueous solution is neutralized and crystallized is preferred.

For example, the exemplified compound 1 can be synthesized by the following reaction formula.

(Synthesis of Exemplified Compound 1)

77.3 g (75.0 mmol) of benzonitrile, 34.0 g (25.0 mmol) of benzoyl hydrazine and 107.0 g (77.4 mmol) of potassium carbonate were added to 350 ml of n-butanol and the mixture was stirred at 120 ° C for 24 hours under nitrogen atmosphere. The reaction solution was cooled to room temperature, the precipitate was filtered, and the filtrate was concentrated under reduced pressure. 20 ml of isopropanol was added to the concentrate, and the precipitate was filtered out. The precipitate obtained by filtration was dissolved in 80 ml of methanol, 300 ml of pure water was added, and acetic acid was added dropwise until the pH of the solution reached 7. The precipitated crystals were filtered off, washed with pure water, and blow-dried at 50 ° C to obtain 38.6 g of Exemplified Compound 1. The yield was 70% on the basis of benzoylhydrazine.

The ¹ H-NMR spectrum of the obtained Exemplified Compound 1 is as follows.

(Synthesis of Exemplified Compound 6)

Exemplified Compound 6 can be synthesized by the following reaction formula.

2.5 g (19.5 mmol) of 1,3-dicyanobenzene, 7.9 g (58.5 mmol) of benzoyl hydrazine and 9.0 g (68.3 mmol) of potassium carbonate were added to 40 ml of n-butanol and the mixture was stirred at 120 DEG C for 24 hours Respectively. After cooling the reaction solution, 40 ml of pure water was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was separated by filtration and washed with pure water. Water and ethyl acetate were added to the obtained solid and liquid separation was performed, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude crystals were purified by silica gel chromatography (ethyl acetate / heptane) to obtain 5.5 g of Exemplified Compound 6. The yield was 77% based on 1,3-dicyanobenzene.

The ¹ H-NMR spectrum of the obtained Exemplified Compound 6 is as follows.

(Synthesis of Exemplified Compound 176)

The exemplified compound 176 can be synthesized by the following reaction formula.

80 g (0.67 mol) of acetophenone and 52 g (0.27 mol) of dimethyl isophthalate were added to 520 ml of dehydrated tetrahydrofuran, and 52.3 g (1.34 mol) of sodium amide was added dropwise while stirring under ice cooling with nitrogen. The mixture was stirred for 3 hours under ice-cooling water, and then stirred for 12 hours under water-cooling. Concentrated sulfuric acid was added to the reaction mixture to neutralize the mixture, and pure water and ethyl acetate were added thereto for liquid separation, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Methanol was added to the obtained crude crystals, and the mixture was suspended and washed to obtain 55.2 g of Intermediate A.

55 g (0.15 mol) of Intermediate Compound A was added to 300 ml of tetrahydrofuran and 200 ml of ethanol, and 18.6 g (0.37 mol) of hydrazine monohydrate was added little by little while stirring at room temperature. After completion of dropwise addition, the mixture was heated to reflux for 12 hours. Pure water and ethyl acetate were added to the reaction mixture to effect separation, and the organic layer was washed with pure water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude crystals were purified by silica gel chromatography (ethyl acetate / heptane) to obtain 27 g of Exemplified Compound 176.

The ¹ H-NMR spectrum of the obtained Exemplary Compound 176 is as follows. In addition, in order to avoid the complication of the chemical shift due to the presence of the tautomer, a few drops of trifluoroacetic acid was added to the measurement solvent and the measurement was carried out.

Other compounds can also be synthesized by the same method.

&Lt; Method of using the compound having the structure represented by the general formula (1) >

The compound having the structure represented by the general formula (1) according to the present invention may be contained in the cellulose acylate film in an appropriate amount, and the amount thereof added is preferably 0.5 to 10 mass% in the cellulose acylate film Do. Within this range, the effect of suppressing the fluctuation of the phase difference with respect to the humidity fluctuation is high, and the amount of the byproducts is so large that the continuous production suitability is not deteriorated. Particularly, it is preferable to include 0.5 to 5 mass%.

The compound having the structure represented by the general formula (1) may be added to the resin forming the cellulose acylate film as a powder, dissolved in a solvent, added to the resin forming the cellulose acylate film You can.

The organic ester according to the present invention is an organic ester having a melting point within a range of -60 to 120 占 폚 and a 1% mass reduction temperature Td1 by differential thermal and thermogravimetric measurement within a range of 100 to 350 占 폚. The organic ester is not particularly limited, but the organic ester is preferably at least one selected from sugar esters, polycondensation esters, and polyhydric alcohol esters, and the polycondensation ester is preferably a polycondensation ester containing no nitrogen atom Ester is preferred.

(Measurement of melting point of organic ester)

The melting point was measured using EXSTAR6220DSC, a simultaneous differential thermal and simultaneous thermogravimetric analyzer manufactured by Seiko Instruments. 10 mg of the sample compound was placed in an aluminum pan, and the melting point was determined from the endothermic peak and the exothermic peak when the temperature was changed from 30 캜 to 350 캜 and from 350 캜 to 30 캜 at 10 캜 / min. When measuring a compound having a melting point of 0 ° C or lower, the melting point was determined from an endothermic peak at -50 ° C to 30 ° C and a temperature from 30 ° C to -50 ° C at 5 ° C / min.

The organic ester according to the present invention should have a melting point within a range of -60 to 120 占 폚 and preferably within a range of -45 占 폚 to 90 占 폚 in order to exhibit the effect of the present invention.

If the melting point of the organic ester is within the range of -60 to 120 占 폚, it is preferable that the organic ester is dispersed in the production line and is liable to be liquefied after being cooled, so that it is within this range from the viewpoint of manifesting the effect of the present invention.

(Measurement of 1% mass reduction temperature of organic ester)

The 1% mass reduction temperature of the organic ester, Td1, can be measured, for example, by adding 10 mg of a sample compound to an aluminum pan using EXSTAR6200TG / DTA, a simultaneous differential thermal and simultaneous thermogravimetry apparatus manufactured by SEIKO INSTRUMENTS, The temperature was raised to 100 占 폚 and then left to stand for 40 minutes. Thereafter, the mass change was monitored by heating to 400 占 폚 at 10 占 폚 / min, and the temperature at which the mass was reduced by 1 mass% do. The measurement is also carried out under dry air (dew point -30 ° C).

In order to exhibit the effect of the present invention, the organic ester according to the present invention should have a 1% mass reduction temperature within a range of 100 to 300 占 폚, and preferably within a range of 200 to 270 占 폚.

When the temperature at which the 1% mass of the organic ester is reduced is 100 ° C or more, the viscosity at the time of liquefaction after cooling and cooling is adequate, the bulk of the nitrogen-containing heterocyclic compound can be reduced, and the 1% , The organic ester is dispersed in an amount necessary for decreasing the volume of the non-produced acid of the nitrogen-containing heterocyclic compound, so that a sufficient effect can be obtained.

The content of the organic ester of the present invention is preferably in the range of 0.5 to 20 mass% in the cellulose acylate film of the present invention. When the content is within this range, the nitrogen-containing heterocyclic compound is scattered, and the organic ester is also scattered, and the non-product is cooled in the production line to be liquefied and attached to the filter as a highly viscous deposit. It is possible to easily capture the non-product of the compound in the form of a filter on the filter and to reduce the volume of the non-product by the viscosity thereof, so that the filter clogging can be reduced and the filter life can be increased.

The organic ester is preferably used in combination with two or more different compounds. In particular, the following sugar ester and polycondensation ester are preferably used in combination. The content of each compound in the case of using in combination is not particularly limited, but it is preferable from the viewpoint of stabilization of the optical properties of the cellulose acylate film that the content of the sugar ester is increased.

Hereinafter, sugar esters, polycondensation esters, and polyhydric alcohol esters will be described as organic esters preferably used in the present invention.

In the present invention, among the following preferred organic esters, compounds having the melting point and the 1% mass reduction temperature Td1 falling within the range of the present invention can be appropriately selected and used.

The sugar ester according to the present invention is preferably a sugar ester in which at least one of a pyranose ring or a furanose ring is contained in an amount of 1 to 12, and all or a part of OH groups of the structure is esterified.

The sugar ester according to the present invention is a compound containing at least any one of a furanose ring and a pyranose ring, and may be a monosaccharide or a polysaccharide having 2 to 12 sugar structures. The sugar ester is preferably a compound in which at least one OH group of the sugar structure is esterified. In the sugar ester according to the present invention, the average degree of ester substitution is preferably in the range of 4.0 to 8.0, more preferably in the range of 5.0 to 7.5.

The sugar ester according to the present invention is not particularly limited, but includes sugar esters represented by the following general formula (A).

In general formula (A)

_{(HO) m -G- (OC (} = O) -R 2) n

In the general formula (A), G represents a residue of a monosaccharide or a disaccharide, R ² represents an aliphatic group or an aromatic group, and m is the total number of hydroxyl groups directly bonded to a residue of a monosaccharide or a disaccharide , n is the sum of the numbers of - (OC (= O) -R ² ) groups directly bonded to the monosaccharide or disaccharide residue, ³ ? m + n? 8 and n?

The sugar ester having the structure represented by the general formula (A) is difficult to be isolated as a single kind of compound in which the number of hydroxy groups (m) and the number of - (OC (= O) -R ² ) groups (n) , And it is known that a compound in which several different components of m and n are mixed in the formula is known. Therefore, the performance as a mixture in which the number of hydroxy groups (m) and the number of - (OC (= O) -R ² ) groups (n) respectively is important. In the case of the cellulose acylate film of the present invention, Sugar esters having a degree of polymerization within the range of 5.0 to 7.5 are preferred.

In the above general formula (A), G represents a residue of a monosaccharide or a disaccharide. Specific examples of monosaccharides include, for example, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose and ricin.

Specific examples of the compound having a sugar ester monosaccharide residue represented by the general formula (A) are shown below, but the present invention is not limited to these exemplified compounds.

Specific examples of the disaccharide moiety include, for example, trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, isotrehalose and the like.

Specific examples of the compound having a disaccharide residue of a sugar ester represented by the general formula (A) are shown below, but the present invention is not limited to these exemplified compounds.

In the general formula (A), R ² represents an aliphatic group or an aromatic group. Here, the aliphatic group and the aromatic group may each independently have a substituent.

In the general formula (A), m is the sum of the number of hydroxy groups directly bonded to the monosaccharide or disaccharide residue, and n is - (OC (= O) -R < ² >) groups. Then, 3? M + n? 8 is required, and 4? M + n? 8 is preferable. Also, n? 0. When n is 2 or more, the - (OC (= O) -R ² ) groups may be the same or different.

The aliphatic group in the definition of R ² may be straight chain, branched or cyclic, preferably 1 to 25 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 2 to 15 carbon atoms. Specific examples of the aliphatic group include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert- butyl, amyl, isoamyl, , Cyclohexyl, n-heptyl, n-octyl, bicyclooctyl, adamantyl, n-decyl, tert-octyl, dodecyl, hexadecyl, octadecyl and didecyl.

The aromatic group in the definition of R ² may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or more preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms. Specific examples of the aromatic hydrocarbon group include rings of benzene, naphthalene, anthracene, biphenyl, terphenyl, and the like. As the aromatic hydrocarbon group, a benzene ring, a naphthalene ring and a biphenyl ring are particularly preferable. As the aromatic heterocyclic group, a ring containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom is preferable. Specific examples of the heterocycle include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, Benzothiazole, quinoline, quinazoline, cinnoline, phthyridine, acridine, phenanthroline, phenazine, tetrazole, benzene, oxazole, oxazole, quinoline, isoquinoline, phthalazine, naphthyridine, Imidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaine, and the like. The aromatic heterocyclic group is particularly preferably a pyridine ring, a triazine ring or a quinoline ring.

Next, preferred examples of the sugar ester represented by the formula (A) are shown below, but the present invention is not limited to these exemplified compounds. The melting point and 1% mass reduction temperature Td1 of all of the following exemplary compounds are within the scope of the present invention.

The sugar ester may contain two or more different substituent groups in one molecule and may contain two or more aromatic substituent groups in one molecule and two or more different aliphatic substituent groups in the molecule. May be contained in one molecule.

It is also preferable that two or more kinds of sugar esters are mixed and contained. It is also preferable to use a plurality of sugar esters having different degrees of substitution, and it is also preferable that sugar esters containing aromatic substituent groups and sugar esters containing aliphatic substituent groups are contained at the same time.

Synthesis Example: Synthesis of sugar ester represented by the general formula (A)

The following is an example of the synthesis of a sugar ester suitable for use in the present invention.

34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of anhydrous benzoic acid and 379.7 g (4.8 mol) of pyridine were added to four-necked colbene equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas- And the temperature was elevated while bubbling nitrogen gas through a nitrogen gas introducing tube with stirring, and the esterification reaction was carried out at 70 ° C for 5 hours. Subsequently, the inside of the colb is reduced to 4 × 10 ² Pa or less, excess pyridine is distilled off at 60 ° C., the pressure in corbene is reduced to 1.3 × 10 Pa or less and the temperature is raised to 120 ° C. to obtain an anhydrous benzoic acid Most were distilled off. Subsequently, 1 L of toluene and 300 g of an aqueous sodium carbonate solution of 0.5 mass% were added, stirred at 50 캜 for 30 minutes, and then allowed to stand, and the toluene layer was collected. Finally, 100 g of water was added to the separated toluene layer, and the mixture was rinsed at room temperature for 30 minutes. Then, the toluene layer was collected, and toluene was distilled off at 60 캜 under reduced pressure (4 x 10 ² Pa or less) -1, A-2, A-3, A-4 and A-5. The obtained mixture was analyzed by HPLC and LC-MASS to find that 7 mass% of A-1, 58 mass% of A-2, 23 mass% of A-3, 9 mass% of A- Mass%, and the average ester substitution degree of the sugar ester was 6.57. A part of the obtained mixture was purified by silica gel column chromatography to obtain A-1, A-2, A-3, A-4 and A-5 having a purity of 100%.

The amount of the sugar ester added is preferably in the range of 0.5 to 20 mass%, more preferably in the range of 1 to 15 mass% with respect to the cellulose acylate film, from the viewpoint of enhancing the optical stability against environmental fluctuations, Is more preferable.

In the cellulose acylate film of the present invention, as the organic ester, it is preferable to use a polycondensation ester having a structure represented by the following general formula (4).

