KR101239448B1 - Cellulose acylate film, optical compensation film, polarizing film and liquid crystal display - Google Patents

Abstract

Provided are a polarizer protective film and an optical compensation film that can be used in an image display device having a small wavelength dependency, that is, an improved display color.

A cellulose acylate film in which the front retardation Re _(λ) of the film at the wavelength λ (nm) and the retardation Rth _(λ) in the film thickness direction satisfy the following formulas (III) and (IV) and polarizer protection using the same Improvement of display color is achieved by the support of a film or an optical compensation film.

_{(Ⅲ) 0 ≤Re (630)} ≤10 In addition, | Rth ₍₆₃₀₎ | ≤25

(IV) | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤10 and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ ≤35

Description

Cellulose Acylate Film, Optical Compensation Film, Polarizing Film and Liquid Crystal Display {CELLULOSE ACYLATE FILM, OPTICAL COMPENSATION FILM, POLARIZING FILM AND LIQUID CRYSTAL DISPLAY}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cellulose films useful for retardation films and liquid crystal displays, optical materials such as optical compensation films, polarizing plates and the like, and liquid crystal displays.

Conventionally, the cellulose acylate film has been used as a photographic support or various optical materials because of its toughness and flame retardancy. In particular, recently, it has been widely used as an optical transparent film for liquid crystal display devices. Cellulose acylate films are excellent as optical materials for polarizing devices such as liquid crystal display devices in terms of high optical transparency and high optical isotropy. (Viewing angle compensation) It has been used as a support body of the optical compensation film which can be performed.

In the polarizing plate, which is one of the members for the liquid crystal display device, a protective film of the polarizer is formed on at least one side of the polarizer by bonding. Common polarizers are obtained by dyeing stretched polyvinyl alcohol (PVA) based films with iodine or dichroic dyes.                         

In most cases, as a protective film of a polarizer, the cellulose acylate film which can be directly bonded with respect to PVA, especially the triacetyl cellulose film, is used. It is important that the protective film of this polarizer is excellent in optical isotropy, and the optical characteristic of the protective film of the polarizer greatly influences the characteristic of a polarizing plate.

In recent liquid crystal display devices, the improvement of viewing angle characteristics is required more strongly, and optically transparent films such as a protective film of a polarizer and a support of an optical compensation film are required to be more optically isotropic. It is important that optically isotropic is small the retardation value expressed by the product of birefringence and thickness of an optical film. In particular, in order to improve the display from the oblique direction, it is necessary to reduce the retardation Rth in the film thickness direction as well as the retardation Re in the front direction. Specifically, when evaluating the optical properties of the optically transparent film, it is required that Re measured at the front of the film is small and that Re does not change even when the angle is measured at different angles.

There existed the cellulose acylate film which made Re of the front small so far, but the cellulose acylate film with small Re change by an angle, ie, small Rth, was difficult to produce. Therefore, using a polycarbonate film or a thermoplastic cycloolefin film instead of a cellulose acylate film, an optically transparent film having a small change in the angle of Re has been proposed (for example, Patent Documents 1 and 2 and Nippon Zeon Co., Ltd.). (Manufactured) or ARTON (JSR Inc.). However, these optically transparent films have problems in bonding with PVA because the films are hydrophobic when used as protective films for polarizers. There is also a problem that the optical properties of the entire film surface are nonuniform.                         

As this solution, it is strongly desired to improve the cellulose acylate film excellent in the bonding titration with respect to PVA by further reducing the optical anisotropy. Specifically, it is an optically isotropic optical transparent film in which Re on the front of the cellulose acylate film is almost zero, and the angle change of the retardation is also small, that is, Rth is almost zero.

In manufacture of a cellulose acylate film, generally, a compound called a plasticizer is added in order to improve film forming performance. As a kind of plasticizer, phosphoric acid triester, phthalic acid ester, such as triphenyl phosphate and biphenyl diphenyl phosphate, etc. are disclosed (for example, refer nonpatent literature 1). Among these plasticizers, it is known to have an effect of lowering the optical anisotropy of the cellulose acylate film, and specific fatty acid esters are disclosed (for example, see Patent Document 3). However, the effect of lowering the optical anisotropy of the cellulose acylate film using these conventionally known compounds cannot be said to be sufficient.

In recent liquid crystal display devices, there is also a demand for improvement of display color. For this reason, optically transparent films such as a polarizer protective film and an optical compensation film supporter not only reduce Re or Rth in the visible region with a wavelength of 400 to 800 nm, but also change Re or Rth due to wavelength, that is, wavelength dispersion. Needs to be.

Patent Document 1 Japanese Unexamined Patent Publication No. 2001-318233

Patent Document 2 Japanese Unexamined Patent Publication No. 2002-328233

Patent Document 3 Japanese Unexamined Patent Publication No. 2001-247717                         

Non-Patent Document 1 Lecture on Plastic Materials, Vol. 17, Daily Industrial Newspaper, Fibrin-Based Resin, 121 pages (45 Years of Fire Extinguishing (1970))

The 1st subject of this invention is providing the cellulose acylate film with small optical anisotropy (Re, Rth), substantially optical isotropic, and small wavelength dispersion of optical anisotropy (Re, Rth).

The 2nd subject of this invention is to show that optical materials, such as an optical compensation film and a polarizing plate produced by the cellulose acylate film with small optical anisotropy and small wavelength dispersion, have excellent viewing angle characteristics, and the liquid crystal display device using these It is to offer.

In order to solve the said 1st and 2nd subjects, the inventors of this invention earnestly examined, and the optical anisotropy is fully reduced using the compound which suppresses the cellulose acylate in a film being oriented in in-plane and film thickness direction, Re is zero and Rth is close to zero.

In the present invention, the optical anisotropy (Re, Rth) in the cellulose acylate film is smaller, and the retardation Re ₍₆₃₀₎ is _(≤10 0≤Re ₍₆₃₀₎₎ 10㎚ below a plane at a wavelength of 630㎚ also It is preferable that the absolute value of the retardation Rth _{630 in} the film thickness direction is 25 nm or less (| Rth | ≤ 25 nm). More preferably, 0 ≤ Re ₍₆₃₀₎ ≤ 5 and | Rth | ≤ 20 nm, and 0 ≤ Re ₍₆₃₀₎ ≤ 2 and | Rth | ≤ 15 nm are particularly preferred.

In addition, the inventors of the present invention, as a result of diligent study, have an absorption in an ultraviolet region having a wavelength of 200 to 400 nm to prevent coloring of the film and control the wavelength dispersion of Re _(λ) and Rth _(λ) of the film. The difference between Re and Rth, | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ |, and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ |

In this invention, as a cellulose acylate film with a small wavelength dispersion, it is preferable that | Re ₍₄₀₀₎ -Re _{(700) <=} 10 and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≤35. More preferably, | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤5 and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≤25, | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤3 and | Rth It is especially preferable that ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≦ 15.

It was also confirmed that these compounds were well compatible with cellulose acylate when the cellulose acylate film was actually produced, so that the film did not become cloudy or the physical strength of the film was sufficient.

Moreover, the inventors of this invention discovered that the said 1st and 2nd problem can be solved also by using what the acyl substitution degree of cellulose acylate is 2.85-3.00 with high result as a result of earnestly examining.

Furthermore, the inventors of the present invention have found out that by providing an optically anisotropic layer on a cellulose acylate film having small optical anisotropy and small wavelength dispersion, the optical compensation film having excellent viewing angle characteristics can be provided.                     

The subject of this invention was achieved by the cellulose acylate film described below.

(1) A cellulose acylate film, wherein Re _(λ) defined by the following formula (I) and Rth _(λ) defined by the following formula (II) satisfy the following formula (III) and (IV).

(I) Re _(λ) = (nx-ny) × d

(II) Rth _(λ) = {(nx + ny) / 2-nz} × d

_{(Ⅲ) 0 ≤Re (630)} ≤10 In addition, | Rth ₍₆₃₀₎ | ≤25

(IV) | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤10 or | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≤35

[Wherein Re _(λ) is the front retardation value (unit: nm ₎ at wavelength _λ nm, and Rth _(λ) is the retardation value (unit: nm) in the film thickness direction at wavelength _λ nm. Nx is a refractive index in the slow axis direction in the film plane, ny is a refractive index in the fast axis direction in the film plane, nz is a refractive index in the thickness direction of the film, and d is the thickness of the film.]

(2) The cellulose acylate film according to (1), wherein Re _(λ) and Rth _(λ) satisfy the following formula (V) and (VI).

_{(Ⅴ) 0 ≤Re (630)} ≤5 also | Rth ₍₆₃₀₎ | ≤20

(VI) | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤5 and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≤25

(3) The compound which reduces retardation Rth _((lambda) ) of a film film thickness direction is contained in the range which satisfy | fills following formula (VII) and (VII), The cellulose as described in (1) or (2) characterized by the above-mentioned. Acylate film.

(Iii) (Rth (A) -Rth (O)) / A ≤-1.0

(Iii) 0.01 ≤ A ≤ 30

From here,

Rth (A): Rth (nm) of the film containing A% of the compound which reduces Rth _((lambda) )

Rth (O): Rth (nm) of the film which does not contain the compound which reduces Rth _((lambda) )

A: Weight (%) of the compound when the weight of the film raw material polymer is 100.

to be.

(4) acyl substitution degree of cellulose acylate is 2.85-3.00,

0.01-30 weight% of compounds which reduce Re _((lambda)) and Rth _((lambda)) with respect to cellulose acylate solid content are contained, The cellulose acylate film as described in (3) characterized by the above-mentioned.

(5) The cellulose acylate according to (4), wherein the acyl substituent of the cellulose acylate is substantially only an acetyl group, its total substitution is 2.85 to 3.00, and the average degree of polymerization of the cellulose acylate is 180 to 550. film.

(6) The acyl substituent of the cellulose acylate is substantially at least two kinds of acetyl group, propionyl group and butanoyl group, and the total substitution degree is 2.50 to 3.00,                     

0.01-30 weight% of compounds which reduce Re _((lambda)) and Rth _((lambda)) with respect to cellulose acylate solid content are contained, The cellulose acylate film as described in (3) characterized by the above-mentioned.

(7) Re _(λ) and Rth _(λ) are lowered to contain 0.01 to 30% by weight of a compound having an octanol-water partition coefficient (LogP value) of 0 to 7 based on cellulose acylate solids. The cellulose acylate film in any one of (1)-(6) mentioned.

(8) A compound in which Re _(λ) and Rth _(λ) are lowered and the octanol-water partition coefficient (LogP value) is 0 to 7 is a compound represented by any one of Chemical Formulas 1 to 19. Cellulose acylate film according to the above).

(In Formula 1, each of R ¹⁰¹ -R ¹⁰³ independently represents an aliphatic group having 1 to 20 carbon atoms. R ¹⁰¹ -R ¹⁰³ may be linked to each other to form a ring.)

(In the formula 2 and 3, Z is a carbon atom, an oxygen atom, a sulfur atom, or -NR ²⁰⁵ - represents a, R ²⁰⁵ may have a represents a hydrogen atom or an alkyl group of 5 or 6-membered ring constituted by containing Z is a substituent. Y ²⁰¹ -Y ²⁰² each independently represents an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group, an amide group or a carbamoyl group, and Y ²⁰¹ -Y ²⁰² may be linked to each other to form a ring. Represents an integer of 1 to 5, and n represents an integer of 1 to 6.)

In Formulas 4-12, Y ³¹ -Y ⁷⁰ each independently represents an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. A carbamoyl group or a hydroxyl group, and V ³¹ -V ⁴³ each independently represent a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, and L ³¹ -L ⁸⁰ is each independently a single bond or 1 to 40 carbon atoms or 0 carbon atoms; It represents a divalent saturated linking group of ~20. V ³¹ -V ⁴³ and L ³¹ -L ⁸⁰ may have a substituent further.)

In Formula 13, R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. The total number of carbon atoms in R ³¹ , R ^32, and R ³³ is 10 or more, and R ³¹ , R ³² and R ³³ may each have a substituent, and R ³¹ and R ³² may combine to form a ring.)

(In Formula 14, R ¹⁰⁴ and R ¹⁰⁵ each independently represent an alkyl group or an aryl group. The total number of carbon atoms of R ¹⁰⁴ and R ¹⁰⁵ is 10 or more, and R ¹⁰⁴ and R ¹⁰⁵ may each have a substituent.)

R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group. X ²¹ represents a divalent linking group formed of at least one group selected from the following linking group group 1. Y ²¹ represents hydrogen It represents an atom, an alkyl group, an aryl group, or an aralkyl group.

(Coupler group 1)

Single bond, -O-, -CO-, -NR ^24- , alkylene group and arylene group. R ²⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.)

(Formula 16 of Q ^1, Q ² and Q ³ independently represent a 5 to 6 membered ring, respectively. X ⁶¹ is B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, P = O is indicated.)

In Formula 17, X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, P═O. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom or a substituent.)

(In Formula 18, R ¹¹¹ represents an alkyl group or an aryl group, and R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group. The alkyl group and the aryl group may also have a substituent.)

As general formula (18), it is preferably a compound represented by the following general formula (19).

In formula (19), R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ each independently represent an alkyl group or an aryl group, wherein the alkyl group may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms. More preferably 1 to 15, most preferably 1 to 12. As the cyclic alkyl group, a cyclohexyl group is particularly preferable, and an aryl group preferably has 6 to 36 carbon atoms and 6 to 24 carbon atoms. More preferably).

The alkyl group and the aryl group may have a substituent, and examples of the substituent include a halogen atom (for example, chlorine, bromine, fluorine and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. , Acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group, more preferably halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, sulfonylamino group and acylamino group, especially Preferably, they are an alkyl group, an aryl group, a sulfonylamino group, and an acylamino group.

(9) Re _(λ) and Rth _(λ) are lowered so that the compound having an octanol-water partition coefficient (LogP value) of 0 to 7 is a polyhydric alcohol ester compound, a carboxylic acid ester compound, a polycyclic carboxylic acid compound and a bisphenol derivative. It is 1 or more types selected, The cellulose acylate film as described in (7).

(10) To any one of (1)-(9) characterized by containing the compound which reduces (DELTA) Rth defined by following formula (i) in the range which satisfy | fills following formula (iii) and (XI). The cellulose acylate film described.

(Ⅸ) ΔRth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ |

(Ⅹ) (ΔRth (B) -ΔRth (O)) / B ≤-2.0

(XI) 0.01 ≤B ≤30

From here,

Rth ₍₄₀₀₎ : Rth (nm) at 400 nm

Rth ₍₇₀₀₎ : Rth (nm) at ₇₀₀ nm

ΔRth (B): ΔRth (nm) of a film containing B% of a compound that reduces ΔRth

ΔRth (O): ΔRth (nm) of the film containing no compound that lowers ΔRth

B: Weight (%) of the compound when the weight of the film raw material polymer was 100.

to be.

(11) 0.01 to 30% by weight of a compound that reduces | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | with respect to cellulose acylate solid content. The cellulose acylate film in any one of (1)-(10) which makes it a.

(12) A compound having a decrease in | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | and having absorption in an ultraviolet region having a wavelength of 200 to ₄₀₀ nm with respect to the cellulose acylate solid content. 0.01-30 weight% is contained, The cellulose acylate film in any one of (1)-(11) characterized by the above-mentioned.

(13) The cellulose acylate according to any one of (1) to (12), wherein the spectral transmittance at a wavelength of 380 nm is 45% or more and 95% or less, and the spectral transmittance at a wavelength of 350 nm is 10% or less. film.

(14) The cellulose acylate film according to any one of (1) to (13), wherein the benzotriazole compound having a molecular weight of 320 or less is substantially not contained.

(15) The cellulose according to any one of (1) to (14), wherein the amount of change in Re _(λ) and Rth _(λ) of the film is 15 nm or less, respectively, when treated at 60 ° C at 90% RH for 240 hours. Acylate film.

(16) The amount of change of Re and Rth of a film is 15 nm or less when it processes at 80 degreeC 240 hours, The cellulose acylate film in any one of (1)-(15) characterized by the above-mentioned.

(17) A compound which reduces the ΔRth which contains a compound that lowers Rth in a range satisfying formulas (iii) and (iii) described in (3) and is defined by formula (iii) described in (10) ( The cellulose acylate film contained in the range which satisfy | fills Formula (VII) and (XI) as described in 10), When volatilized at 80 degreeC 240 hours, the volatilization volatilized in the film of the compound which reduces Rth and the compound which reduces (DELTA) Rth The amount is 30% or less, respectively, The cellulose acylate film according to any one of (1) to (16).                     