The polycondensation ester is preferably contained in the range of 0.5 to 20 mass%, more preferably in the range of 1 to 15 mass% with respect to the cellulose acylate film, from the viewpoint of its plastic effect in addition to the effect of the present invention , And particularly preferably in a range of 1 to 10 mass%.

In general formula (4)

B ₃ - (G ₂ -A) _n -G ₂ -B ₄

In the general formula (4), B ₃ and B ₄ each independently represent an aliphatic or aromatic monocarboxylic acid residue or a hydroxy group. G ₂ represents an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms. A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms. n represents an integer of 1 or more.

In the present invention, the polycondensation ester is a polycondensation ester containing a repeating unit obtained by reacting a dicarboxylic acid with a diol, A represents a carboxylic acid residue in the polycondensation ester, and G ₂ represents an alcohol residue.

The dicarboxylic acid constituting the polycondensation ester is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, preferably an aromatic dicarboxylic acid. The dicarboxylic acid may be one kind or a mixture of two or more kinds. Particularly, it is preferable to mix aromatic and aliphatic.

The diol constituting the polycondensation ester is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, and more preferably a diol having 1 to 4 carbon atoms. The diol may be a single type or a mixture of two or more types.

Among them, it is preferable to include a repeating unit obtained by reacting at least a dicarboxylic acid containing an aromatic dicarboxylic acid with a diol having a carbon number of 1 to 8, and it is preferable to contain a repeating unit obtained by reacting an aromatic dicarboxylic acid with an aromatic dicarboxylic acid More preferably a repeating unit obtained by reacting a carboxylic acid with a diol having 1 to 8 carbon atoms.

Both ends of the molecule of the polycondensation ester may be sealed or not sealed.

Specific examples of the alkylene dicarboxylic acid constituting A in the general formula (4) include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid) And divalent groups derived from 4-butanedicarboxylic acid (adipic acid), 1,5-pentanedicarboxylic acid (pimelic acid), and 1,8-octanedicarboxylic acid (sebacic acid). Specific examples of the alkenylene dicarboxylic acid constituting A include maleic acid and fumaric acid. Specific examples of the aryldicarboxylic acid constituting A include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, 1,5- Naphthalene dicarboxylic acid, and the like.

A may be a single kind, or two or more kinds may be combined. Among them, A is preferably a combination of an alkylene dicarboxylic acid having 4 to 12 carbon atoms and an aryl dicarboxylic acid having 8 to 12 carbon atoms.

G ₂ in the general formula (4) represents a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms, a divalent group derived from an aryl glycol having 6 to 12 carbon atoms, or a divalent group having 4 to 12 carbon atoms Of the oxyalkylene glycol.

Examples of the divalent group derived from an alkylene glycol having 2 to 12 carbon atoms in G ₂ include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, Propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2- Glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylol pentane), 2-n-butyl- Methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl- 1,6-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-octadecanediol.

Examples of the divalent group derived from an aryl glycol having 6 to 12 carbon atoms in G ₂ include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol) , 1,4-dihydroxybenzene (hydroquinone), and the like. Examples of the divalent group derived from oxyalkylene glycol having 4 to 12 carbon atoms in G include divalent groups derived from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like Lt; / RTI >

G ₂ may be a single kind or a combination of two or more kinds. Among them, G ₂ is preferably a divalent group derived from an alkylene glycol having 2 to 12 carbon atoms, more preferably 2 to 5, and most preferably 2 to 4.

B ₃ and B ₄ in the general formula (4) are each a monovalent group derived from an aromatic ring-containing monocarboxylic acid or an aliphatic monocarboxylic acid, or a hydroxy group.

The aromatic ring-containing monocarboxylic acid in the monovalent group derived from the aromatic ring-containing monocarboxylic acid is a carboxylic acid containing an aromatic ring in the molecule and not only the aromatic ring is bonded directly to the carboxyl group, And a carboxyl group. Examples of the monovalent group derived from an aromatic ring-containing monocarboxylic acid include benzoic acid, para-tert-butylbenzoic acid, orthotoluenic acid, meta-toluic acid, paratoluic acid, dimethylbenzoic acid, ethylbenzoic acid, And monovalent groups derived from acetoxybenzoic acid, phenylacetic acid, 3-phenylpropionic acid, and the like. Among them, benzoic acid and para-toluic acid are preferable.

Examples of the monovalent group derived from an aliphatic monocarboxylic acid include monovalent groups derived from acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid and the like. Among them, a monovalent group derived from an alkyl monocarboxylic acid having 1 to 3 carbon atoms in the alkyl moiety is preferable, and an acetyl group (monovalent group derived from acetic acid) is more preferable.

The weight average molecular weight of the polycondensate ester according to the present invention is preferably in the range of 500 to 3000, more preferably in the range of 600 to 2000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

Specific examples of the polycondensation ester having the structure represented by the general formula (4) are shown below, but the present invention is not limited thereto. The melting point and 1% mass reduction temperature Td1 of all of the following exemplary compounds are within the scope of the present invention.

Hereinafter, specific synthesis examples of the polycondensation esters described above will be described.

180 g of ethylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were put into a 2 L four-necked flask equipped with a thermometer, a stirrer and a full cooling tube, The temperature was gradually raised with stirring until the temperature reached 230 占 폚. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted ethylene glycol was distilled off under reduced pressure at 200 DEG C to obtain a polycondensation ester P1. An acid value of 0.20, and a number average molecular weight of 450.

251 g of 1,2-propylene glycol, 103 g of phthalic anhydride, 244 g of adipic acid, 610 g of benzoic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were put into a 2 L four-necked flask equipped with a thermometer, , And the temperature is gradually raised while stirring in a nitrogen stream until the temperature becomes 230 캜. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 占 폚 to obtain the following polycondensation ester P2. An acid value of 0.10 and a number average molecular weight of 450.

330 g of 1,4-butanediol, 244 g of phthalic anhydride, 103 g of adipic acid, 610 g of benzoic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, , And the temperature is gradually raised while stirring in a nitrogen stream until the temperature becomes 230 캜. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, the unreacted 1,4-butanediol was distilled off under reduced pressure at 200 占 폚 to obtain a polycondensation ester P3. An acid value of 0.50 and a number average molecular weight of 2000.

251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 610 g of benzoic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer and a super cooling tube, Deg.] C, the temperature is gradually raised with stirring. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 DEG C to obtain a polycondensation ester P4. An acid value of 0.10, and a number average molecular weight of 400.

251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 680 g of p-toluic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked flask equipped with a thermometer, The temperature is gradually raised with stirring until the temperature becomes 230 캜 in the air stream. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 占 폚 to obtain the following polycondensation ester P5. An acid value of 0.30, and a number average molecular weight of 400.

180 g of 1,2-propylene glycol, 292 g of adipic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer and a super cooling tube, The temperature is gradually raised with stirring until the temperature becomes 200 ° C. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 占 폚 to obtain a polycondensation ester P6. An acid value of 0.10, and a number average molecular weight of 400.

244 g of 1,2-propylene glycol, phthalic anhydride, 103 g of adipic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer and a full cooling tube, The temperature is gradually raised with stirring until the temperature becomes 200 占 폚 in a stream of nitrogen. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 占 폚 to obtain a polycondensation ester P7. An acid value of 0.10 and a number average molecular weight of 320.

251 g of ethylene glycol, 244 g of phthalic anhydride, 120 g of succinic acid, 150 g of acetic acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer and a cooling tube, Deg.] C, the temperature is gradually raised with stirring. Dehydration condensation reaction was carried out while observing the polymerization degree. After completion of the reaction, unreacted ethylene glycol was distilled off under reduced pressure at 200 캜 to obtain a polycondensation ester P8. An acid value of 0.50, and a number average molecular weight of 1200.

In the same manner as in the above polycondensation ester P2, polycondensation ester P9 having an acid value of 0.10 and a number average molecular weight of 315 was obtained by changing the reaction conditions.

In the cellulose acylate film of the present invention, it is also preferable to contain a polyhydric alcohol ester.

The polyhydric alcohol ester is a compound containing an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably 2 to 20, aliphatic polyhydric alcohol esters.

The polyhydric alcohol preferably used in the present invention is represented by the following general formula (5).

(5) R < ₁₁ > - (OH) _n

Provided that R ₁₁ is an organic group having an n number of carbon atoms, n is a positive integer of 2 or more, and the OH group is an alcoholic and / or phenolic hydroxyl group.

Examples of preferred polyhydric alcohols include, for example, the following, but the present invention is not limited thereto.

Propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,2-butanediol, 1,2-butanediol, 1,3-propanediol, Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylol propane, trimethylol ethane, xylitol and the like.

Particularly preferred are triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylol propane and xylitol.

The monocarboxylic acid used in the polyhydric alcohol ester is not particularly limited and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids and the like can be used. The use of an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is preferable because it improves the moisture permeability and retention.

Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

As the aliphatic monocarboxylic acid, a linear or branched chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Incorporation of acetic acid increases compatibility with cellulose acetate, and it is preferable to use acetic acid and other monocarboxylic acids in combination.

Preferred aliphatic monocarboxylic acids are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2- ethylhexanoic acid, undecanoic acid, But are not limited to, trimellitic acid, trimellitic acid, decyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, , Saturated fatty acids such as lactic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.

Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

Examples of preferable aromatic monocarboxylic acids include those obtained by introducing one to three alkoxy groups such as alkyl groups, methoxy groups or ethoxy groups into benzene rings of benzoic acids such as benzoic acid and toluic acid, those having biphenylcarboxylic acid and naphthalenecarboxylic acid , Tetralin carboxylic acid, and the like, or derivatives thereof. The term " aromatic monocarboxylic acid " Particularly preferred is benzoic acid.

The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, more preferably in the range of 350 to 750. A larger molecular weight is preferred because it is less volatile, and a smaller molecular weight is desirable from the viewpoint of water vapor permeability and compatibility with cellulose acylate.

The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. In addition, the OH group in the polyhydric alcohol may be all esterified, or a part thereof may be left as an OH group.

Specific compounds of polyhydric alcohol esters are exemplified below. All the following exemplary compounds have a melting point and a 1% mass reduction temperature Td1 within the range of the present invention.

The polyhydric alcohol ester according to the present invention is preferably contained in the range of 0.5 to 20 mass% with respect to the cellulose acylate film from the viewpoint of obtaining the effect of the present invention and the plastic effect, and is preferably in the range of 1 to 15 mass% , More preferably in a range of 1 to 10% by mass.

The polyhydric alcohol ester according to the present invention can be synthesized according to a conventionally known general synthesis method.

In the cellulose acylate film of the present invention, a phosphate ester can be used. Examples of the phosphoric ester include triaryl phosphoric acid ester, diaryl phosphoric acid ester, monoaryl phosphoric acid ester, aryl phosphonic acid compound, aryl phosphine oxide compound, condensed aryl phosphoric acid ester, halogenated alkyl phosphoric acid ester, halogen-containing condensed phosphoric acid ester, A phosphoric acid ester, a halogen-containing phosphorous acid ester, and the like.

Specific examples of the phosphoric acid ester include triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris (β-chloroethyl) phosphate, tris (dichloropropyl) Phosphate, tris (tribromoneopentyl) phosphate, and the like.

In the present invention, esters (glycolate compounds) of glycolic acid can be used as one kind of polyhydric alcohol esters.

The glycolate compound applicable to the present invention is not particularly limited, but alkyl phthalyl alkyl glycolates can be preferably used.

Alkyl phthalyl alkyl glycolates include, for example, methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, Butyl phthalyl ethyl glycolate, butyl phthalyl ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, and octyl phthalyl ethyl glycolate. Of these, ethyl phthalyl Ethyl glycolate.

The cellulose acylate film of the present invention preferably contains an ultraviolet absorber from the viewpoint of improving the light resistance. The ultraviolet absorber is intended to improve light resistance by absorbing ultraviolet rays of 400 nm or less. Particularly, the transmittance at a wavelength of 370 nm is preferably in the range of 2 to 30%, more preferably in the range of 4 to 20% , And more preferably 5 to 10%.

The ultraviolet absorber preferably used in the present invention is a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a triazine ultraviolet absorber, and particularly preferably a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber.

Benzotriazole, (2-2H-benzotriazol-2-yl) -6- (3,5-di-sec- (Straight chain and branched dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone and the like, and also Tinuvin 109, Tinuvin 171, Tinuvin 234 , Tinuvin 326, Tinuvin 327, Tinuvin 328, and Tinuvin 928), all of which can be preferably used as a commercial product manufactured by BASF Japan. Of these, halogen-free ones are preferred.

In addition, a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as an ultraviolet absorber.

The cellulose acylate film of the present invention preferably contains two or more ultraviolet absorbers.

As the ultraviolet absorber, a polymer ultraviolet absorber can be preferably used. In particular, a polymer-type ultraviolet absorber described in JP-A-6-148430 is preferably used. It is preferable that the ultraviolet absorber does not have a halogen group.

The ultraviolet absorber may be added by dissolving the ultraviolet absorber in an alcohol such as methanol, ethanol or butanol, or an organic solvent such as methylene chloride, methyl acetate, acetone, or dioxolane, or a mixed solvent thereof, Or may be added during the composition.

The organic solvent and the cellulose acylate which are not dissolved in the organic solvent such as the inorganic powder are dispersed using a dissolver or a sand mill and then added to the dope.

The amount of the ultraviolet absorber to be used is not constant depending on the kind of the ultraviolet absorber and the conditions of use, but when the dry film thickness of the cellulose acylate film is 15 to 50 탆, the amount of the ultraviolet absorber is in the range of 0.5 to 10% , More preferably in the range of 0.6 to 4 mass%.

Antioxidants are also called deterioration inhibitors. When an organic electroluminescent display device or the like is placed in a state of high humidity and high temperature, deterioration of the cellulose acylate film may occur.

The antioxidant has a role of retarding or preventing the degradation of the cellulose acylate film by, for example, halogen in the residual solvent amount in the cellulose acylate film or phosphoric acid in the phosphoric acid plasticizer, etc. Therefore, the cellulose acylate It is preferable to be contained in the late film.

As such an antioxidant, a hindered phenol-based compound is preferably used, and examples thereof include 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- Bis (n-octylthio) -6- (4-hydroxy-phenyl) propionate, 3,5-di-t-butyl anilino) -1,3,5-triazine, 2,2-thio-diethylene bis [3- (3,5- ) Propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tris- Di-t-butyl-4-hydroxybenzyl) -isocyanurate and the like.