(18) The cellulose acylate film according to any one of (1) to (17), which is made of a dope solution of cellulose acylate having a transparency of 85% or more.

(19) The film thickness of film is 10-120 micrometers, The cellulose acylate film in any one of (1)-(18) characterized by the above-mentioned.

(20) Glass transition temperature (Tg) is 80-165 degreeC, The cellulose acylate film in any one of (1)-(19) characterized by the above-mentioned.

(21) The difference between the Rth value at 25 ° C 10% RH and the Rth value at 25 ° C 10% RH {= (Rth at 25 ° C 10% RH)-(Rth value at 25 ° C 10% RH)} It is 0-50 nm, The cellulose acylate film in any one of (1)-(20).

(22) The cellulose acylate film according to any one of (1) to (21), wherein the equilibrium moisture content at 25 ° C 80% RH is 4% or less.

(23) When treated at 60 ° C. and 95% RH for 24 hours, the water vapor transmission rate (in terms of film thickness of 80 μm) is 400 g / (m 2 · 24 hr) or more and 2000 g / (m 2 · 24 hr) or less (1) to The cellulose acylate film in any one of (22).

(24) Haze is 0.01 to 2%, The cellulose acylate film in any one of (1)-(23) characterized by the above-mentioned.

(25) The cellulose acylate film according to any one of (1) to (24), which has silicon dioxide fine particles having a secondary average particle diameter of 0.2 µm or more and 1.5 µm or less.                     

(26) The cellulose acylate film according to any one of (1) to (25), wherein the total amount of the compound having a molecular weight of 3000 or less is 5 to 45% by weight with respect to the cellulose acylate weight.

(27) The cellulose acylate film according to any one of (1) to (26), wherein a mass change of 0 to 5% when left still for 48 hours at 80 ° C. and 90% RH is used.

(28) The dimensional change when left standing for 24 hours under the condition of 60 ° C and 95% RH and the dimensional change when standing for 24 hours under the condition of 90 ° C and 5% RH are all 0 to 5%. The cellulose acylate film in any one of)-(27).

(29) Elastic modulus is 200-500 kgf / mm <2>, The cellulose acylate film in any one of (1)-(28) characterized by the above-mentioned.

(30) The cellulose acylate film according to any one of (1) to (29), wherein the photoelastic coefficient is 50 × 10 ⁻¹³ cm 2 / dyne or less.

(31) The contact angle of the film surface after alkali saponification process is 55 degrees or less, The cellulose acylate film in any one of (1)-(30) characterized by the above-mentioned.

(32) The cellulose acylate film according to any one of (1) to (31), wherein the following formula is satisfied.

| Re (MAX) -Re (MIN) | ≤3 Or | Rth (MAX) -Rth (MIN) | ≤5

[In formula, Re (MAX) and Rth (MAX)-are the maximum retardation values of Re film (MIN) and Rth (MIN) of the film which is 1 m square cut out arbitrarily. "

(33) Color difference (DELTA) E * ab of a film is 20 or less before and after irradiating super xenon for 240 hours, The cellulose acylate film in any one of (1)-(32) characterized by the above-mentioned.

(34) In the cellulose acylate film according to any one of (1) to (33), an optically anisotropic layer having Re ₍₆₃₀₎ of 0 to 200 nm and | Rth ₍₆₃₀₎ | of 0 to 400 nm is formed. Optical compensation film, characterized in that.

(35) The optical compensation film according to (34), wherein the optically anisotropic layer contains a discotic liquid crystal layer.

(36) The optical compensation film according to (34) or (35), wherein the optically anisotropic layer contains a rod-like liquid crystal layer.

(37) The optical compensation film according to any one of (34) to (36), wherein the optically anisotropic layer contains a polymer film.

(38) At least 1 sort (s) of polymeric material chosen from the group which the polymer film which forms an optically anisotropic layer becomes from polyamide, polyimide, polyester, polyether ketone, polyamideimide polyesterimide, and polyaryl ether ketone. The optical compensation film as described in (37) characterized by containing the.

(39) A cellulose acylate film according to any one of (1) to (33), or an optical compensation film according to any one of (34) to (38) as a protective film for at least one polarizer. Polarizer.

(40) The polarizing plate according to (39), wherein at least one of a hard coat layer, an antiglare layer, and an antireflection layer is formed on the surface.

(41) Any one of the cellulose acylate film as described in any one of (1)-(33), the optical compensation film as described in any one of (34)-(38), and the polarizing plate as described in (39) or (40). Liquid crystal display device having a.

(42) Any one of the cellulose acylate film as described in any one of (1)-(33), the optical compensation film as described in any one of (34)-(38), and the polarizing plate as described in (39) or (40). VA or IPS liquid crystal display device having a.

(43) The IPS liquid crystal display device of (42) having a polarizing plate on both sides of the liquid crystal cell, wherein the liquid crystal cell of at least one polarizing plate has a cellulose acylate film according to any one of (1) to (33). A liquid crystal display device.

Best Mode for Carrying Out the Invention

[Cellulose Acylate Raw Material Cotton]

Examples of the cellulose which is a cellulose acylate raw material used in the present invention include cotton linter and wood pulp (softwood pulp, softwood pulp), and the like. do. For a detailed description of these raw celluloses, for example, plastic material lecture (17) fibrin resin (Marusawa, Uda, Daily Industrial Newspaper, 1970) or the Society of the Invention Publications 2001-1745 (pages 7 to 8). The cellulose described in) can be used, and the cellulose acylate film of the present invention is not particularly limited.

[Cellulose Acylate Substitution Degree]

Next, the cellulose acylate of the present invention produced by using the cellulose described above as a raw material will be described. In the cellulose acylate of the present invention, the hydroxyl group of the cellulose is acylated, and the substituents can be used for all of the acetyl group having 2 carbon atoms of the acyl group to 22 carbon atoms. In the cellulose acylate of the present invention, the degree of substitution substituted with the hydroxyl group of cellulose is not particularly limited, but the degree of binding of acetic acid substituted with the hydroxyl group of cellulose and / or fatty acids having 3 to 22 carbon atoms is measured and calculated by calculation. The degree of substitution can be obtained. As a measuring method, it can carry out according to ASTM D-817-91.

As mentioned above, in the cellulose acylate of this invention, although it does not specifically limit about the substitution degree substituted by the hydroxyl group of cellulose, It is preferable that the acyl substitution degree substituted by the hydroxyl group of cellulose is 2.50-3.00. Furthermore, it is preferable that it is 2.75-3.00, and, as for acyl substitution degree, it is more preferable that it is 2.85-3.00.

The acyl group having 2 to 22 carbon atoms in the acetic acid and / or fatty acid having 3 to 22 carbon atoms substituted with a hydroxyl group of cellulose may be an aliphatic group or an allyl group, and is not particularly limited. These are, for example, alkylcarbonyl esters, alkenylcarbonyl esters or aromatic carbonyl esters of cellulose, aromatic alkylcarbonyl esters, and the like, and may each have a further substituted group. Preferred examples of these acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, Nonyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferred, and acetyl, propionyl and butanoyl are more preferred. Do.

As a result of earnestly examining by the inventor of this invention, when the acyl substituent substituted by the hydroxyl group of the cellulose mentioned above substantially consists of at least two types of acetyl group / propionyl group / butanoyl group, the whole substitution degree is 2.50-3.00. In the case of, it was found that the optical anisotropy of the cellulose acylate film can be reduced. More preferable acyl substitution degree is 2.60-3.00, More preferably, it is 2.65-3.00.

[Polymerization degree of cellulose acylate]

The polymerization degree of the cellulose acylate used preferably in this invention is 180-700 in viscosity average polymerization degree, 180-550 is more preferable in cellulose acetate, 180-400 is still more preferable, 180-350 is especially preferable. When the degree of polymerization is too high, the viscosity of the dope solution of cellulose acylate becomes high, and film production becomes difficult by casting. If the degree of polymerization is too low, the strength of the produced film is lowered. The average degree of polymerization can be measured by an extreme viscosity method such as Uda et al. (Kazuo Uda, Hideo Hideo, Journal of Textile Science, Vol. 18, No. 1, pp. 105-120, 1962). Is disclosed in detail in Japanese Patent Application Laid-Open No. 9-95538.

Moreover, the molecular weight distribution of the cellulose acylate used preferably in this invention is evaluated by gel permeation chromatography, the polydispersity index Mw / Mn (Mw is mass mean molecular weight, Mn is number average molecular weight) is small, molecular weight distribution It is preferable that is narrow. As a specific value of Mw / Mn, it is preferable that it is 1.0-3.0, It is more preferable that it is 1.0-2.0, It is most preferable that it is 1.0-1.6.

When the low molecular weight component is removed, the average molecular weight (polymerization degree) increases, but the viscosity is lower than that of the usual cellulose acylate, which is useful. The cellulose acylate with few low molecular weight components can be obtained by removing the low molecular weight component from the cellulose acylate synthesized by a conventional method. Removal of the low molecular weight component can be carried out by washing the cellulose acylate with a suitable organic solvent. Moreover, when manufacturing the cellulose acylate with few low molecular weight components, it is preferable to adjust the amount of sulfuric acid catalysts in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is in the above range, a cellulose acylate (uniform in molecular weight distribution) can be synthesized even from the viewpoint of molecular weight distribution. When used at the time of preparation of the cellulose acylate of the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, particularly cellulose acylate having a water content of 0.7% by mass or less. Generally, cellulose acylate contains water and 2.5-5 mass% is known. In this invention, in order to make it the moisture content of this cellulose acylate, it is necessary to dry and the method will not be specifically limited if it becomes the target moisture content. These cellulose acylates of the present invention are described in detail in pages 7 to 12 of the invention association publication (Publication No. 2001-1745, published on March 15, 2001, Invention Association). have.

The cellulose acylate of the present invention can be used by mixing a single or another two or more kinds of cellulose acylates as long as it is in the above-described ranges such as a substituent, a degree of substitution, a degree of polymerization, a molecular weight distribution, and the like.

[Additive to Cellulose Acylate]

In the cellulose acylate solution of the present invention, various additives (e.g., a compound that lowers optical anisotropy, a wavelength dispersion regulator, a UV inhibitor, a plasticizer, a deterioration inhibitor, a fine particle, an optical property regulator, etc.) according to the use in each preparation step are used. Can be added and these are demonstrated below. Moreover, although the addition time may be added at any time in a dope preparation process, you may add and implement the process of adding and preparing an additive to the last preparation process of a dope preparation process.

At least 1 sort (s) containing the compound which reduces the optical anisotropy of the cellulose acylate film of this invention, especially the retardation Rth of the film thickness direction represented by following formula (i) in the range which satisfy | fills following formula (ii) and (iii). It is desirable to.

(Ⅰ) Rth = ((nx + ny) / 2-nz) × d

(Ii) (Rth (A) -Rth (O)) / A <-1.0                     

(Iii) 0.01 ≦ A ≤30,

Formulas (ii) and (iii)

(Ii) (Rth (A) -Rth (O)) / A <-2.0

(Iii) 0.05 ≦ A ≤25,

It is more preferable that it is

(Ii) (Rth (A) -Rth (O)) / A <-3.0

(Iii) 0.1 ≤ A ≤ 20

More preferably.

[Structural Features of Compounds Reducing the Optical Anisotropy of Cellulose Acylate Films]

The compound which reduces the optical anisotropy of a cellulose acylate film is demonstrated. As a result of earnestly examining the inventors of the present invention, the optical anisotropy is sufficiently reduced by using a compound which suppresses the cellulose acylate in the film from being oriented in the in-plane and film thickness directions, and Re is zero (0) and Rth is zero. To get closer. For this purpose, the compound which lowers optical anisotropy is sufficiently compatible with cellulose acylate, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, in the case where there are a plurality of planar functional groups such as aromatic groups, a structure having these functional groups on the non-plane rather than the same plane is advantageous.

(LogP value)                     

When producing the cellulose acylate film of the present invention, as described above, octanol-water partition coefficient (logP value) in the compound which inhibits the cellulose acylate in the film from being oriented in the in-plane and film thickness direction and lowers the optical anisotropy. Is preferably 0-7.

Compounds having a logP value of greater than 7 lack compatibility with cellulose acylate, and are susceptible to clouding and fractionation of the film. Moreover, since the compound whose logP value is smaller than 0 has high hydrophilicity, the water resistance of a cellulose acetate film may deteriorate. As a logP value, the more preferable range is 1-6, Especially preferable range is 1.5-5.

The octanol-water partition coefficient (logP value) can be measured by the flask immersion method described in JIS Japanese Industrial Standard Z 7260-107 (2000). The octanol-water partition coefficient (logP value) may also be approximated by computational or empirical methods on behalf of the measurements. As a calculation method, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), the Viswanadhan's fragmentation method (J. Chem. Inf. ComPut. Sci., 29, 163 (1989).), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984).) And the like are preferably used. However, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is more preferred. When the value of logP of a compound varies depending on the measuring method or the calculation method, it is preferable to determine whether the compound is within the scope of the present invention by the creepen fragmentation method.                     

[Physical Properties of Compounds Degrading Optical Anisotropy]

The compound which lowers optical anisotropy may contain an aromatic group, and does not need to contain it. Moreover, it is preferable that the compound which reduces optical anisotropy is 150 or more and 3000 or less, It is preferable that they are 170 or more and 2000 or less, It is especially preferable that they are 200 or more and 1000 or less. If it is the range of these molecular weights, a specific monomer structure may be sufficient and the oligomer structure and polymer structure which the monomer unit couple | bonded two or more may be sufficient.

The compound which lowers the optical anisotropy is preferably a liquid at 25 ° C or a solid having a melting point of 25 to 250 ° C, more preferably a liquid at 25 ° C or a solid having a melting point of 25 to 200 ° C. Moreover, it is preferable that the compound which reduces optical anisotropy does not volatilize in the dope casting | flow_spread of a cellulose acylate film preparation, and a drying process.

It is preferable that the addition amount of the compound which reduces optical anisotropy is 0.01-30 mass% of cellulose acylate, It is more preferable that it is 1-25 mass%, It is especially preferable that it is 5-20 mass%.

The compound which lowers optical anisotropy may be used independently, and may mix and use 2 or more types of compounds in arbitrary ratios.

The time of adding the compound which reduces optical anisotropy may be any time in a dope preparation process, and you may carry out at the end of a dope preparation process.

The compound which reduces optical anisotropy is 80-99% of the average content of the compound in the center part of the cellulose acylate film in the part which becomes 10% of the total film thickness on the surface of at least one side. . The amount of the compound present in the present invention can be determined by measuring the amount of the compound on the surface and the central portion, for example, by a method using the infrared absorption spectrum described in JP-A-8-57879.

Although the specific example of the compound which reduces the optical anisotropy of the cellulose acylate film used preferably by this invention below is shown, this invention is not limited to these compounds.

The compound of Formula 1 will be described.

In the general formula (1), each of R ¹⁰¹ -R ¹⁰³ independently represents an aliphatic group having 1 to 20 carbon atoms. R ¹⁰¹ -R ¹⁰³ may be connected to each other to form a ring.

R ¹⁰¹ -R ¹⁰³ will be described in detail. R ¹⁰¹ -R ¹⁰³ is preferably an aliphatic group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. The aliphatic group here is preferably an aliphatic hydrocarbon group, more preferably an alkyl group (including chain, branched and cyclic alkyl groups), alkenyl group or alkynyl group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, decyl, Dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl , Bicyclo [2.2.2] octane-3-yl, and the like, and examples of the alkenyl group include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl etc. are mentioned, As an alkynyl group, ethynyl, a propargyl, etc. are mentioned, for example.

The aliphatic group represented by R ¹⁰¹ -R ¹⁰³ may be substituted, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group (linear, branched, cyclic alkyl group, bicycloalkyl group, Active methine group), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of substituted position), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-acylcar Bamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxyl group or its salt, oxalyl group, oxamoyl group, cyano group, carbon Imidoyl group (Carbonimidoyl group), formyl group, hydroxy group, alkoxy group (including groups containing ethyleneoxy group or propyleneoxy group unit repeatedly), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or Is an aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thiourido group, imide group, (alkoxy Or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonylureido group, N-acylureido group, N-acylsulfamoylamino group, 4 Heterocyclic groups containing radical nitrogen atoms (e.g. pyridinio groups, imidazolio groups, quinolini groups, isoquinolini groups), isocyano groups, imino groups, (alkyl or aryl) sulfonyl groups , (Alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acyl sulfamoyl group, N-sulfonyl sulfamoyl group or salt thereof, phosphino group, phosphinyl group, phosphinyloxy group, phosph Pinylamino group, a silyl group, etc. are mentioned. have.