Particularly preferred are 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t- Glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferable. Also, for example, a hydrazine-based metal inactive agent such as N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, Di-t-butylphenyl) phosphite, or the like may be used in combination.

The amount of these compounds to be added is preferably in the range of 1 ppm to 1.0%, more preferably in the range of 10 to 1000 ppm, based on the weight of the cellulose acylate film.

&Lt; Particles (Mat) >

The cellulose acylate film may further contain fine particles (made of a mat) if necessary in order to improve the slidability of the surface.

The fine particles may be inorganic fine particles or organic fine particles. Examples of the inorganic fine particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, And the like. Among them, silicon dioxide and zirconium oxide are preferable, and silicon dioxide is more preferable in order to reduce the haze increase of the obtained film.

Examples of the fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Sephaster KE- P30, KE-P50, and KE-P100 (manufactured by Nippon Shokubai Co., Ltd.). Above all, Aerosil R972V, NAX50, Seesuter KE-P30 and the like are particularly preferred because they reduce the coefficient of friction while keeping the turbidity of the obtained film low.

The primary particle diameter of the fine particles is preferably in the range of 5 to 50 nm, more preferably in the range of 7 to 20 nm. When the primary particle diameter is large, the effect of increasing the slidability of the obtained film is large, but the transparency tends to decrease. Therefore, the fine particles may be contained as secondary aggregates having a particle diameter in the range of 0.05 to 0.3 탆. The size of the primary particles or the secondary aggregates of the fine particles is determined by observing the primary particles or the secondary aggregates at a magnification of 50 to 200,000 times with a transmission electron microscope and as an average value of the particle diameters of the primary particles or the secondary aggregates .

The content of the fine particles is preferably in the range of 0.05 to 1.0 mass%, and more preferably in the range of 0.1 to 0.8 mass% with respect to the resin forming the cellulose acylate film.

&Lt;

In order to improve the display quality of an image display device such as a liquid crystal display device, a retardation control agent is added to a cellulose acylate film, or an orientation film is formed to provide a liquid crystal layer, and the phase difference from the polarizing plate protective film and the liquid crystal layer is made complex , The cellulose acylate film can be imparted with an optical compensation ability.

Examples of the retardation control agent include aromatic compounds having two or more aromatic rings as described in European Patent No. 911,656A2, and rod-shaped compounds described in JP-A-2006-2025. Two or more kinds of aromatic compounds may be used in combination. The aromatic ring of the aromatic compound is preferably an aromatic heterocycle including an aromatic heterocycle in addition to an aromatic hydrocarbon ring. An aromatic heterocycle is generally an unsaturated heterocycle. Among them, the 1,3,5-triazine ring described in JP-A-2006-2026 is preferable.

The compound having the structure represented by the general formula (1) also functions as a retardation control agent. As a result, a compound having a structure represented by the general formula (1) can impart both functions of retardation control and optical value fluctuation suppression to humidity fluctuation as a single compound.

The addition amount of the retardation control agent is preferably in the range of 0.5 to 20 mass%, more preferably in the range of 1 to 10 mass%, based on 100 mass% of the resin used as the film base.

&Lt; Process for producing cellulose acylate film &

As a method of producing the cellulose acylate film of the present invention, it is possible to use a production method such as a general inflation method, a T-die method, a calendering method, a cutting method, a fining method, an emulsion method and a hot press method. The solution casting method and the melt casting film forming method can be selected from the viewpoints of suppressing the occurrence of cracks, suppression of optical defects such as die lines, and the like. From the viewpoint of obtaining a uniform and smooth surface, desirable.

(A) solution casting method

Hereinafter, a production example of producing the cellulose acylate film of the present invention by the solution casting method will be described.

The preparation of the cellulose acylate film of the present invention is a step of preparing a dope by dissolving additives such as at least cellulose acylate, a nitrogen-containing heterocyclic compound and an organic ester in a solvent, a step of forming a dope on a belt- A step of drying the flexible dope as a web, a step of peeling off the metal support, a step of stretching, a step of drying, and a step of winding after cooling. The cellulose acylate film of the present invention preferably contains cellulose acylate in a solid content of 60 to 95 mass%.

(1) Dissolution Process

A cellulose acylate, a nitrogen-containing heterocyclic compound according to the present invention, a sugar ester, a polycondensation ester, a polyhydric alcohol ester, or the like, in an organic solvent mainly composed of a good solvent for cellulose acylate A step of mixing a solution of a nitrogen-containing heterocyclic compound, a sugar ester, a polycondensation ester, a polyhydric alcohol ester or other compound according to the present invention into the cellulose acylate solution to prepare a dope by dissolving the compound with stirring; Is a step of forming a dope which is a solution.

When the cellulose acylate film of the present invention is prepared by the solution casting method, the organic solvent useful for forming the dope can be used without limitation as long as it dissolves cellulose acylate and other compounds at the same time.

Examples of the chlorinated organic solvent include methylene chloride and examples of the non-chlorinated organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, , Ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro Propanol, nitroethane and the like, and methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.

The dope preferably contains, in addition to the organic solvent, a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40 mass%. When the proportion of alcohol in the dope is high, the web gels to facilitate peeling from the metal support. When the ratio of alcohol is small, it accelerates the dissolution of cellulose acylate and other compounds in the non-chlorinated organic solvent system There is also. In the cellulose acylate film-forming composition of the present invention, a method of forming a film by using a dope in which the alcohol concentration is in the range of 0.5 to 15.0 mass% can be applied in order to enhance the planarity of the resulting cellulose acylate film.

In particular, the dope composition is preferably a dope composition obtained by dissolving cellulose acylate and other compounds in a range of 15 to 45 mass% in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms .

Examples of the straight chain or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Of these, methanol and ethanol are preferable from the viewpoints of stability of dope, relatively low boiling point, and good drying property.

The dissolution of the cellulose acylate, the nitrogen-containing heterocyclic compound, the sugar ester, the polycondensation ester, and the polyhydric alcohol ester or other compounds may be carried out at a normal pressure, a method performed at a boiling point or lower of the main solvent, A method which is carried out by a cooling dissolution method as described in JP-A-9-95544, JP-A-9-95557 or JP-A-9-95538, -21379, or a method of performing pressurization at a boiling point or higher of the main solvent is preferable.

The concentration of the cellulose acylate in the dope is preferably in the range of 10 to 40 mass%. A compound is added to the dope during or after dissolution and dissolved and dispersed. The solution is filtered with a filter medium, defoamed, and sent to the next step by a liquid-feeding pump.

It is preferable to use a filter medium having a collection particle diameter of 0.5 to 5 占 퐉 and a filtration time of 10 to 25 sec / 100 ml for a filtration time.

In this method, only the aggregate can be removed by using a filter material having a collection particle diameter of 0.5 to 5 占 퐉 and a filtration time of 10 to 25 sec / 100 ml for the aggregation remaining at the time of particle dispersion or the aggregation occurring at the time of addition of the initiator . Since the concentration of the particles in the main droplet is sufficiently thin compared to the addition liquid, the aggregated particles adhere to each other at the time of filtration, and the filtration pressure does not increase suddenly.

Fig. 1 is a diagram schematically showing an example of a dope preparing step, a softening step and a drying step of a solution casting film-forming method preferable in the present invention.

The large aggregate is removed from the charging kiln 41 by the filter 44, and is sent to the stock kiln 42. Thereafter, various additive liquids are added from the stock kiln 42 to the main furnace melting furnace 1.

Thereafter, the main dope is filtered in the main filter 3, and the ultraviolet absorbent added liquid is added inline from the conduit 16 to the main filter.

In most cases, the main scrap may contain about 10 to 50% by mass of recovered scrap.

The recovered scrap is obtained by finely pulverizing the cellulose acylate film. The recovered scrap is obtained by cutting off both side portions of the film, which is generated when the cellulose acylate film is formed, or by using a cellulose acylate film Fabric is used.

As the raw material for the resin used in the dope preparation, pellets of cellulose acylate and other compounds may be preferably used.

(2) Flexible process

(2-1) Dope flexing

An endless metal support 31, for example, a stainless steel belt, or a rotating metal drum 31, which feeds the dope to the pressure die 30 through a feed pump (for example, a pressurized metering gear pump) Or the like, at a flexible position on a metal support.

The metal support in the casting step is preferably mirror-finished on the surface, and as the metal support, a stainless steel belt or a drum finished by plating the cast iron surface is preferably used. The width of the cast may be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m. The surface temperature of the metal support of the flexible process is set to a range of -50 ° C to a temperature at which the solvent does not foam by boiling, more preferably -30 to 0 ° C. A higher temperature is preferable because it can speed up the drying speed of the web. However, when the temperature is too high, the web may be foamed or the planarity may deteriorate. A suitable support temperature is appropriately determined at 0 to 100 캜, more preferably in the range of 5 to 30 캜. Alternatively, it is preferable that the web be gelled by cooling to peel off the drum in a state containing a large amount of residual solvent. A method of controlling the temperature of the metal support is not particularly limited, but there is a method of blowing hot air or cold air, or a method of bringing hot water to the side of the metal support. Since the heat is efficiently transferred to the use of the hot water, the time until the temperature of the metal support becomes constant is short, which is preferable. In the case of using warm air, in consideration of the temperature drop of the web due to the latent heat of evaporation of the solvent, winds higher in temperature than the target temperature may be used while preventing the foaming while using warm air above the boiling point of the solvent. In particular, it is preferable to change the temperature of the support body and the temperature of the drying wind during the period from the softening to the peeling, and to perform the drying efficiently.

It is preferable to use a press die which can adjust the slit shape of the nipping portion of the die and make the film thickness uniform. The pressure die includes a coated hanger die and a T die, all of which are preferably used. The surface of the metal support is mirror-finished. Two or more pressure dies may be provided on the metal support in order to increase the film forming speed, and the doping amount may be divided into two or more layers.

(3) Solvent Evaporation Process

A web (a dope is formed on a flexible support and the formed dope is referred to as a web) is heated on a flexible support to evaporate the solvent.

In order to evaporate the solvent, there are a method of blowing air from the web side, a method of transferring heat from the back surface of the support by liquid, a method of transferring heat from the front and back by radiant heat, and the like. . Also, a method of combining them is also preferably used. It is preferable to dry the web on the supporter after the softening on the support in an atmosphere of 40 to 100 캜. In order to maintain the temperature in the range of 40 to 100 占 폚, it is preferable to warm the warm air at this temperature to the upper surface of the web or to heat it by means of infrared rays or the like.

From the standpoint of surface quality, moisture permeability and releasability, it is preferable to peel the web from the support within 30 to 120 seconds.

(4) Peeling process

And peeling the web from which the solvent has evaporated on the metal support at the peeling position. The peeled web is sent to the next process.

The temperature at the peeling position on the metal support is preferably in the range of 10 to 40 占 폚, and more preferably in the range of 11 to 30 占 폚.

The amount of the residual solvent at the time of peeling the web on the metal support at the time of peeling is preferably in the range of 50 to 120 mass% depending on the strength of the drying condition, the length of the metal support, etc. However, When the web is peeled off at many points of time, if the web is too soft, the flatness is deteriorated in peeling, and peeling tension or vertical stripes tend to occur due to the peeling tension, so that the amount of residual solvent at the time of peeling is determined in balance of economic speed and quality.

The amount of residual solvent in the web is defined by the following formula (Z).

The formula (Z)

Residual solvent amount (%) = (mass before heat treatment of web-mass after heat treatment of web) / (mass after heat treatment of web) 占 100

The heat treatment at the time of measuring the residual solvent amount means that the heat treatment is performed at 115 캜 for one hour.

The peel tension at the time of peeling the metal support and the film is usually in the range of 196 to 245 N / m, but it is preferable to peel off with a tension of 190 N / m or less when wrinkles tend to occur at peeling.

In the present invention, the temperature at the peeling position on the metal support is preferably in the range of -50 to 40 占 폚, more preferably in the range of 10 to 40 占 폚, and most preferably in the range of 15 to 30 占 폚 desirable.

(5) Drying and drawing process

The drying process may be divided into a preliminary drying process and a main drying process.

The web obtained by peeling from the metal support is dried. The web may be dried while conveying the web by a plurality of rollers disposed at upper and lower sides, or both ends of the web may be fixed with a clip such as a tenter dryer and dried while being conveyed.

The means for drying the web is not particularly limited, and generally can be performed by hot air, infrared rays, heating rollers, microwaves or the like, but from the standpoint of simplicity, it is preferable to conduct the hot air.

It is effective that the drying temperature in the drying step of the web is preferably a heat treatment at a glass transition point of the film of -5 DEG C or less and at 100 DEG C or more for 10 minutes or more and 60 minutes or less. The drying is carried out at a temperature in the range of 100 to 200 ° C, more preferably in the range of 110 to 160 ° C.

The cellulose acylate film of the present invention is preferably stretched in the MD direction and / or the TD direction, and is preferably stretched in the TD direction by at least a tenter stretching apparatus.

The stretching may be uniaxial stretching or biaxial stretching. In biaxial stretching, stretching may be performed in one direction, and the tension in the other direction may be relaxed to shrink.

The cellulose acetate film of the present invention preferably has a Tg of from (Tg + 15) to (Tg + 15) when the glass transition temperature is Tg in the MD direction and / or the TD direction, preferably the TD direction, (Tg + 50) < 0 > C. When stretched in the above-mentioned temperature range, adjustment of the retardation is easy, the stretching stress can be lowered, and the haze is lowered. In addition, a polarizing plate cellulose acylate film having excellent planarity and coloring property of the film itself can be obtained by suppressing the occurrence of rupture. The stretching temperature is preferably in the range of (Tg + 20) to (Tg + 40) deg.

Here, the glass transition temperature Tg is the midpoint glass transition temperature (Tmg) measured according to JIS K7121 (1987), which is measured using a commercially available differential scanning calorimeter at a heating rate of 20 캜 / min.

The glass transition temperature Tg of a specific cellulose acylate film is measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K7121 (1987).

In the cellulose acylate film of the present invention, it is preferable that the web is stretched at least 1.1 times in the TD direction. The range of the stretching is preferably 1.1 to 1.5 times, more preferably 1.05 to 1.3 times the original width. Within the above range, the movement of molecules in the film is large and a desired retardation value is obtained, and the behavior of the dimensional change of the film can be controlled within a desired range.

When the residual solvent amount is 40% by mass or more after the film is formed, the film is preferably stretched in the MD direction. When the amount of the residual solvent is less than 40% by mass, the film is preferably stretched in the TD direction.