These groups may be further combined to form a complex substituent, and examples of such substituents include an ethoxyethoxyethyl group, a hydroxyethoxyethyl group, an ethoxycarbonylethyl group, and the like. Moreover, R <^101> -R <^103> may contain a phosphate ester group as a substituent, and the compound of General formula (1) can also have a some phosphate ester group in the same molecule.

The compounds of the formulas (2) and (3) are described.

In the formula 2 and 3, Z is a carbon atom, an oxygen atom, a sulfur atom, -NR ²⁰⁵ - represents a, R ²⁰⁵ represents a hydrogen atom or an alkyl group. The 5- or 6-membered ring composed of Z may have a substituent, or a plurality of substituents may be bonded to each other to form a ring. Examples of the 5 or 6 membered ring containing Z include tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, thiane, pyrrolidine, piperidine, indolin, isoindolin, chromman, isochrome And tetrahydro-2-furanone, tetrahydro-2-pyron, 4-butanlactam, 6-hexanolactam and the like.

Moreover, the 5- or 6-membered ring comprised containing Z contains a lactone structure or lactam structure, ie, the cyclic ester or cyclic amide structure which has an oxo group in the adjacent carbon of Z. Examples of such cyclic ester or cyclic amide structures include 2-pyrrolidone, 2-piperidone, 5-pentanolide, 6-hexanolide.                     

R ²⁰⁵ is a hydrogen atom or preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms (including linear, branched and cyclic alkyl groups). Indicates. ^Examples of the alkyl group represented by R ²⁰⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, Decyl, dodecyl, eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-a Dandanyl, bicyclo [2.2.2] octan-3-yl, and the like. The alkyl group represented by R ²⁰⁵ may further have a substituent, and examples of the substituent include a group which may be substituted with R ¹⁰¹ -R ^{103 described} above.

Y ²⁰¹ -Y ²⁰² each independently represents an ester group, an alkoxycarbonyl group, an amide group or a carbamoyl group. As ester group, Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, n-butylcarbonyloxy, iso-butylcarbonyloxy, t-butylcarbonyloxy, sec-butylcarbonyloxy, n-pentylcarbonyloxy, t-amylcarbonyloxy, n-hexylcarbonyloxy, cyclo Hexylcarbonyloxy, 1-ethylpentylcarbonyloxy, n-heptylcarbonyloxy, n-nonylcarbonyloxy, n-undecylcarbonyloxy, benzylcarbonyloxy, 1-naphthalenecarbonyloxy, 2-naphthalene Carbonyloxy, 1-adamantanecarbonyloxy, etc. can be illustrated. The alkoxycarbonyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, n- Propyloxycarbonyl, isopropyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl, iso-butyloxycarbonyl, sec-butyloxycarbonyl, n-pentyloxycarbonyl, t-amyloxy Carbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-ethylpropyloxycarbonyl, n-octyloxycarbonyl, 3,7-dimethyl-3- Octyloxycarbonyl, 3,5,5-trimethylhexyloxycarbonyl, 4-t-butylcyclohexyloxycarbonyl, 2,4-dimethylpentyl-3-oxycarbonyl, 1-adamantaneoxycarbon Carbonyl, 2-adamantaneoxycarbonyl, dicyclopentadienyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, n-tetradecyloxy Viterbo carbonyl, and the like can be given to n- hexadecyl -1,3 Brassica Viterbo carbonyl. As an amide group, Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetamide, ethylcarboxamide, n-propylcarboxe Mid, isopropylcarboxamide, n-butylcarboxamide, t-butylcarboxamide, iso-butylcarboxamide, sec-butylcarboxamide, n-pentylcarboxamide, t-amylcarboxamide, n-hexylcarboxamide, cyclohexylcarboxamide, 1-ethylpentylcarboxamide, 1-ethylpropylcarboxamide, n-heptylcarboxamide, n-octylcarboxamide, 1-adamantanecarbox Mid, 2-adamantane carboxamide, n-nonyl carboxamide, n-dodecyl carboxamide, n-pentacarboxamide, n-hexadecyl carboxamide, etc. can be illustrated. The carbamoyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example methylcarbamoyl, dimethylcarbamoyl or ethyl. Carbamoyl, diethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, iso-butylcarbamoyl, sec-butylcarbamoyl , n-pentylcarbamoyl, t-amylcarbamoyl, n-hexylcarbamoyl, cyclohexylcarbamoyl, 2-ethylhexylcarbamoyl, 2-ethylbutylcarbamoyl, t-octylcarbamoyl , n-heptylcarbamoyl, n-octylcarbamoyl, 1-adamantanecarbamoyl, 2-adamantanecarbamoyl, n-decylcarbamoyl, n-dodecylcarbamoyl, n- Tetradecylcarbamoyl, n-hexadecylcarbamoyl and the like. Y ²⁰¹ -Y ²⁰² may be connected to each other to form a ring. Y ^201- Y ²⁰² may further have a substituent, and the group which may be substituted by said R <^101> -R <^103> is mentioned as an example.

The compound of Formula 4-12 is demonstrated.

In the formulas (4) to (12), Y ³¹ -Y ⁷⁰ each independently represent an ester group, an alkoxycarbonyl group, an amide group, a carbamoyl group, or a hydroxy group. As ester group, Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, n-butylcarbonyloxy, iso-butylcarbonyloxy, t-butylcarbonyloxy, sec-butylcarbonyloxy, n-pentylcarbonyloxy, t-amylcarbonyloxy, n-hexylcarbonyloxy, cyclo Hexylcarbonyloxy, 1-ethylpentylcarbonyloxy, n-heptylcarbonyloxy, n-nonylcarbonyloxy, n-undecylcarbonyloxy, benzylcarbonyloxy, 1-naphthalenecarbonyloxy, 2-naphtha Lencarbonyloxy, 1-adamantanecarbonyloxy, etc. are mentioned. The alkoxycarbonyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, n -Propyloxycarbonyl, isopropyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl, iso-butyloxycarbonyl, sec-butyloxycarbonyl, n-pentyloxycarbonyl, t-amyl 1-ethylpropyloxycarbonyl, n-octyloxycarbonyl, 3,7-dimethyl-, such as oxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, 2-ethylhexyloxycarbonyl 3-octyloxycarbonyl, 3,5,5-trimethylhexyloxycarbonyl, 4-t-butylcyclohexyloxycarbonyl, 2,4-dimethylpentyl-3-oxycarbonyl, 1-adamantane Oxycarbonyl, 2-adamantaneoxycarbonyl, dicyclopentadienyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, n-tetradecyloxy Carbonyl, and the like n- hexadecyl de Viterbo -1,3 Brassica carbonyl. As an amide group, Preferably it is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetamide, ethylcarboxamide, n-propylcarboxe Mid, isopropylcarboxamide, n-butylcarboxamide, t-butylcarboxamide, iso-butylcarboxamide, sec-butylcarboxamide, n-pentylcarboxamide, t-amylcarboxamide, n-hexylcarboxamide, cyclohexylcarboxamide, 1-ethylpentylcarboxamide, 1-ethylpropylcarboxamide, n-heptylcarboxamide, n-octylcarboxamide, 1-adamantanecarbox Mid, 2-adamantane carboxamide, n-nonyl carboxamide, n-dodecyl carboxamide, n-pentacarboxamide, n-hexadecyl carboxamide, etc. are mentioned. The carbamoyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, methyl carbamoyl, dimethylcarbamoyl, ethylcarba Moyl, diethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, iso-butylcarbamoyl, sec-butylcarbamoyl, n -Pentylcarbamoyl, t-amylcarbamoyl, n-hexylcarbamoyl, cyclohexylcarbamoyl, 2-ethylhexylcarbamoyl, 2-ethylbutylcarbamoyl, t-octylcarbamoyl, n -Heptylcarbamoyl, n-octylcarbamoyl, 1-adamantanecarbamoyl, 2-adamantanecarbamoyl, n-decylcarbamoyl, n-dodecylcarbamoyl, n-tetradecyl Carbamoyl, n-hexadecylcarbamoyl, and the like. Y <^31> -Y <^70> may have a substituent further and the group which may be substituted by said R <^101> -R <^103> is mentioned as an example.