In order to stretch in the MD direction, the peel tension is desirably peeled to 130 N / m or more, and particularly preferably 150 to 170 N / m. Since the web after peeling is in a state of high residual solvent, stretching in the MD direction can be performed by maintaining the same tensile force as the peeling tension. As the web dries and the amount of the residual solvent decreases, the elongation in the MD direction decreases.

The drawing magnification in the MD direction can be calculated from the rotating speed of the belt support and the tenter operating speed.

In order to stretch in the TD direction, for example, the entire drying step or a part of the steps as disclosed in Japanese Patent Application Laid-Open No. 62-46625 may be carried out by clipping or finishing the widthwise direction (Called a tenter system), among which a tenter system using a clip and a pin tenter system using a fin are preferably used.

The retardation value Ro and the retardation value Rt in the thickness direction of the cellulose acylate film of the present invention necessarily have retardation by stretching, but the retardation value Rt in the thickness direction is measured by an automatic scanning birefringence meter (Axo Scan Mueller Matrix Polarimeter ) to, in the environment and, of wavelength 590nm of 23 ℃ · 55% RH, subjected to three-dimensional refractive index measurement can be calculated from the refractive index n _x, n _y, n _z obtained by use.

The cellulose acylate film of the present invention is characterized in that retardation value Ro in the in-plane direction defined by the following formula (i) is in the range of 40 to 70 nm and retardation value Rt in the thickness direction defined by the following formula (ii) It is preferable that the thickness is in the range of 100 to 300 nm from the viewpoint of improving the visibility in the VA mode liquid crystal display device. The cellulose acylate film can be adjusted within the range of the retardation value by stretching while at least adjusting the stretch ratio in the TD direction.

Formula (i): Ro = (n x -n y) × d (nm)

Formula (ii): Rt = {( n x + n y) / 2-n z} × d (nm)

After a predetermined heat treatment or cooling treatment, it is preferable to provide a slitter before winding to cut off the end portion in order to obtain a good winding appearance. It is preferable to perform knurling on both ends of the width.

Knurling can be formed by pressing a heated embossing roller. The embossing roller is provided with fine irregularities. By pressing the irregularities, irregularities can be formed on the film and the end portion can be made bulky.

The knurl height at both ends of the width of the retardation film of the present invention is preferably 4 to 20 탆 and the width is 5 to 20 mm.

Further, in the present invention, it is preferable that the knurling is performed after completion of drying in the film-forming step of the film and before winding.

(6) Coiling process

When the amount of the residual solvent in the web becomes 2% by mass or less, the step of winding the film as a film, the amount of the residual solvent is 0.4% by mass or less, whereby a film having good dimensional stability can be obtained.

As the winding method, a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like.

(B) Melting and softening method

The method for producing the cellulose acylate film of the present invention by the melt softening method comprises the steps of: B1) a step of producing a melt pellet (pelletizing step), B2) a step of melt-kneading the melt pellets and then extruding (melt extrusion step) B3) a step of cooling and solidifying the molten resin to obtain a web (cooling and solidifying step), and B4) a step of stretching the web (stretching step).

B1) Pelletizing process

The composition containing cellulose acylate, which is the main component of the cellulose acylate film, is preferably pre-kneaded and pelletized. The pelletization can be carried out by a known method. For example, a resin composition containing the above-described cellulose acylate and, if necessary, additives such as a plasticizer is melted and kneaded by an extruder, and then extruded from a die into a strand shape . The molten resin extruded into a strand shape can be water-cooled or air-cooled, and then cut to obtain pellets.

It is preferable that the raw material of the pellet is dried before being supplied to the extruder in order to prevent the decomposition.

The antioxidant and the thermoplastic resin may be mixed with each other, or the antioxidant dissolved in a solvent may be impregnated with a thermoplastic resin or may be mixed with the antioxidant sprayed into the thermoplastic resin. The ambient atmosphere of the feeder portion of the extruder and the outlet portion of the die is preferably an atmosphere such as dehumidified air or nitrogen gas in order to prevent deterioration of the raw materials of the pellets.

In the extruder, it is preferable to perform kneading at a low shear force or at a low temperature so as not to cause deterioration of the resin (decrease in molecular weight, coloring, gelation, etc.). For example, in the case of kneading with a twin-screw extruder, it is preferable to use a deep groove-type screw to rotate the two screws in the same direction. In order to uniformly knead, it is preferable that the shapes of the two screws are intermeshed with each other.

B2) Melt extrusion process

The obtained melt pellets and, if necessary, other additives are fed from the hopper to the extruder. The supply of the pellets is preferably carried out under vacuum, under reduced pressure or in an inert gas atmosphere in consideration of the prevention of oxidative decomposition of the pellets. In the extruder, the melt pellets as the film material and other additives as required are melt-kneaded.

The melting temperature of the film material in the extruder varies depending on the type of the film material, but is preferably in the range of Tg to (Tg + 100) 占 폚, And is preferably within the range of (Tg + 10) to (Tg + 90) deg.

When an additive such as a plasticizer or a fine particle is added in the middle of an extruder, a mixing device such as a static mixer may be further disposed downstream of the extruder in order to uniformly mix these components.

The molten resin extruded from the extruder is filtered, if necessary, by a leaf disk filter or the like, further mixed with a static mixer or the like, and extruded from the die into a film form.

The extrusion flow rate is preferably stabilized by using a gear pump. It is preferable that the leaf disk filter used for removing foreign matter is a stainless steel fiber sintered filter. The stainless steel fiber sintering filter is obtained by entangling a stainless steel fiber body complexly and then compressing it and sintering the contact portions so that the density can be changed according to the thickness and compression amount of the fiber to adjust the filtration accuracy.

The melting temperature of the resin at the outlet portion of the die can be within a range of about 200 to 300 占 폚.

B3) Cooling and solidification process

The resin extruded from the die is nipped with a cooling roller and an elastic touch roller to make the film-like molten resin into a predetermined thickness. Then, the film-shaped molten resin is cooled stepwise by a plurality of cooling rollers to solidify.

The surface temperature of the cooling roller can be set to Tg (占 폚) or less when the glass transition temperature of the obtained film is Tg (占 폚). The surface temperatures of the plurality of cooling rollers may be different.

The elastic touch roller is also referred to as a tightly closed rotating body. A commercially available elastic touch roller may be used. The surface temperature of the film on the elastic touch roller side may be in the range of Tg to (Tg + 110) 占 폚 of the film.

The film-like molten resin solidified from the cooling roller is peeled off with a peeling roller or the like to obtain a web. When peeling the film-like molten resin, it is preferable to adjust the tension to prevent deformation of the obtained web.

B4) Stretching process

The obtained web is stretched by a stretching machine to obtain a film. The stretching is performed in one of the width direction, the transport direction, or the oblique direction of the web.

The drawing method of the web, the draw ratio and the drawing temperature can be the same as described above.

&Lt; Physical Properties of Cellulose Acylate Film >

(Hayes)

The cellulose acylate film of the present invention preferably has a haze of less than 1%, more preferably less than 0.5%. When the haze is less than 1%, transparency of the film becomes higher, which makes it easier to use as a film for optical use. The haze can be measured using a haze meter (model NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K7136.

(Equilibrium moisture content)

The cellulose acylate film of the present invention preferably has an equilibrium moisture content of 4% or less at 25 캜 and a relative humidity of 60%, and more preferably 3% or less. By setting the equilibrium moisture content to 4% or less, it is preferable because it is easy to cope with humidity change and optical properties and dimensions are hardly changed. The equilibrium moisture content was determined by allowing the sample film to stand for 24 hours in a room humidity-conditioned at 23 占 폚 and 80% RH after being left in a room at 23 占 폚 and a relative humidity of 20% for 4 hours or more, (CA-20 type, manufactured by Kagaku Kogyo Co., Ltd.) is used to dry and vaporize water at a temperature of 150 占 폚, and then quantitated by the Karl Fischer method.

(Film length, width, film thickness)

The cellulose acylate film of the present invention is preferably long, and is preferably a length of about 100 to 10000 m, and is wound in a roll form. The width of the cellulose acylate film of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.

The film thickness of the film is preferably in the range of 10 to 100 mu m from the viewpoints of reduction in thickness of the display device and productivity. If the film thickness is 10 mu m or more, a film strength or phase difference of a certain level or more can be produced. When the film thickness is 100 mu m or less, fluctuation of the retardation due to heat or humidity can be suppressed. Preferably in the range of 20 to 70 mu m.

The film thickness unevenness of the film is preferably in the range of 0 to 5 占 퐉 in the thickness direction or the width direction, more preferably in the range of 0 to 3 占 퐉, and still more preferably in the range of 0 to 2 占 퐉.

It is preferable that the polarizing plate of the present invention is such that the cellulose acylate film of the present invention is bonded to at least one surface of the polarizer using a water-soluble or active energy ray-curable adhesive.

It is preferable that a polyester film or an acrylic film is bonded to the polarizer using a water-shed or active-energy ray-curable adhesive on the surface of the polarizer opposite to the surface to which the cellulose acylate film is bonded, It is preferable that the variation of the phase difference is made smaller.

When the polarizing plate of the present invention is used as a polarizing plate on the viewer side, it is preferable to provide an antiglare layer or a clear hard coating layer, an antireflection layer, an antistatic layer, an antifouling layer, or the like on the viewer side film of the polarizing plate.

[Polarizer]

The polarizer, which is a main component of the polarizing plate of the present invention, is an element that allows only light of a polarization plane in a certain direction to pass. A currently known polarizer is a polyvinyl alcohol polarizing film. The polyvinyl alcohol polarizing film includes a polyvinyl alcohol film stained with iodine and a dichroic dye stained.

As the polarizer, a polarizer in which a polyvinyl alcohol aqueous solution is formed, uniaxially stretched, dyed, uniaxially stretched, and preferably subjected to a durability treatment with a boron compound can be used. The film thickness of the polarizer is preferably 2 to 30 占 퐉, particularly preferably 2 to 15 占 퐉.

Further, an ethylene-modified polyvinyl alcohol having an ethylene unit content of 1 to 4 mol%, a degree of polymerization of 2000 to 4000 and a saponification degree of 99.0 to 99.99 mol% described in JP-A-2003-248123 and JP-A-2003-342322 Alcohol is also preferably used. Among them, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 占 폚 is preferably used. The polarizer using the ethylene-modified polyvinyl alcohol film has excellent polarizing performance and durability, and has less color unevenness, and is particularly preferably used in a large-sized liquid crystal display device.

&Lt; Polarizer of laminated film type &

The polarizing plate of the present invention is preferably made of a thin film, and the thickness of the polarizer is preferably in the range of 2 to 15 탆 from the viewpoint of achieving both strength and thinning of the polarizing plate.

As such a polarizer of a thin film, it is possible to manufacture a laminated film type polarizer by the method described in Japanese Patent Application Laid-Open Nos. 11-116111, 1186161, 128631/1994, desirable.

The polarizing laminated film has a polarizer layer including a polyvinyl alcohol-based resin layer in which a dichroism dye is adsorbed and oriented, and itself can be used as a polarizing plate. As a preferred embodiment of the present invention, after the polarizing laminated film is formed by the above process, the polyvinyl alcohol layer of the polarizing laminated film is peeled from the base film, and the polyvinyl alcohol layer is laminated on the polarizer . According to the above method, since the thickness of the polarizer layer can be set to 15 탆 or less, a thin polarizer can be obtained.

[Production of polarizing plate]

The polarizing plate of the present invention can be manufactured by a general method. It is preferable to bond the cellulose acylate film of the present invention to a surface of at least one polarizer produced by alkali saponifying the polarizer side of the cellulose acylate film of the present invention by immersion in an iodine solution and using a completely saponified polyvinyl alcohol aqueous solution (water-soluble). Another polarizing plate protective film can be bonded to the other side. The cellulose acylate film of the present invention is preferably provided on the side of the liquid crystal cell of the polarizer when it becomes a liquid crystal display device, and a conventional polarizing plate protective film can be used as the outer film of the polarizer.

For example, as a conventional polarizing plate protective film, commercially available cellulose ester films (for example, Konica Minolta Tact KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC6UA, KC4UY, KC4UE, KC8UY, KC8UXW-RHA-NC, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC8UXW-RHA-NC) are preferably used.

[Active Energy ray curable adhesive]

In the polarizing plate of the present invention, it is also preferable that the cellulose acylate film of the present invention and the polarizer are bonded by an active energy ray curable adhesive.

As the active energy ray curable adhesive, it is preferable to use the following ultraviolet curing type adhesive.

In the present invention, by applying an ultraviolet curable adhesive to the bonding between the cellulose acylate film and the polarizer, a polarizing plate having high strength and excellent planarity can be obtained even if it is a thin film.

&Lt; Composition of ultraviolet curable adhesive >

As the ultraviolet curable adhesive composition for a polarizing plate, there are known a photo radical polymerization type composition using photo radical polymerization, a photo cation polymerization type composition using photo cation polymerization, and a hybrid type composition using photo radical polymerization and photo cation polymerization in combination.

Examples of the photo-radical polymerization type composition include compositions containing a radical polymerizing compound containing a polar group such as a hydroxyl group or a carboxyl group and a radical polymerizing compound not containing a polar group in a specific ratio as described in JP-A-2008-009329 It is known. In particular, the radical polymerizing compound is preferably a compound having a radically polymerizable ethylenic unsaturated bond. Preferable examples of the compound having a radically polymerizable ethylenically unsaturated bond include a compound having a (meth) acryloyl group. Examples of the compound having a (meth) acryloyl group include an N-substituted (meth) acrylamide-based compound, a (meth) acrylate-based compound and the like. (Meth) acrylamide means acrylamide or methacrylamide.

As the photo cationic polymerization type composition, there may be mentioned (a) a cationic polymerizable compound, (?) A photo cationic polymerization initiator, (?) A photoacid generator having a wavelength longer than 380 nm , A photosensitizer exhibiting maximum absorption in the ultraviolet curable adhesive agent, and (?) A naphthalene-based photosensitizer. However, other ultraviolet curable adhesives may be used.

(1) Pretreatment process

The pretreatment step is a step of performing the adhesion facilitating treatment to the adhesion surface of the cellulose acylate film with the polarizer. Examples of the adhesion facilitating treatment include corona treatment and plasma treatment.

(Application step of ultraviolet curing type adhesive)

In the application step of the ultraviolet curing type adhesive, the ultraviolet curing type adhesive is applied to at least one of the bonding surfaces of the polarizer and the cellulose acylate film. When the ultraviolet curing type adhesive is applied directly to the surface of the polarizer or the cellulose acylate film, the application method is not particularly limited. For example, various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, a method may be employed in which an ultraviolet curable adhesive is poured between the polarizer and the cellulose acylate film, and then pressed with a roller or the like to spread out uniformly.

(2) Bonding process

After the ultraviolet curing type adhesive is applied by the above method, it is treated in the bonding step. In this bonding step, for example, when an ultraviolet curable adhesive is applied to the surface of the polarizer in the previous coating step, the cellulose acylate film is superimposed thereon. Further, in the case of applying the ultraviolet curable adhesive to the surface of the cellulose acylate film for the first time, the polarizer is superimposed thereon. In addition, when an ultraviolet curable adhesive is poured between the polarizer and the cellulose acylate film, the polarizer and the cellulose acylate film are superimposed in this state. Normally, in this state, the film is sandwiched between pressing rollers or the like from the side of the cellulose acylate film on both sides and pressed. As the material of the pressure roller, metal or rubber can be used. The pressure rollers disposed on both sides may be the same material or different materials.

(3) Curing process

In the curing step, ultraviolet rays are irradiated to an ultraviolet curing type adhesive which is uncured and a cationic polymerizable compound (for example, an epoxy compound or an oxetane compound) or a radical polymerizing compound (for example, an acrylate compound, an acrylamide compound And the like) is cured, and the polarizer and the cellulose acylate film are superimposed on each other via the ultraviolet curable adhesive. When the cellulose acylate film is bonded to one surface of the polarizer, the active energy ray may be irradiated from either the polarizer side or the cellulose acylate film side. When the cellulose acylate film is bonded to both surfaces of the polarizer, ultraviolet rays are irradiated on the both surfaces of the polarizer in a state in which the cellulose acylate film is superimposed with the ultraviolet curable adhesive interposed therebetween to simultaneously cure the ultraviolet curable adhesive on both sides It is advantageous.

The irradiation condition of the ultraviolet ray may be any suitable condition as long as it is a condition capable of curing the ultraviolet curable adhesive applied in the present invention. The irradiation amount of the ultraviolet rays is preferably in the range of 50 to 1500 mJ / cm < 2 > and more preferably in the range of 100 to 500 mJ / cm &

When the production process of the polarizing plate is performed in a continuous line, the line speed varies depending on the curing time of the adhesive, but is preferably in the range of 1 to 500 m / min, more preferably in the range of 5 to 300 m / min, 10 to 100 m / min. If the line speed is 1 m / min or more, productivity can be secured, or the damage to the cellulose acylate film can be suppressed, and a polarizer excellent in durability can be produced. When the line speed is 500 m / min or less, the curing of the ultraviolet curing type adhesive becomes sufficient, so that the ultraviolet curing type adhesive layer having the desired hardness and excellent adhesiveness can be formed.

[Polyester film and acrylic film]

It is preferable that a polyester film or an acrylic film is bonded to the polarizer using a water-shed or active-energy ray-curable adhesive on the surface of the polarizer opposite to the surface to which the cellulose acylate film is bonded, Is a preferable form from the viewpoint of obtaining a high polarizing plate. The bonding may be any of the above water-curing adhesives and ultraviolet curing adhesives which are active energy ray curable adhesives, but from the viewpoint of the effect of the present invention, it is preferable to use an ultraviolet curable adhesive.

In the present invention, the outer film (polarizing plate protective film) may be formed of a polyester film or an acrylic film having low moisture permeability, or an inner film (phase difference film) as a cellulose acylate film having improved fluctuation of phase difference with respect to humidity variation of the present invention It is presumed that the influence of moisture from the outside can be reduced and the moisture in the inside can be easily released and thus the polarizing plate can be obtained in which the durability against the humidity fluctuation of the polarizing plate is improved in general.

(1) Polyester film

The polyester resin forming the polyester film is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,4 Naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, diphenylcarboxylic acid, diphenoxyethane dicarboxylic acid, diphenylsulfonic acid, anthracene dicarboxylic acid, 1,3-cyclo Cyclohexane dicarboxylic acid, hexahydroterephthalic acid, hexahydroterephthalic acid, malonic acid, dimethyl malonic acid, succinic acid, 3,3-cyclohexanedicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Diethyl succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, dimeric acid, sebacic acid, And dicarboxylic acids such as ethylene glycol, propylene glycol, hexamethylene glycol , Neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- Or a diol such as hexadiol, 2,2-bis (4-hydroxyphenyl) propane or bis (4-hydroxyphenyl) sulfone, or a mixture of at least one dicarboxylic acid Or a copolymer obtained by polycondensing two or more kinds of diols or a copolymer obtained by polycondensing at least one kind of diol with two or more dicarboxylic acids and a blend resin obtained by blending two or more homopolymers or copolymers One polyester resin may be mentioned. Among them, a polyethylene terephthalate resin is preferably used. The above resins may be mixed and used.

The polyester film is obtained, for example, by a method in which the above-mentioned polyester resin is melt-extruded into a film form and cooled and solidified by a casting drum to form a film. As the polyester film in the polarizing plate of the present invention, any of an unstretched film and a stretched film can be used. For example, in the case where birefringence is required to be small, an unstretched film can be suitably used. Further, in the case where birefringence is used for optical compensation of a liquid crystal display device, a stretched film can be suitably used. In addition, a stretched film, particularly a biaxially stretched film, is suitably used in terms of strength.

The polyester film is excellent in durability as compared with the TAC film, but unlike the TAC film, the polyester film tends to have birefringence. Therefore, when this is used as a polarizing plate protective film, irregular color irregularity occurs when viewed from the oblique direction, do.

For this reason, the polyester film is preferably a polyester film having an in-plane retardation value of 3,000 to 30,000 nm. At this time, it is preferable that the polarizing plate protective film on the outgoing light side of the polarizing plate disposed on the outgoing light side of the liquid crystal cell is a polyester film having a retardation value of 3000 to 30000 nm. The ratio (Ro / Rt) of the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction of the polyester film is preferably 0.200 or more. With such a configuration, it is possible to obtain a spectrum approximated to the light source of the spectrum of the transmitted light at any viewing angle, and it is possible to ensure good visibility without irregular color unevenness. Further, mechanical strength suitable for thinning can be provided.

Such a polyester film may use polyethylene terephthalate or polyethylene naphthalate, but may contain other copolymerizable components. These resins have excellent transparency as well as excellent thermal and mechanical properties, and can easily control the retardation value by stretching. In particular, polyethylene terephthalate is the most preferable material because it has a large intrinsic birefringence and a relatively large retardation value even if the thickness of the film is thin.

The retardation value can be obtained by measuring the refractive index and the thickness in the biaxial direction and can be measured by a commercially available automatic birefringence measuring device such as KOBRA-21ADH (Oji-Keisei Kikuchi Kogyo Co., Ltd.) or Axoscan .

The polyester film can be produced by a general method for producing a polyester film. For example, an unoriented polyester extruded into a sheet form by melting a polyester resin is stretched in the longitudinal direction at a temperature not lower than the glass transition temperature using the speed difference of the roll, and then stretched in the transverse direction by a tenter And a heat treatment is carried out.

The polyester film according to the present invention may be a uniaxially stretched film or a biaxially stretched film, but when a biaxially stretched film is used as a polarizer protective film, uneven color irregularity is seen even when viewed from above the film surface However, caution is necessary because irregular color irregularities may be observed when observed from the oblique direction.

This phenomenon is considered to be due to the fact that the biaxially stretched film is made of an ellipsoid of refractive index having a different refractive index in the running direction, the width direction and the thickness direction, and the retardation in the in-plane direction becomes zero according to the transmission direction of light in the film The refractive index ellipsoid appears to be the origin). Therefore, when the liquid crystal display screen is viewed from a specific direction in the oblique direction, there is a case where a point where the retardation value in the in-plane direction becomes zero is generated, and irregular color heterogeneity occurs concentrically around the point . When the angle from the position directly above the film surface (normal direction) to the position where the irregular color irregularity is visible is denoted by?, The angle? Increases as the birefringence in the film surface increases, and irregular color irregularity becomes less visible . Since the angle &thetas; tends to decrease in the biaxially stretched film, the unevenness of the uniaxially stretched film tends to be less visible, which is preferable.

However, in the case of a complete uniaxial (uniaxial symmetry) film, the mechanical strength in the direction perpendicular to the alignment direction is remarkably lowered, which is undesirable. The polyester film according to the present invention is a polyester film having a biaxial (biaxial) symmetry in a range that does not cause substantially irregular color irregularity, or a range in which a irregular color irregularity is not generated in a viewing angle range required for a liquid crystal display screen ).

(Retardation in the in-plane direction) of the polarizing plate protective film and the ratio of the retardation (Rt) value in the thickness direction of the polarizing plate protective film to the retardation of the polarizing plate protective film It is preferable to control so as to fall within a specific range. The smaller the difference between the in-plane retardation and the thickness-direction retardation, the more the isotropic action of birefringence depends on the viewing angle, so that the change in retardation with respect to the viewing angle decreases. Therefore, it is considered that iridescence-like color unevenness is hardly generated in accordance with the observation angle.

The ratio (Ro / Rt) of the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction of the polyester film according to the present invention is preferably 0.200 or more, more preferably 0.500 or more, Is not less than 0.600. As the ratio (Ro / Rt) of the retardation value Ro in the in-plane direction to the retardation value Rt in the thickness direction is larger, the action of birefringence increases the isotropy so that irregular color heterogeneity occurs in accordance with the observation angle It gets harder. In the case of a complete uniaxial (uniaxial) film, the value (Ro / Rt) of the ratio between the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction is 2.0. However, as described above, the mechanical strength in the direction perpendicular to the alignment direction is remarkably lowered as the film becomes closer to the complete uniaxial (uniaxial) film.

On the other hand, the ratio (Ro / Rt) of the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction of the polyester film according to the present invention is preferably 1.2 or less, more preferably 1.0 or less. (Ro / Rt) of the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction is not required to be 2.0, and is preferably 1.2 or less Is enough. Even if the above ratio is 1.0 or less, it is sufficiently possible to satisfy the viewing angle characteristics required for a liquid crystal display device (left and right 180 degrees, upper and lower 120 degrees).

The film forming conditions of the polyester film according to the present invention will be described in detail. The longitudinal stretching temperature and transverse stretching temperature are preferably 80 to 130 占 폚, particularly preferably 90 to 120 占 폚. The longitudinal stretching magnification is preferably 1.0 to 3.5 times, particularly preferably 1.0 to 3.0 times. The transverse stretching ratio is preferably 2.5 to 6.0 times, particularly preferably 3.0 to 5.5 times. In order to control the retardation within the above range, it is preferable to control the ratio between the longitudinal stretching magnification and the transverse stretching magnification. If the difference in elongation magnification between the transverse and longitudinal directions is too small, it is difficult to increase the retardation, which is not preferable. Setting the stretching temperature to a lower value is also a preferable countermeasure for increasing the retardation. In the subsequent heat treatment, the treatment temperature is preferably 100 to 250 占 폚, particularly preferably 180 to 245 占 폚. In order to suppress the fluctuation of the retardation, it is preferable that the thickness irregularity of the film is small. Since the stretching temperature and stretching ratio greatly affect the thickness irregularity of the film, it is necessary to optimize the film forming conditions even from the viewpoint of thickness unevenness. In particular, when the longitudinal stretching magnification is lowered in order to increase the retardation, the longitudinal thickness unevenness may be deteriorated. Since the longitudinal thickness unevenness has a region in which the stretching magnification is extremely deteriorated in a certain range, it is preferable to set the film forming conditions at a position outside this range.

The thickness irregularity of the film is preferably 5.0% or less, more preferably 4.5% or less, even more preferably 4.0% or less, and particularly preferably 3.0% or less.

As described above, in order to control the retardation value of the film to a specific range, it can be performed by appropriately setting the stretch magnification, the stretching temperature, and the film thickness. For example, a higher retardation value can be obtained as the stretching ratio, the stretching temperature, and the thickness of the film become thicker. On the contrary, a lower retardation value is easier to obtain as the stretching ratio is lower, the stretching temperature is higher, and the film thickness is thinner. However, if the thickness of the film is increased, the retardation value in the thickness direction tends to become large. Therefore, it is preferable to appropriately set the film thickness in the range described later. In addition to the control of the retardation value, it is necessary to set the final film forming conditions in consideration of the physical properties required for processing and the like.

The thickness of the polyester film according to the present invention is arbitrary, but is preferably in the range of 15 to 300 mu m, more preferably in the range of 15 to 200 mu m. Even in the case of a film having a thickness of less than 15 占 퐉, in principle, it is possible to obtain a retardation value of 3000 nm or more. However, in this case, the anisotropy of the mechanical properties of the film becomes remarkable, and cracking, tearing, and the like are liable to occur, and practical utility as an industrial material is remarkably lowered. A particularly preferable lower limit of the thickness is 25 占 퐉. On the other hand, if the upper limit of the thickness of the polyester film exceeds 300 탆, the thickness of the polarizing plate becomes too thick, which is not preferable. From the standpoint of practicality as a polyester film, the upper limit of the thickness is preferably 200 mu m. An upper limit of a particularly preferable thickness is 100 mu m which is equivalent to a general TAC film. In order to control the retardation value within the range of the present invention within the above-mentioned thickness range, the polyester used as the film base is preferably polyethylene terephthalate.

In the polyester film according to the present invention, various additives may be used. Examples of other additives include plasticizers, ultraviolet absorbers, fluorine-based surfactants, exfoliating agents, matting agents, deterioration inhibitors, optical anisotropy control agents, infrared absorbers and the like.

(2) Acrylic films

An acrylic resin contained in an acrylic film (hereinafter also referred to as an acrylic resin film) means a (meth) acrylic resin, and includes both an acrylic resin and a methacrylic resin. Hereinafter, the acrylic resin will be described.

The acrylic resin is a (meth) acrylic resin as described above, and means a polymer of an acrylic acid ester or a methacrylic acid ester. As the polymer of the methacrylic ester, for example, it is preferable to include a polymer mainly comprising alkyl methacrylate. The monomer composition of the alkyl methacrylate is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on 100% by mass of the total of all the monomers %, And the alkyl methacrylate is 99 mass% or less. The acrylic resin may be a homopolymer of alkyl methacrylate or a copolymer of 50 mass% or more of alkyl methacrylate and 50 mass% or less of a monomer other than alkyl methacrylate. As the alkyl methacrylate, usually those having 1 to 4 carbon atoms in the alkyl group are used, and among them, methyl methacrylate is preferably used.