V ³¹ -V ⁴³ each independently represents a hydrogen atom or an aliphatic group having preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Herein, the aliphatic group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group (including chain, branched and cyclic alkyl groups), alkenyl group or alkynyl group. As an alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, decyl, dodecyl , Eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, 2,6-dimethylcyclohexyl, 4-t-butylcyclohexyl, cyclopentyl, 1-adamantyl, 2-adamantyl, b Cyclo [2.2.2] octan-3-yl, and the like, and examples of the alkenyl group include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl and 2-cyclo Hexen-1-yl etc. are mentioned, As an alkynyl group, ethynyl, a propargyl, etc. are mentioned, for example. V <^31> -V <^43> may have a substituent further and the group which may be substituted by said R <^101> -R <^103> is mentioned as an example.

L ³¹ -L ⁸⁰ each independently represents a divalent saturated linking group having 0 to 40 atoms and 0 to 20 carbon atoms. Here, the number of atoms of L ³¹ -L ⁸⁰ being 0 means that the groups at both ends of the linking group form a single bond directly. Preferred examples of L ³¹ -L ⁷⁷ include alkylene groups (eg methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, methylethylene, ethylethylene, etc.), cyclic divalent groups (eg For example, cis-1,4-cyclohexylene, trans-1,4-cyclohexylene, 1,3-cyclopentylidene, etc.), ether, thioether, ester, amide, sulfone, sulfoxide, sulfide , Sulfonamide, ureylene, thioureylene and the like. These divalent groups may be bonded to each other to form a divalent complex group, and examples of the compound substituent are-(CH ₂ ) ₂ O (CH ₂ ) ₂ -,-(CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ )-,-(CH ₂ ) ₂ S (CH ₂ ) ₂ -,-(CH ₂ ) ₂ O ₂ C (CH ₂ ) ₂ -and the like. L ³¹ -L ⁸⁰ may further have a substituent, and examples of the substituent include a group which may be substituted with R ¹⁰¹ -R ^{103 described} above.

Preferred examples of the compound formed by the combination of Y ³¹ -Y ⁷⁰ , V ³¹ -V ⁴³ and L ³¹ -L ^{80 in} the formulas (4) to 12 include citric acid esters (for example, O-acetyl citrate, O-acetyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, O-acetyl citrate tri (ethyloxycarbonylmethylene) ester, etc.), oleic acid ester (e.g. ethyl oleate, butyl oleate, 2-ethylhexyl oleate) , Phenyl oleate, cyclohexyl oleate, octyl oleate, etc., ricinolic acid esters (e.g., methylacetyl ricinolate), sebacic acid esters (e.g. dibutyl sebacate, etc.), carboxylic acid esters of glycerin (e.g. tria Cetine, tributyrin, etc.), glycolic acid ester (for example, butylphthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butylglycol) Cholate, methylphthalylmethylglycolate, propylphthalylpropylglycolate, butylphthalylbutylglycolate, octylphthalyloctylglycolate, etc., carboxylic esters of pentaerythritol (e.g. pentaerythritol tetraacetate, pentaerythritol tetrabutyl) Carboxylic acid ethers of dipentaerythritol (e.g., dipentaerythritol hexaacetate, dipentaerythritol hexabutylate, dipentaerythritol tetraacetate, and the like), and carboxylic acid esters of trimethylolpropane (trimethylol propane acetate, trimethyl) All propane diacetate monopropionate, trimethylol propane tripropionate, trimethylol propane tributylate, trimethylol propane tripivaloate, trimethylol propane tri (t-butyl acetate), trimethylol propanedi2-ethyl Sanate, trimethylol propane tetra 2-ethylhexanate, trimethylol propane diacetate monooctanate, trimethylol propane trioctanate, trimethylol propane tri (cyclohexane carboxylate), and the like. Glycerol esters described in Japanese Patent Application Publication No. 2000-63560, diglycerol esters, citric acid esters described in Japanese Patent Application Laid-Open No. 11-92574, pyrrolidone carboxylic acid esters (2-pyrroli) Don-5-methyl carboxylate, 2-pyrrolidone-5-ethyl carboxylate, 2-pyrrolidone-5-butyl carboxylate, 2-pyrrolidone-5-carboxylic acid 2-ethylhexyl), cyclohexanedicarboxylic acid ester ( cis-1,2-cyclohexanedicarboxylic acid dibutyl, trans-1,2-cyclohexanedicarboxylic acid dibutyl, cis-1,4-cyclohexanedicarboxylic acid dibutyl, trans-1,4-cyclohexanedi Dibutyl carboxylate, etc.), xili And the like carboxylic acid ester (xylitol pentaacetate, xylitol tetraacetate, xylitol penta propionate, etc.).

Examples of the compound represented by the formulas (1) to (12) of the present invention are given below, but the present invention is not limited thereto. In addition, about the general formula (1), compounds C-1 to C-76 are illustrated, and for the general formulas (2) to (12), compounds C-201 to C-231 and C-401 to C-448 are illustrated. The value of logP described in the table or in parentheses is obtained by the creepen fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987).).

The compounds of the formulas (13) and (14) are described below.                     

In Formula 13, R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Moreover, it is especially preferable that the sum total of carbon ^number of R <^31> , R <^32> and R < ³³ > is 10 or more. In the formula (14), R ¹⁰⁴ and R ¹⁰⁵ each independently represent an alkyl group or an aryl group. The total number of carbon atoms of R ¹⁰⁴ and R ¹⁰⁵ is 10 or more, and the alkyl group and the aryl group may each have a substituent. As the substituent, a fluorine atom, an alkyl group, an aryl group, an alkoxy group sulfone group and a sulfonamide group are preferable, and an alkyl group, an aryl group, an alkoxy group, a sulfone group and a sulfonamide group are particularly preferable. In addition, the alkyl group may be linear, branched or cyclic, preferably having 1 to 25 carbon atoms, more preferably 6 to 25, and having 6 to 20 (eg methyl, ethyl, propyl). , Isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, nonyl, adamantyl, decyl, t-octyl, undecyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, didecyl) are particularly preferred. The aryl group preferably has 6 to 30 carbon atoms, and particularly preferably 6 to 24 carbon atoms (for example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl and triphenylphenyl). Preferable examples of the compound represented by the formula (13) or the formula (14) are shown below, but the present invention is not limited to these specific examples.

The compound of Formula 15 will be described.

[Formula 15]

In Formula 15, R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, amyl, isoamyl). It is preferred that at least one of R ²¹ , R ²² and R ^{23 be} an alkyl group having 1 to 3 carbon atoms (eg methyl, ethyl, propyl, isopropyl). X ²¹ is a single bond, —O—, —CO—, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, for example methylene, ethylene, propylene) or an arylene group (preferably Preferably it is 6-24 carbon atoms, More preferably, it is 6-12. For example, it is preferable that it is a bivalent coupling group formed with 1 or more types chosen from phenylene, biphenylene, naphthylene), -O It is particularly preferable that it is a divalent linking group formed of at least one group selected from an alkylene group or an arylene group. Y ²¹ is a hydrogen atom, an alkyl group (preferably having 2 to 25 carbon atoms, more preferably 2 to 20. For example, ethyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, t-octyl, Dodecyl, cyclohexyl, dicyclohexyl, adamantyl), aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18. For example, phenyl, biphenyl, terphenyl, naphthyl ) Or an aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20. For example, benzyl, credyl, t-butylphenyl, diphenylmethyl, triphenylmethyl), It is especially preferable that they are an alkyl group, an aryl group, or an aralkyl group. A combination of -X ²¹ -Y ²¹ is preferably a small number of bullets -X ²¹ -Y ²¹ is 0 to 40, and that of 1 to 30, and more preferably, it is most preferred that the 1 to 25. Although the preferable example of the compound represented by these general formula (15) is shown below, this invention is not limited to these specific examples.

Below, the compound of General formula (16) is demonstrated.