The monomer other than alkyl methacrylate may be a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule or a polyfunctional monomer having two or more polymerizable carbon-carbon double bonds in the molecule. In particular, monofunctional monomers are preferably used, and examples thereof include alkyl acrylates such as methyl acrylate and ethyl acrylate, styrene monomers such as styrene and alkyl styrene, acrylonitrile and methacrylate such as acrylonitrile and methacrylonitrile And unsaturated nitriles such as acrylonitrile and acrylonitrile. When alkyl acrylate is used as the copolymerization component, the number of carbon atoms thereof is usually from 1 to 8.

As the acrylic resin, it is preferable not to have a glutarimide derivative, a glutaric acid anhydride derivative, a lactone ring structure, or the like. This acrylic resin may not have sufficient mechanical strength and moisture resistance as an acrylic resin film.

In the present invention, from the viewpoint that the content of the organic solvent in the dope can be reduced, the drying time can be shortened, and the surface shape of the formed film is excellent, the weight average molecular weight of the acrylic resin Mw) is preferably not less than 80000, and furthermore, the weight average molecular weight of the acrylic resin is preferably in the range of 100000 to 400000 from the viewpoint of further improving the film surface shape upon lamination.

The upper limit of the weight average molecular weight of the acrylic resin can be maintained at 4000000 as the upper limit because the compatibility of the solution can be maintained without excessively increasing the viscosity and the compatibility of the organic solvent and the additive can be ensured during the preparation of the dope .

The weight average molecular weight of the acrylic resin used in the present invention can be measured by the above gel permeation chromatography.

In order to improve the flexibility of the acrylic film to improve the handling property, it is preferable that the acrylic resin is blended with rubber elastomer particles. The rubber elastomer particle is a particle containing a rubber elastomer, and may be a particle composed only of a rubber elastomer, or may be a multi-layered particle having a rubber elastomer layer. Examples of the rubber elastomer include olefin elastomer, diene elastomer, styrene-diene elastomer copolymer, and acrylic elastomer. Among them, an acrylic elastomer is preferable in terms of surface hardness, light resistance and transparency of an acrylic resin film.

The acrylic elastomer is preferably a polymer mainly composed of an alkyl acrylate and may be a homopolymer of alkyl acrylate or a copolymer of 50 mass% or more of alkyl acrylate and 50 mass% or less of a monomer other than alkyl acrylate. As the alkyl acrylate, usually those having 4 to 8 carbon atoms in the alkyl group are used. Examples of monomers other than alkyl acrylate include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene monomers such as styrene and alkyl styrene, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Monofunctional monomers, alkenyl esters of unsaturated carboxylic acids such as (meth) acrylic acid allyl and (meth) acrylic acid methallyl, dialkyl esters of dibasic acids such as maleic acid diallyl, alkylene glycol di (meth) And unsaturated carboxylic acid diesters of glycols such as polyfunctional monomers.

The rubber elastomer particles containing an acrylic elastomer are preferably particles of a multi-layer structure having a layer of an acrylic elastomer, and a rubber layer of a two-layer structure having a polymer layer mainly composed of methacrylic acid alkyl on the outer side of the acrylic elastomer Or a three-layer structure having a polymer layer mainly composed of methacrylic acid alkyl on the inner side of the acrylic elastomer. Examples of the monomer composition of the polymer mainly composed of alkyl methacrylate constituting the layer formed on the outer side or in the inner side of the acrylic elastomer include a monomer composition of a polymer mainly composed of alkyl methacrylate, This is similar to the example of composition. Such multi-layered acrylic rubber elastomer particles can be produced by the method described in, for example, Japanese Patent Publication No. 55-27576.

As the rubber elastomer particles, those having a number average particle diameter of 10 to 300 nm of the rubber elastomer contained therein can be used. Thereby, when the acrylic resin film is laminated on the polarizing film by using the adhesive, it is possible to make the acrylic resin film difficult to peel off from the adhesive layer. The number average particle diameter of the rubber elastic body is preferably 50 nm or more and 250 nm or less.

In the rubber elastomer particles in which the outermost layer is a polymer mainly composed of methyl methacrylate and in which the acrylic elastomer is wrapped, when it is mixed with the acrylic resin as the matrix, the outermost layer of the rubber elastomer particles is mixed with the matrix resin It blends. Therefore, when the acrylic elastomer is stained with ruthenium oxide on the cross section and observed with an electron microscope, the rubber elastomer particles can be observed as particles in which the outermost layer is removed. Specifically, in the case of using a rubber elastomer particle having a two-layer structure in which the inner layer is an acrylic elastomer and the outer layer is a polymer mainly composed of methyl methacrylate, the acrylic elastomer portion of the inner layer is dyed, do. When the innermost layer is a polymer mainly composed of methyl methacrylate and the intermediate layer is an acrylic elastomer and the outermost layer is a polymer mainly composed of methyl methacrylate, Is not dyed, and only the acrylic elastomer portion of the intermediate layer is observed as a dyed two-layered structure.

In the present specification, the number average particle diameter of the rubber elastomer particles is such that when the rubber elastomer particles are mixed with the matrix resin and the cross section is dyed with ruthenium oxide, the number of diameters It is the average value.

In the acrylic film, the compounding amount of the rubber elastomer particles is not particularly limited. For example, it is preferable that the transparent acrylic resin contains 25 to 45 mass% of rubber elastomer particles having a number average particle diameter of 10 to 300 nm.

The acrylic resin may be produced by, for example, obtaining rubber elastomer particles and then polymerizing monomers to be a raw material of the acrylic resin in the presence thereof to produce an acrylic resin of the matrix. After obtaining the rubber elastomer particles and the acrylic resin, Or may be produced by mixing both of them by melt-kneading or the like.

The glass transition temperature Tg of the acrylic resin is preferably in the range of 80 to 120 占 폚. The acrylic resin preferably has a high surface hardness when molded into a film, specifically, a pencil hardness (load of 500 g, in accordance with JIS K5600-5-4) of B or more.

The acrylic resin film preferably has a flexural modulus (JIS K7171) of 1500 MPa or less from the viewpoint of flexibility of the acrylic resin. The flexural modulus of elasticity is more preferably 1300 MPa or less, and more preferably 1200 MPa or less. The flexural modulus of elasticity varies depending on, for example, the type and amount of acrylic resin in the acrylic resin film or the rubber elastomer particles. For example, as the content of the rubber elastomer particles increases, the flexural modulus generally decreases. Further, the use of a copolymer of an alkyl methacrylate and an alkyl acrylate or the like, rather than a homopolymer of an alkyl methacrylate, generally results in a smaller flexural modulus.

The use of the acrylic elastomer particles having the above two-layer structure as compared with the case of using the acrylic elastomer particles having the three-layer structure as the rubber elastomer particles generally results in a decrease in the flexural modulus of elasticity, When the elastomer particles are used, the flexural modulus generally decreases. Further, in the rubber elastomer particles, the smaller the average particle diameter of the rubber elastic body or the larger the amount of the rubber elastic body, the lower the bending elastic modulus generally becomes. Therefore, it is preferable to adjust the type and amount of the acrylic resin or rubber elastic particles in the above-mentioned predetermined range so that the flexural modulus of elasticity becomes 1500 MPa or less.

In the case where the acrylic film has a multilayer structure, the layer that may be present other than the acrylic resin composition layer is not particularly limited in its composition. For example, the layer may be an acrylic resin containing no rubber elastomer particles or a composition thereof, The content of the rubber elastomer particles or the average particle diameter of the rubber elastic body in the rubber elastomer particles may be a layer containing an acrylic resin which is not specified above.

Layer structure including a layer of acrylic resin or a layer of an acrylic resin containing no rubber elastomer particles or a layer of the composition, and may be a layer / rubber of an acrylic resin composition A three-layer structure comprising an acrylic resin containing no elastomer particles or a layer of the composition / a layer of an acrylic resin composition. In the acrylic film having a multilayer structure, the surface of the layer of the acrylic resin composition may be a surface bonded to the polarizer.

When the acrylic film has a multilayer structure, the contents of the rubber elastomer particles and the respective layers of the compounding agent may be different from each other. For example, a layer containing an ultraviolet absorber and / or an infrared absorber and a layer not containing an ultraviolet absorber and / or an infrared absorber interposed therebetween may be laminated. The content of the ultraviolet absorber in the layer of the acrylic resin composition may be higher than the content of the ultraviolet absorber in the acrylic resin not containing the rubber elastomer particles or the layer of the composition. Specifically, 10% by mass, more preferably 1 to 5% by mass, and the latter may preferably be 0 to 1% by mass and more preferably 0 to 0.5% by mass. Thus, the color tone of the polarizing plate is not deteriorated , Ultraviolet rays can be efficiently blocked, and deterioration of the polarization degree during long-term use can be prevented.

The acrylic film may be an unoriented nonoriented film or a stretched film. When the stretching treatment is not performed, the thickness of the polarizing plate tends to become thick because the film thickness becomes thick, but on the other hand, the handling property of the acrylic film becomes good because the film thickness is thick. Such an acrylic film can be obtained from an unstretched film (raw film) obtained by film-forming an acrylic resin composition. On the contrary, when the film is stretched, the phase difference only becomes easier to be expressed, and the film thickness of the acrylic film is thinned by stretching, and the stiffness is also improved. The stretched film can be produced by stretching an unoriented film by an arbitrary method.

The acrylic resin can be formed into an unstretched film by any method. It is preferable that the unoriented film is transparent and substantially free from in-plane retardation. As a film forming method, for example, an extrusion molding method in which a molten resin is extruded and formed into a film form, a solvent casting method in which a resin dissolved in an organic solvent is poured on a flat plate and then a solvent is removed is employed.

As a specific example of the extrusion molding method, there can be mentioned, for example, a method of forming a film while sandwiching an acrylic resin composition between two rolls. At this time, by making the rigidity of the roll surface different from each other, it is possible to make one side of the acrylic resin film an active surface and the other side roughed.

As a specific example of the extrusion molding method, there can be mentioned, for example, a method of forming a film while sandwiching an acrylic resin composition between two metal rolls. The metal roll in this case is preferably a mirror-surface roll. Thereby, an unstretched film excellent in surface smoothness can be obtained. Further, in the case of obtaining a multi-layered structure as the acrylic film, the acrylic resin composition may be extruded and multilayered together with other acrylic resin composition. The thickness of the unstretched film thus obtained is preferably in the range of 5 to 200 mu m, more preferably in the range of 10 to 85 mu m.

&Quot; Liquid crystal display device &

By using the polarizing plate bonded with the cellulose acylate film of the present invention for a liquid crystal display, the liquid crystal display of the present invention having various visibility can be manufactured.

The polarizing plate of the present invention can be used in liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB. And is preferably a VA (MVA, PVA) type liquid crystal display device.

In the liquid crystal display device, two polarizing plates, that is, a polarizing plate on the viewer's side and a backlight side are usually used, and it is also preferable to use the polarizing plate of the present invention as both polarizing plates. In particular, it is preferable that the polarizing plate of the present invention is used as a polarizing plate on the side of the viewer to directly contact the external environment. At that time, it is preferable that the cellulose acylate film of the present invention is disposed on the liquid crystal cell side as a retardation film.

The polarizing plate on the backlight side may be a polarizing plate other than the polarizing plate of the present invention. In this case, both sides of the polarizer may be coated with a commercially available cellulose acylate film (for example, Konica Minolta Tact KC8UX, KC5UX, KC4UX, KC8UCR3 , KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UA, KC2UAH, KC4UAH, KC6UAH, (Manufactured by Fuji Photo Film Co., Ltd., Fuji Photo Film T60UZ, Fuji Photo Film T80UZ, Fuji Photo Film TD80UL, Fuji Photo Film TD60UL, Fuji Photo Film TD40UL, Fuji Photo Film R02, Fuji Photo Film R06, manufactured by Fuji Photo Film Co., Ltd.).

As the polarizing plate on the backlight side, the cellulose acylate film of the present invention may be used on the liquid crystal cell side of the polarizer, and the commercially available cellulose acylate film, polyester film, acrylic film, polycarbonate film, A polarizing plate to which a cycloolefin polymer film is bonded may be also preferably used.

By using the polarizing plate of the present invention, it is possible to obtain a liquid crystal display device having excellent visibility, such as display unevenness and frontal contrast, even in a liquid crystal display of a large screen with a screen of 30 or more in particular.

Further, the polarizing plate of the present invention can be suitably used in an organic electroluminescence display device in addition to a liquid crystal display device. For example, a cellulose acylate film of the present invention is stretched in the direction of 45 ° to the conveying direction, and a polarizer having an absorption axis in the conveying direction is joined to the cellulose acylate film by a roll-to-roll method, When used in an organic electroluminescence display device, a display device with high visibility can be obtained.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, " part " or "% " is used, and " mass part " or " mass% "

&Lt; Compound used in Examples >

Table 1 shows the cellulose acylates C1 to C7 used in the examples.

<Nitrogen-containing heterocyclic compound>

Nitrogen-containing heterocyclic compounds were selected from the group of the exemplified compounds and represented by the No. of Exemplary Compounds.

P2: polycondensation ester Example Compound P2

P5: polycondensation ester Example Compound P5

P9: polycondensation ester Example Compound P9

P16: polycondensation ester Example Compound 1-16

S1: per ester: BzSc (benzyl sucrose: mixture of a1 to a4 in which the sugar residue is B-2 and the substituent is described), average ester substitution degree = 5.5

T1: Polyhydric alcohol ester Examples 2-16

H1: Nitrogen-containing heterocyclic compound Comparative Example Triazole-based compound Molecular weight 846

H2: Nitrogen-containing heterocyclic compound Comparative Example Triazole compound Molecular weight 83

H3: Organic ester Comparative Example Polyester (PET (A)): Melting point: 150 占 폚, Td1: 350 占 폚

(Measurement of melting point of organic ester)

(Measurement of the 1% mass reduction temperature Td1 of the organic ester)

The 1% mass reduction temperature of the organic ester was measured using an EXSTAR 6200TG / DTA apparatus, which is a simultaneous differential thermal and simultaneous thermogravimetric analyzer, manufactured by Seiko Instruments Inc., in an amount of 10 mg of the sample compound in an aluminum pan, The temperature was raised to 400 ° C at a rate of 10 ° C / min, and the mass change was monitored. The temperature at which the mass decreased by 1% by mass was set to a 1% mass reduction temperature . The measurement was also carried out under dry air (dew point -30 占 폚).

Example 1

Fine particles (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass

Ethanol 89 parts by mass

The mixture was stirred with a dissolver for 50 minutes, and then dispersed with martone gaugeolin.

&Lt; Fine Particle Addition Solution 1 >

The fine particle dispersion 1 was slowly added while sufficiently stirring in a dissolution tank containing methylene chloride. Further, dispersion was carried out in the attritor so that the particle size of the secondary particles became a predetermined size. This was filtered with Finetmet NF (manufactured by Nippon Seisen Co., Ltd.) to prepare a fine particle addition liquid 1.

99 parts by mass of methylene chloride

Fine particle dispersion 1 5 parts by mass

A primer of the following composition was prepared. First, methylene chloride and ethanol were added to the pressure-dissolving tank. A cellulose acylate C1 having an acetyl group substitution degree of 2.41 was added to the pressurized dissolution tank containing the solvent with stirring. This was heated and completely dissolved while stirring. This was filtered using Azumi Rossi No. 244 manufactured by Azumi Co., Ltd. to prepare a main dope.

365 parts by mass of methylene chloride

50 parts by mass of ethanol

Cellulose acylate C1 100 parts by mass

Nitrogen-containing heterocyclic compound 1 3 parts by mass

Organic ester P2 5 parts by mass

Fine particle addition liquid 1 1 part by mass

The above-mentioned dope was prepared by putting the above into the closed drum 1 and dissolving it with stirring.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast (cast) film was 75%, and then peeled off on a stainless steel belt support at a peel tension of 130 N / m. The peeled cellulose acylate film was stretched by 30% in the transverse direction using a tenter while applying heat at 150 캜. The residual solvent at the start of the stretching was 15%.

Subsequently, drying was completed while conveying the drying zone to a plurality of rollers. The drying temperature was 130 占 폚, and the conveying tension was 100 N / m. Thus, a cellulose acylate film 101 having a dried film thickness of 40 占 퐉 was obtained.

&Lt; Preparation of cellulose acylate films 102 to 135 >

(C2 to C7, and mixture (mass ratio)) of the cellulose acylate film 101, the kind of the nitrogen-containing heterocyclic compound, and the kind of the organic ester were changed as shown in Tables 2 and 3 Thus, cellulose acylate films 102 to 135 were prepared.

«Evaluation»

&Lt; Measurement of retardation value >

The retardation value of the cellulose acylate film was measured at a wavelength of 590 nm under an environment of a temperature of 23 캜 and a relative humidity of 55% by using an in-plane retardation value Ro defined by the following formula (i) ) Was measured using Axoscan manufactured by Axometrics, Inc. The retardation value (Rt)

Specifically, the produced cellulose acylate film under 23 ℃, a 55% RH environment, according to the 590nm wavelength subjected to refractive index measurement at the 10 regions 3d, the refractive index n average value of _x, n _y, n _z The retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction were calculated according to the following formula.

As a result, the retardation value Ro in the in-plane direction was within the range of 50 ± 5 nm and the retardation value Rt in the thickness direction was within the range of 120 ± 10 nm.

Formula (i): Ro = (n x -n y) × d (nm)

Formula (ii): Rt = {( n x + n y) / 2-n z} × d (nm)

Similarly to the measurement of the sum of one surface haze value and the internal haze value, the sample film was cut into 6 cm pieces, glycerin was applied to both sides, and a glass plate (Micro Slide Glass No. S9111, manufactured by MATSUNAMI) having a thickness of 1 mm was used And the haze was measured in accordance with JIS K7136, and only the glycerin was sandwiched between two glass plates which were separately measured. The haze was subtracted from the haze, and the value obtained by subtracting the haze Was calculated as an internal haze value. The haze was measured using a haze meter (Model NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

The internal haze is used to evaluate the turbidity inside the film due to the bleeding out of additives or the like after the film production process and the film production. The lower the value, the better the haze.

&Lt;

The fluctuation of the retardation with respect to the humidity variation was evaluated for the sample film according to the following method.

(Method of measuring phase difference variation)

Measuring environment: The in-plane retardation Ro of the sample film and the retardation Rt in the thickness direction of the sample film were measured (measured value I) using an Axoscan manufactured by Axometrics at 23 占 폚 and 55% RH.

Next, the sample film was immersed in water for 24 hours, and the water was wiped off lightly. After 30 seconds, the retardation Rt was again measured (measured value II)

The absolute value of the measured value (I-II) was defined as? Rt (nm). The smaller the value, the higher the stability of the phase difference relative to the humidity fluctuation.

The evaluation device 50 was constructed as shown in Fig. 2 and used as a system for evaluating the clogging of the filter in a pseudo manner to evaluate the filter life.

The filter 51 uses a mesh filter of 1 mm mesh.

The nitrogen-containing heterocyclic compound and the organic ester are collected in a total amount of 1 g in a mass ratio constituting the cellulose acylate film and heated to 170 캜. As shown in the figure, the pressure of 8000 Pa was monitored by a pressure gauge 53 with a pressure reducing pump 54, air was allowed to flow into the lower flask, and the volatile nitrogen compound 52 and the non-product 52 of the organic ester The state of clogging of the filter 51 was visually evaluated while passing through a circulation path of cooling water of 2 DEG C to the cylinder.

If it is ◯ or more, it can be judged that there is continuous production suitability in the production line.

◎: Not blocked at all

○: Almost unobstructed

△: Obstructed to the naked eye

X: It is extremely clogged.

The composition and evaluation results of the cellulose acylate film are shown in Tables 2 and 3.

From Table 2 and Table 3, it can be seen that the cellulose acylate film of the present invention has excellent durability against humidity fluctuation because the internal haze is small, the retardation value fluctuation with respect to humidity fluctuation is small, and the filter life is long. It can be seen that the continuous production suitability is high.

Example 2

&Lt; Preparation of cellulose acylate film 201 >

In the production of the cellulose acylate 107 of Example 1, a cellulose acylate film 201 was produced in the same manner as in the production of the cellulose acylate film 201 except for the following procedure.

365 parts by mass of methylene chloride

50 parts by mass of ethanol

Cellulose acylate C1 100 parts by mass

Nitrogen-containing heterocyclic compound 176 3 parts by mass

Organic ester S1 10 parts by mass

Organic ester P2 2 parts by mass

Fine particle addition liquid 1 1 part by mass

The cellulose acylate films 202, 203, 204, and 205 were prepared in the same manner as in the preparation of the cellulose acylate film 201 except that the constitution of the cellulose acylate, the nitrogen-containing heterocyclic compound, and the organic ester was changed as shown in Table 4 Were prepared and evaluated in the same manner as in Example 1.

The composition and evaluation results of the cellulose acylate film are shown in Table 4.

From Table 4, it can be seen that the filter life becomes longer by using two kinds of organic esters in combination with the nitrogen-containing heterocyclic compound.

Example 3

Using the cellulose acylate films 101, 108, 113, 114, 115, 132, 201, 204, and 205 produced in Example 1 and Example 2, a polarizing plate and a liquid crystal display device were manufactured according to the following procedure.

(Preparation of Polarizer)

A polyvinyl alcohol film having a thickness of 70 탆 was swelled with water at 35 캜. The obtained film was immersed in an aqueous solution containing 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds and immersed in an aqueous solution at 45 캜 containing 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. The resulting film was uniaxially stretched under the conditions of a stretching temperature of 55 캜 and a draw ratio of 5. The uniaxially stretched film was washed with water and dried to obtain Polarizer 1 having a thickness of 15 탆.

(Production of polarizing plate)

As a cellulose acylate film to be bonded to one side of the polarizer, KC6UA manufactured by Konica Minolta, having a thickness of 60 mu m, which is a commercially available polarizing plate protective film, was used.

Step 1: Each of the cellulose acylate films 101, 108, 113, and 114, which had been saponified at the side bonded to the polarizer, was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C for 90 seconds, 115, 132, 201, 204, 205 and KC6UA.

Step 2: The polarizer was immersed for 1 to 2 seconds in a polyvinyl alcohol bonding preparation with a solid content of 2% by mass.

Step 3: Excess adhesive adhering to the polarizer in Step 2 is lightly wiped off, and the cellulose acylate films 101, 108, 113, 114, 115, 132, 201, 204 and 205 (The cellulose acylate film and KC6UA were arranged such that the slow axis was orthogonal to the absorption axis of the polarizing plate).

Step 4: The cellulose acylate film, the polarizer, and KC6UA laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveying speed of about 2 m / min.

Step 5: A sample obtained by bonding the cellulose acylate film, the polarizer, and KC6UA prepared in Step 4 in a dryer at 80 캜 was dried for 2 minutes to prepare polarizers 301 to 309.

(Production of liquid crystal display devices 301 to 309)

The polarizers on both sides of the 40-type display BRAVIA X1 previously manufactured by SONY were peeled off, and the polarizers 301 to 309 were bonded to both sides of the glass surface of the liquid crystal cell.

At that time, the polarizing plates were bonded in such a manner that the surfaces of the cellulose acylate films 101, 108, 113, 114, 115, 132, 201, 204 and 205 were on the liquid crystal cell side and in the same direction as the previously polarized polarizing plates And the liquid crystal display devices 301 to 309 corresponding to the polarizing plates 301 to 309 were respectively fabricated.

&Lt; Evaluation of liquid crystal display device &

Each of the manufactured liquid crystal display devices 301 to 309 was evaluated for contrast and color unevenness.

The prepared liquid crystal display devices were each lit continuously for 1 hour in a backlight of a liquid crystal display device in an environment of 23 ° C and 55% RH, and then the front contrast was measured.

For the measurement, the luminance from the normal direction of the display screen of the white display and the black display was measured on the liquid crystal display device by EZ-Contrast 160D manufactured by ELDIM, and the ratio was used as the front contrast.

Front contrast = (luminance of white display measured from the normal direction of the display device) / (luminance of black display measured from the normal direction of the display)

The front contrast of any 10 points of the liquid crystal display was measured and evaluated according to the following criteria.

?: Front contrast of 5000 or more

○: Front contrast is 4500 or more and less than 5000

?: Front contrast of 4000 or more and less than 4500

X: Front contrast less than 4000

The prepared liquid crystal display device was laid down on the stand and put on a part of a polarizing plate for evaluation to contain water (manufactured by Asahi Kasei Co., Ltd.). The film was covered with 100 탆 PET so that the coat did not dry, a black display signal was input from a PC to the television, and the television was left on for 24 hours (the room temperature was set at 23 캜 and the panel temperature was 38 캜). After 24 hours, the coat was removed and L *, a *, and b * were measured (CS2000, manufactured by Konica Minolta) from the portion where the coat was present and the portion where the coat was present from the direction of? = 45 占? * ab were obtained, and color heterogeneity was evaluated according to the following criteria.

A: not less than 0 but not more than 1.0: no occurrence of color irregularity

?: Not less than 1.0 but not more than 1.50: Very slight color irregularity was observed, but there was no problem in practical use

?: More than 1.50 and not more than 2.4: slight occurrence of color unevenness was seen, but there was no problem in practical use

X: exceeding 2.4: strong color unevenness occurs, and there is a problem in moisture resistance

The evaluation results are shown in Table 5.

It can be seen from Table 5 that the polarizing plate using the cellulose acylate film of the present invention and the liquid crystal display equipped with the polarizing plate of the present invention have high contrast and excellent fluctuation resistance against occurrence of color unevenness with respect to humidity.

Example 4

According to the following procedure, a polyester film and an acrylic film were produced.

(Production Example 1-Polyester A)

After the temperature of the esterification reaction vessel was elevated to 200 占 폚, 86.4 parts by mass of terephthalic acid and 64.6 parts by mass of ethylene glycol were fed and 0.017 part by mass of antimony trioxide, 0.064 parts by mass of magnesium acetate tetrahydrate, And 0.16 parts by mass of ethylamine. Subsequently, pressure elevation was carried out, and the esterification reaction was carried out under the conditions of gauge pressure 0.34 MPa and 240 deg. C, and then the esterification reaction vessel was returned to normal pressure and 0.014 mass part of phosphoric acid was added. Further, the temperature was raised to 260 DEG C over 15 minutes, and 0.012 parts by mass of trimethyl phosphate was added. Subsequently, after 15 minutes, dispersion treatment was carried out with a high-pressure disperser. After 15 minutes, the obtained esterification reaction product was transferred to a polycondensation reaction can, and a polycondensation reaction was carried out under reduced pressure at 280 占 폚.

After completion of the polycondensation reaction, filtration treatment was carried out with a nylon filter having a 95% cut diameter of 5 占 퐉, extruded from a nozzle into a strand shape, and cooled using cooling water previously subjected to filtration treatment (pore diameter: , Solidified, and cut into pellets. The obtained polyethylene terephthalate resin (A) had an intrinsic viscosity of 0.62 dl / g and substantially no inert particles and no internal precipitated particles. (Hereinafter abbreviated as PET (A)).

(Production Example 2-Polyester B)

Then, 10 parts by mass of a dried ultraviolet absorber (2,2 '- (1,4-phenylene) bis (4H-3,1-benzoxadinon-4-one), PET (A) (Intrinsic viscosity: 0.62 dl / g) were mixed, and a polyethylene terephthalate resin (B) containing ultraviolet absorber was obtained (hereinafter abbreviated as PET (B)) by using a kneading extruder.

(Preparation Example 3-Preparation of Adhesive Modifying Coating Solution)

The transesterification reaction and the polycondensation reaction were carried out by a conventional method, and 46 mol% of terephthalic acid, 46 mol% of isophthalic acid and 5 mol% of sodium 5-sulfonate isophthalate (relative to the entire dicarboxylic acid component) (As a whole glycol component) of 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol as a glycol component was prepared. Subsequently, 51.4 parts by mass of water, 38 parts by mass of isopropyl alcohol, 5 parts by mass of n-butyl cellosolve and 0.06 parts by mass of a nonionic surfactant were mixed with heating and stirred at 77 占 폚, And 5 parts by mass of a metal base-containing copolymerizable polyester resin were added. After the mixture was continuously stirred until the mass of the resin disappeared, the resin aqueous dispersion was cooled to room temperature to obtain a homogeneous water dispersible copolymer polyester resin having a solid content concentration of 5.0% Solution. After 3 parts by mass of agglomerated silica particles (Silysia 310, manufactured by Fuji Silysia Co., Ltd.) were dispersed in 50 parts by mass of water, 0.54 parts by mass of an aqueous dispersion of Silysia 310 in 99.46 parts by mass of the above- And 20 parts by mass of water was added with stirring to obtain an adhesive modified coating liquid.