[Chemical Formula 16]

Q ¹ , Q ² and Q ³ each independently represent a 5 to 6 membered ring, may be a hydrocarbon ring or a hetero ring, and they may be monocyclic or may form a condensed ring with another ring. As a hydrocarbon ring, Preferably, they are a substituted or unsubstituted cyclohexane ring, a substituted or unsubstituted cyclopentane ring, an aromatic hydrocarbon ring, More preferably, they are an aromatic hydrocarbon ring. As a hetero ring, it is a ring containing preferably at least one of an oxygen atom, a nitrogen atom or a sulfur atom of a 5 to 6 membered ring. More preferably, the hetero ring is an aromatic hetero ring containing at least one of an oxygen atom, a nitrogen atom, or a sulfur atom.

As Q ¹ , Q ² and Q ³ , they are preferably aromatic hydrocarbon rings or aromatic hetero rings. The aromatic hydrocarbon ring is preferably (preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.), and more preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. Hydrocarbon rings, more preferably aromatic hydrocarbon rings having 6 to 12 carbon atoms), and more preferably benzene rings.

As an aromatic hetero ring, Preferably it is an aromatic hetero ring containing an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples of the hetero rings include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, Chiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine And tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As an aromatic hetero ring, Preferably, they are pyridine, triazine, quinoline. As Q <^1> , Q <^2> and Q <^3> , More preferably, it is an aromatic hydrocarbon ring, More preferably, it is a benzene ring. Moreover, Q <^1> , Q <^2> and Q <^3> may have a substituent and the substituent T mentioned later is mentioned.

X ⁶¹ represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent), N, P, P═O, and as X ⁶¹ preferably B, CR ⁷⁰ (preferably an aryl group, substituted as R ⁷⁰⁾ Or unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto group, Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, more preferably aryl group, alkoxy group, aryloxy group, hydroxy group, halogen atom, more preferably alkoxy group, hydroxy group Is a hydroxy group), N, X ⁶¹ is preferably CR ⁷⁰ , N, and particularly preferably CR ⁷⁰ .

As general formula (16), it is preferably a compound represented by the following general formula (17).                     

[Chemical Formula 17]

In formula (17), X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent), N, P, P═O. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each independently a hydrogen atom Or a substituent. If possible, two groups of R ⁴¹ to R ⁶⁵ (for example, R ⁴¹ and R ⁵¹ ) may be connected to each other to form a ring.

X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent), N, P, P═O, and X ⁴² preferably represents B, CR ⁷⁰ (preferably an aryl group, substituted as R ⁷⁰⁾ . Or unsubstituted amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, hydroxy group, mercapto group, Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, more preferably aryl group, alkoxy group, aryloxy group, hydroxy group, halogen atom, more preferably alkoxyl group, hydroxy group And particularly preferably a hydroxy group), N, P = O, more preferably CR ⁷⁰ , N, and particularly preferably CR ⁷⁰ .

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represent a hydrogen atom or a substituent The substituent T mentioned later can be applied as a substituent. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are preferably alkyl groups, Alkenyl, alkynyl, aryl, substituted or unsubstituted amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphate amide group, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom) , Bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably 1 to 30 carbon atoms, more preferably Is 1 to 12, and as a hetero atom, for example, a nitrogen atom, an oxygen atom, Atoms, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzooxazolyl, benzimidazolyl, benzthiazolyl), and silyl groups More preferably, they are an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group, More preferably, they are an alkyl group, an aryl group, and an alkoxy group.

These substituents may be further substituted. In addition, when two or more substituents exist, they may be the same and may differ. In addition, if possible, they may be connected to each other to form a ring.

The substituent T mentioned above is demonstrated below. As the substituent T, for example, an alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example methyl, ethyl, iso-propyl, tert-butyl , n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, and the like), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms), in particular Preferably it is C2-C8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc., an alkynyl group (preferably C2-C20, More preferably, it is C2-C8) 12, particularly preferably 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl and the like, an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms); Especially preferably, it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned), Ring or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example amino, methylamino, dimethylamino, diethylamino, dibenzyl Amino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, ethoxy, butoxy etc. The aryloxy group (preferably C6-C20, More preferably, it is C6-C16, Especially preferably, it is C6-C12, For example, phenyloxy, 2-naphthyloxy, etc. are mentioned. Acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, formyl, pivaloyl, etc. are mentioned. Alkoxycarbonyl group (preferably) 2-20, more preferably C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned, An aryloxycarbonyl group (preferably C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, a phenyloxycarbonyl etc. are mentioned, Acyloxy group (Preferably C2-20, More preferably, they are C2-C16, Especially preferably, it is C2-C10, For example, an acetoxy, benzoyloxy, etc. are mentioned, Acylamino group (Preferably C2-C20, More preferably, it is C1-C10) 2-16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably, it is C2-C16 , Especially preferred Crab has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms), and particularly preferably C7-C12, a phenyloxycarbonylamino etc. are mentioned, for example, sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12 Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably C0-20, more preferably C0-16, particularly preferably C0-12 For example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl and the like, carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms), particularly preferably Is 1 to 12 carbon atoms Examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like, and alkylthio groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Especially preferably, they are C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably C6-C20, More preferably, C6-C16, Especially preferably, Has 6 to 12 carbon atoms, for example, phenylthio, etc., a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, mesyl, tosyl, etc., sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, methanesulfinyl, benzene Sulfinyl, etc.), ureido (preferably burnt) It is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido, etc. are mentioned, The phosphate amide group (preferably Is C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, diethyl phosphate amide, a phenyl phosphate amide, etc.), A hydroxy group, a mercapto group, Halogen Atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably Preferably it is 1-30, more preferably 1-12, and a hetero atom is a nitrogen atom, an oxygen atom, a sulfur atom, for example, imidazolyl, pyridyl, quinolyl, furyl, piperi Dill, morpholino, benzoxazolyl, benzi Midazolyl, benzthiazolyl, and the like, silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms), for example trimethylsilyl, Triphenylsilyl etc.) etc. are mentioned. These substituents may be further substituted. In addition, when there are two or more substituents, they may be same or different. Also, where possible, they may be linked to each other to form a ring.

Although the specific example is shown and demonstrated in detail about the compound represented by General formula (16) below, this invention is not limited at all by the following specific examples.                     

Preferred examples of the compound represented by the formula (18) or the formula (19) are shown below, but the present invention is not limited to these specific examples.

The inventors of the present invention conducted optical examinations by adding a polyhydric alcohol ester compound, a carboxylic acid ester compound, a polycyclic carboxylic acid compound, and a bisphenol derivative having an octanol-water partition coefficient (LogP value) of 0 to 7 to the cellulose acylate. I found out that it lowered.

Specific examples of the polyhydric alcohol ester compound, the carboxylic acid ester compound, the polycyclic carboxylic acid compound, and the bisphenol derivative having an octanol-water partition coefficient (LogP value) of 0 to 7 are shown below.

(Polyhydric alcohol ester compound)

The polyhydric alcohol ester of the present invention is an ester of a dihydric or higher polyhydric alcohol and at least one monocarboxylic acid. Although the following are mentioned as a polyhydric alcohol ester compound, This invention is not limited to these.

(Poly alcohol)

Examples of preferred polyhydric alcohols include, for example, adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, Tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol , Hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylol propane and xylitol are preferable.

(Monocarboxylic acid)

There is no restriction | limiting in particular as monocarboxylic acid in the polyhydric alcohol ester of this invention, A well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. When alicyclic monocarboxylic acid and aromatic monocarboxylic acid are used, it is preferable at the point which improves the water vapor transmission rate, water content, and retention property of a cellulose acylate film.                     

Although the following are mentioned as an example of a preferable monocarboxylic acid, This invention is not limited to this.

As the aliphatic monocarboxylic acid, a fatty acid having a straight or branched chain having 1 to 32 carbon atoms can be preferably used. As for carbon number, it is more preferable that it is 1-20, and it is especially preferable that it is 1-10. It is preferable to contain acetic acid because compatibility with cellulose ester increases, and it is also preferable to mix acetic acid and another monocarboxylic acid.

Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecyl acid, lauric acid, tride Carboxylic acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachinic acid, behenic acid, lignocerinic acid, sertinic acid, heptaconic acid, montanic acid, melic acid, laxelic acid And unsaturated fatty acids such as saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, and the like. These may further have a substituent.