(Production of PET film)

90 parts by mass of PET (A) resin pellets containing no particles and 10 parts by mass of PET (B) resin pellets containing an ultraviolet absorber were dried at 135 ° C for 6 hours under reduced pressure (1 Torr) as raw materials for the base film intermediate layer raw material, (For the intermediate layer II layer), and the PET (A) was dried by a usual method and supplied to the extruder 1 (for the outer layer I and outer layer III), respectively, and dissolved at 285 deg. These two kinds of polymers were each filtered with a filter material (nominal filtration accuracy 10 μm particle size 95% cut) of a stainless steel sintered body and laminated with a two-kind three-layer confluence block, extruded from a nip into a sheet shape, Was wound around a casting drum having a surface temperature of 30 DEG C to cool and solidify to form an unstretched film. At this time, the discharge amount of each extruder was adjusted so that the thickness ratio of the I layer, the II layer and the III layer was 10:80:10.

Subsequently, the adhesive modifying coating liquid was applied on both sides of the unstretched PET film by a reverse roll method so that the coating amount after drying was 0.096 g / m < 2 >, followed by drying at 80 DEG C for 20 seconds.

The unstretched film on which the coating layer was formed was led to a tenter stretcher and led to a hot air zone at a temperature of 125 캜 while grasping the end of the film with a clip and stretched 4.0 times in the width direction. Subsequently, the uniaxially oriented polyester film having a film thickness of 60 占 퐉 was obtained by treating the film at a temperature of 225 占 폚 for 30 seconds while maintaining the stretched width in the width direction and further performing a relaxation treatment of 3% in the width direction.

&Lt; Preparation of acrylic film &

(Acrylic resin and acrylic elastomer particles)

As the acrylic resin, a copolymer having a mass ratio of methyl methacrylate / methyl acrylate of 96/4 was used. As the rubber elastomer particles, acrylic elastomer particles having a three-layer structure including an innermost layer, an intermediate layer and an outermost layer were used. This acryl-based elastomer particle has a structure in which the innermost layer is composed of a hard polymer polymerized by using methyl methacrylate with a small amount of allyl methacrylate and an intermediate layer containing butyl acrylate as a main component and styrene and a small amount of allyl methacrylate , And the outermost layer contains a hard polymer polymerized by using a small amount of ethyl acrylate in methyl methacrylate and has an average particle diameter of 240 nm to an elastic material as an intermediate layer.

(Production of acrylic film)

The pellets in which the acrylic resin and the acrylic elastomer particles were blended in a mass ratio of former / latter = 70/30 were melt-kneaded by a twin-screw extruder to obtain pellets of an acrylic resin composition. The pellets were poured into a single screw extruder having a diameter of 65 mm and extruded through a T-die having a set temperature of 275 DEG C. The both surfaces of the extruded film-like molten resin were polished with a polishing roll (cooling roll) (Elastic roll) whose surface was made of a metal material and filled with a fluid, and cooled to prepare an acrylic film having a thickness of 60 mu m.

Using the cellulose acylate films 101, 108, 201, and 205 produced in Example 1 and Example 2, a polarizing plate and a liquid crystal display device were manufactured according to the following procedure.

(Preparation of Polarizer)

A polarizing laminated film was prepared in order to form a polarizer of a thin film by the following process, and a polarizer of a thin film was obtained by peeling the base film from the polarizing laminated film.

(1) Production of base film

A thermoplastic resin and a rubber component were prepared in turn in the same reaction vessel by a reactor blend method. Specifically, propylene monomer was fed in a gas phase as a first step by using a Ziegler-Natta catalyst, and a propylene homopolymer as a thermoplastic resin was produced. The feed of the propylene monomer was stopped to stop the reaction and the ethylene monomer and the propylene monomer were fed in the vapor phase in the second step as they were in the reaction vessel to produce an ethylene-propylene copolymer as the rubber component, A propylene homopolymer in which the ethylene-propylene copolymer was dispersed in the form of particles was obtained. The content of the ethylene unit in the copolymer was determined from the mass balance at the time of polymerization to be 35 mass%. The content of the ethylene unit in the entire resin (total of the thermoplastic resin and the rubber component) was determined according to the method described on page 616 of the Polymer Handbook (issued by Kinokuniya Shoten in 1995), and from this value, The content of the ethylene-propylene copolymer was calculated to be 29 mass% (i.e., the content of the ethylene-propylene copolymer was 40.8 mass% of the thermoplastic resin).

The resulting mixed resin was melted and kneaded at 250 占 폚 and then melt-extruded at a temperature of 280 占 폚 on a T-die to obtain a base film having a thickness of 100 占 퐉.

(2) Formation of primer layer

Polyvinyl alcohol powder ("Z-200" manufactured by Nippon Gosei Chemical Industry Co., Ltd., average polymerization degree: 1100, average saponification degree: 99.5 mol%) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 3% Lt; / RTI > (Sumirez Resin 650, manufactured by Sumitomo Chemical Co., Ltd.)) was mixed with 5 parts by mass of 6 parts by mass of the polyvinyl alcohol powder. The obtained mixed aqueous solution was coated on the corona-treated surface of the substrate film subjected to the corona treatment using a micro gravure coater and dried at 80 DEG C for 10 minutes to form a 0.2 mu m thick primer layer.

(3) Formation of a polyvinyl alcohol-based resin layer

Polyvinyl alcohol powder ("PVA124" manufactured by Kuraray Co., Ltd., average degree of polymerization: 2400) and an average degree of saponification of 98.0 to 99.0 mol%) were dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 8% . The obtained aqueous solution was coated on the primer layer using a lip coater and dried under the conditions of 80 캜 for 2 minutes, 70 캜 for 2 minutes and subsequently at 60 캜 for 4 minutes to form a primer layer Thereby producing a laminated film in which a polyvinyl alcohol-based resin layer was laminated. The thickness of the polyvinyl alcohol-based resin layer was 9.8 mu m.

(4) Production of stretched film

The laminated film was subjected to uniaxial stretching at a stretch ratio of 5.8 times at a stretching temperature of 160 캜 to obtain a stretched film. The thickness of the obtained stretched film was 28.5 占 퐉, and the thickness of the polyvinyl alcohol-based resin layer was 5.0 占 퐉.

(5) Production of polarizing laminated film

The stretched film was immersed in a warm bath at 60 DEG C for 60 seconds and then dipped in a dyeing solution at 30 DEG C for about 150 seconds as an aqueous solution containing iodine and potassium iodide to stain the polyvinyl alcohol resin layer, The excess iodine solution was rinsed with pure water of 캜. Subsequently, the substrate was immersed in a crosslinking solution at 76 DEG C for 600 seconds as an aqueous solution containing boric acid and potassium iodide. Thereafter, the film was washed with pure water at 10 캜 for 4 seconds, and finally dried at 50 캜 for 300 seconds to obtain a polarizing laminated film. The polyvinyl alcohol-based resin layer of the polarizing laminated film was peeled from the base film, and a polyvinyl alcohol-based resin layer was used as the polarizer 2.

(Preparation of ultraviolet curable adhesive liquid 1)

The following components were mixed and defoamed to prepare an ultraviolet curing type adhesive liquid 1. Further, triarylsulfonium hexafluorophosphate was compounded as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.

45 parts by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate

Polyd GT-301 (alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.)

40 parts by mass

15 parts by mass of 1,4-butanediol diglycidyl ether

Triarylsulfonium hexafluorophosphate 2.3 parts by mass

9,10-dibutoxyanthracene 0.1 part by weight

2.0 parts by mass of 1,4-diethoxynaphthalene

(Production of polarizing plate)

Polarizing plates 401 to 406 were produced according to the following method.

First, the surface of the cellulose acylate film was subjected to a corona discharge treatment. The conditions of the corona discharge treatment were a corona output power of 2.0 kW and a line speed of 18 m / min. Subsequently, on the corona discharge treated surface of the cellulose acylate film, the prepared ultraviolet curing type adhesive liquid 1 was applied and coated with a bar coater so as to have a film thickness after curing of about 3 mu m to form an ultraviolet curing type adhesive layer. To the obtained ultraviolet curable adhesive layer, the polarizer (thickness 5 mu m) side of the prepared polarizing laminated film was bonded, and then the base film was peeled off.

Subsequently, the polyester film and the acrylic film produced above were each subjected to a corona discharge treatment. The conditions of the corona discharge treatment were a corona output power of 2.0 kW and a velocity of 18 m / min.

Subsequently, on the corona discharge treated surface of the polyester film and the acrylic film, the ultraviolet curable adhesive liquid 1 prepared above was applied and coated with a bar coater so as to have a film thickness after curing of about 3 탆 to form an ultraviolet curable adhesive layer.

A polarizer bonded to one side of the cellulose acylate film is bonded to the ultraviolet curing type adhesive layer to form a laminate in which a cellulose acylate film / ultraviolet curing type adhesive layer / polarizer / ultraviolet curing type adhesive layer / polyester film or acrylic film is laminated . At that time, the cellulose acylate film and the polyester film or the acrylic film were joined so that the slow axis and the absorption axis of the polarizer were orthogonal to each other.

Ultraviolet rays were irradiated from both sides of the laminate so that the accumulated light quantity was 750 mJ / cm 2 using an ultraviolet irradiator with a belt conveyor (lamp: D bulb manufactured by Fusion UV Systems Co., Ltd. was used) The adhesive layer was cured to prepare polarizers 401 to 408 having a total film thickness of 91 占 퐉 as shown in Table 6.

(Production of liquid crystal display devices 401 to 408)

The polarizing plates on both sides of the SONY 40 type display BRAVIA X1 which had been preliminarily bonded were peeled off and the polarizing plates 401 to 408 were adhered to both sides of the glass surface of the liquid crystal cell.

At that time, the polarizing plates were bonded in such a manner that the surfaces of the cellulose acylate films 101, 108, 201, and 205 were in the liquid crystal cell side and the absorption axis was directed in the same direction as the previously polarized polarizing plate, And liquid crystal display devices 401 to 408 corresponding to the polarizing plates 401 to 408, respectively.

&Lt; Evaluation of liquid crystal display device &

Each of the manufactured liquid crystal display devices 401 to 408 was evaluated in terms of contrast and color unevenness in the same manner as in Example 3.

The composition of the polarizing plate and the evaluation results are shown in Table 6.

As can be seen from Table 6, since the rate at which water reaches the cellulose acylate film (phase difference film) can be slowed down by using a polyester film or an acrylic film having a high moisture permeability as a polarizing plate protective film, It can be seen that the more excellent the occurrence of the non-uniformity.

In the cellulose acylate film of the present invention, the compound that suppresses the fluctuation of the retardation with respect to humidity is volatilized and scattered in the production line, and adhered in a bulky shape with a large volume, thereby contaminating the wall surface or causing clogging of the filter , It is suitable for use as a polarizing plate or a liquid crystal display device, as an optical film having both stability of retardation against humidity fluctuation and continuous production suitability.

1: melting pot
3, 6, 12, 15: filter
4, 13: stock kiln
5, 14: Pump pump
8, 16: conduit
10: Ultraviolet absorber input kiln
20: junction pipe
21: Mixer
30: pressure die
31: metal belt
32: Web
33: Peeling position
34: Tenter stretching device
35: Drying apparatus
41: Feeding kiln
42: stock kiln
43: pump
44: Filter
50: filter life evaluation device
51: Filter
52: Non-product
53: Pressure gauge
54: Pressure reducing pump

Claims

Cellulose acylate and a compound having a structure represented by the following general formula (1) within a molecular weight range of 100 to 800 and a compound having a melting point within a range of -60 to 120 占 폚, % Mass loss temperature Td1 is in the range of 100 to 350 占 폚. The cellulose acylate film according to claim 1,

(Wherein A ₁ , A ₂ and B each represent an alkyl group, a cycloalkyl group, an aromatic hydrocarbon ring or an aromatic heterocyclic ring), T ₁ and T ₂ each represent a linking group represented by the following general formula (1-2). L ₁ to L ₄ each represent a single bond or a divalent linking group, and n represents an integer of 0 to 5)

The cellulose acylate film according to claim 1, wherein the compound having the structure represented by the general formula (1) is at least one selected from the group consisting of a pyrazole ring, a triazole ring, and a compound having an imidazole ring.

The cellulose acylate film according to claim 2, wherein the compound having the structure represented by the general formula (1) is a compound having a structure represented by the following general formula (3).

The cellulose acylate film according to claim 1, wherein the organic ester is at least one selected from sugar esters, polycondensation esters, and polyhydric alcohol esters.

The cellulose acylate film according to claim 1, wherein the cellulose acylate film contains a compound having a structure represented by the general formula (1) in an amount of 0.5 to 10 mass%, and the organic ester is contained in an amount of 0.5 to 20 mass% By mass of the cellulose acylate film.

The cellulose acylate film according to claim 1, wherein the total acyl group substitution degree of the cellulose acylate is in the range of 2.0 to 2.7, or cellulose acetate propionate.

The retardation film according to claim 1, wherein the in-plane retardation value Ro represented by the following formula (i) in a measurement at an optical wavelength of 590 nm in an environment of 23 캜 and 55% RH is within a range of 40 to 70 nm, Wherein the retardation value Rt in the thickness direction represented by the following formula (ii) is in the range of 100 to 300 nm.
Formula (i): Ro = (n x -n y) × d
Formula (ii): Rt = {( n x + n y) / 2-n z} × d
[In the formulas (i) and (ii), n _x represents the refractive index in the direction x at which the refractive index becomes maximum in the in-plane direction of the film. n _y represents the refractive index in the direction y perpendicular to the direction x in the in-plane direction of the film. and n _z represents the refractive index in the thickness direction z of the film. and d represents the thickness (nm) of the film.

A polarizing plate characterized in that the cellulose acylate film according to any one of claims 1 to 7 is bonded to a polarizer using a water-soluble or active energy ray-curable adhesive.

The polarizing plate according to claim 8, wherein a polyester film or an acrylic film is bonded to the polarizer using a water-soluble or active energy ray-curable adhesive on the surface of the polarizer opposite to the surface to which the cellulose acylate film is bonded Polarizing plate.

A liquid crystal display device comprising the cellulose acylate film according to any one of claims 1 to 7.

A liquid crystal display device comprising the polarizing plate according to claim 8.