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

Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into a benzene ring of benzoic acid such as benzoic acid and toluic acid, an aromatic monocarboxylic acid having two or more benzene rings such as biphenylcarboxylic acid, naphthalincarboxylic acid, tetralincarboxylic acid, Or derivatives thereof. Especially benzoic acid is preferable.                     

The carboxylic acid in the polyhydric alcohol ester of this invention may be one type, and may mix 2 or more types. Moreover, all OH groups in polyhydric alcohol may be esterified, and some may remain as OH group. Preferably, it is preferable to have three or more aromatic rings or cycloalkyl rings in the molecule.

Although the following compounds are mentioned as a polyhydric alcohol ester compound, This invention is not limited to these.                     

(Carboxylic ester compound)

Although the following compounds are mentioned as an example as a carboxylic acid ester compound, This invention is not limited to these. Specifically, for example, phthalic acid esters such as phthalic acid ester and citric acid ester include dimethyl phthalate, diethyl phthalate, dicyclohexyl phthalate, dioctyl phthalate and diethylhexyl phthalate, and acetyl triethyl citrate as citric acid ester. Acetyl tributyl citrate. In addition, butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, trimethyl propane tribenzoate, etc. may also be mentioned. Alkylphthalyl alkyl glycolates are also preferably used for this purpose. Alkyl of alkyl phthalyl alkyl glycolate is an alkyl group having 1 to 8 carbon atoms. As alkyl phthalyl alkyl glycolate, methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl glycolate , Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, Butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolide, octyl phthalyl ethyl glycolate, etc. Methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl Talril propyl glycolate, butyl program talril butyl glycolate, octyl tilpeu talril octyl glycolate are preferred, and particularly preferably used are ethyl program talril ethyl glycolate. Moreover, you may use these alkylphthalyl alkyl glycolate etc. in mixture of 2 or more types.

Although the following compounds are mentioned as a carboxylic acid ester compound, This invention is not limited to these.                     

(Polycyclic Carboxylic Acid Compound)

It is preferable that the polycyclic carboxylic acid compound used by this invention is a compound whose molecular weight is 3000 or less, and it is especially preferable that it is a compound of 250-2000 or less. Although there is no restriction | limiting in particular about the size of a ring with respect to a cyclic structure, It is preferable that it consists of 3-8 atoms, and it is especially preferable that it is a 6-membered ring and / or a 5-membered ring. These may contain carbon, oxygen, nitrogen, silicon or other atoms, some of the ring bonds may be unsaturated bonds, for example, the 6-membered ring may be a benzene ring or a cyclohexane ring. The compound of the present invention may contain a plurality of such cyclic structures, and for example, may have both a benzene ring and a cyclohexane ring in a molecule, two cyclohexane rings, or a derivative of naphthalene or an anthracene derivative. do. More preferably, it is a compound which contains three or more such cyclic structures in a molecule | numerator. It is also preferable that at least one bond of the cyclic structure does not contain an unsaturated bond. Specifically, abietinic acid derivatives such as abietinic acid, dihydroabietinic acid and parastriic acid are typical, and the chemical formulas of these compounds are shown below, but are not particularly limited thereto.

(Bisphenol derivative)

It is preferable that the bisphenol derivative used by this invention is 10000 or less in molecular weight, and if it is this range, a monomer may be sufficient, and an oligomer and a polymer may be sufficient as it. The copolymer with another polymer may be sufficient, and the reactive substituent may be modified at the terminal. Although the chemical formula of these compounds is shown below, it is not specifically limited to these.

Moreover, in said specific example of bisphenol derivative, R1-R4 represents a hydrogen atom or a C1-C10 alkyl group. 1, m, n represent a repeating unit, although there is no limitation in particular, the integer of 1-100 is preferable and the integer of 1-20 is more preferable.                     

[Wavelength dispersion regulator]

The compound (henceforth a wavelength dispersion regulator) which reduces the wavelength dispersion of a cellulose acylate film is demonstrated. In order to make wavelength dispersion of Rth of the cellulose acylate film of this invention favorable, the compound which lowers the wavelength dispersion ₍ DELTA ₎ Rth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of Rth represented by a following formula (i) is a following formula. It is preferable to contain at least 1 sort (s) in the range which satisfy | fills (iv) and (iv).

(Ⅳ) ΔRth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ |

(Ⅴ) (ΔRth (B) -ΔRth (O)) / B ≤-2.0

(Iii) 0.01 ≤ B ≤ 30

The formulas (iii) and (iii)

(Ⅴ) (ΔRth (B) -ΔRth (O)) / B ≤-3.0

(Iii) 0.05 ≤ B ≤ 25

It is more preferable that it is

(V) (ΔRth (B) -ΔRth (O)) / B ≤-4.0

(VI) 0.1 ≤ B ≤ 20

More preferably.

The wavelength dispersion regulator has at least one compound which has an absorption in an ultraviolet region of _{200 to 400} nm and reduces | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of the _film. And the wavelength dispersion of Re and Rth of a cellulose acylate film were adjusted by containing 0.01-30 weight% with respect to the cellulose acylate solid content.

Generally, the value of Re and Rth of a cellulose acylate film becomes a wavelength dispersion characteristic in which the long wavelength side is larger than the short wavelength side. Therefore, it is required to smooth the wavelength dispersion by increasing Re and Rth on the relatively small short wavelength side. On the other hand, the compound having absorption in the ultraviolet region of 200 to 400 nm has a wavelength dispersion characteristic in which the absorbance at the longer wavelength side is larger than the short wavelength side. When this compound itself is isotropically present inside the cellulose acylate film, it is assumed that the birefringence of the compound itself, and further, the wavelength dispersion of Re and Rth, is similar to the wavelength dispersion of absorbance, and the short wavelength side is large.

Therefore, the wavelength dispersion of Re and Rth of a cellulose acylate film is adjusted by using what has absorption in the ultraviolet region of 200-400 nm as mentioned above, and is assumed that the wavelength dispersion of Re and Rth of the compound itself is large in the short wavelength side. Can be. For this purpose, the compound which modulates wavelength dispersion is required to be compatible with cellulose acylate sufficiently uniformly. The absorption band range of the ultraviolet region of such a compound is preferably 200 to 400 nm, more preferably 220 to 395 nm and even more preferably 240 to 390 nm.

In recent years, liquid crystal display devices such as televisions, notebook computers, and mobile portable terminals have been required to have excellent transmittance of optical members used in liquid crystal display devices in order to increase the luminance with less power. In that respect, the compound which has absorption in the ultraviolet region of 200-400 nm, and reduces | reduces | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | of a film is a cellulose acylate film When added to, it is required to have excellent spectral transmittance. In the cellulose acylate film of the present invention, the spectral transmittance at a wavelength of 380 nm is preferably 45% or more and 95% or less, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less.

As mentioned above, it is preferable that the wavelength dispersion regulator used preferably by this invention has a molecular weight of 250-1000 from a volatility viewpoint. More preferably, it is 260-800, More preferably, it is 270-800, Especially preferably, it is 300-800. If it is the range of these molecular weights, a specific monomer structure may be sufficient, and the monomer unit may also be an oligomer structure and a polymer structure couple | bonded with two or more.

It is preferable that a wavelength dispersion regulator does not volatilize in the dope casting of a cellulose acylate film preparation, and a drying process.

(Wavelength dispersion regulator addition amount)

It is preferable that the addition amount of the wavelength-dispersion regulator used preferably in this invention mentioned above is 0.01-30 weight% of cellulose acylate, It is more preferable that it is 0.1-20 weight%, It is especially that it is 0.2-10 weight% desirable.

(Wavelength dispersion modifier addition method)

In addition, these wavelength dispersion regulators may be used independently, and may mix and use 2 or more types of compounds by arbitrary ratios.                     

In addition, the time of adding these wavelength dispersion regulators may be any time in a dope preparation process, and you may carry out at the end of a dope preparation process.

As a specific example of the wavelength-dispersion regulator used preferably for this invention, a benzotriazole type compound, a benzophenone type compound, the compound containing a cyano group, an oxy benzophenone type compound, a salicylic acid ester type compound, a nickel complex salt type, for example Although a compound etc. are mentioned, this invention is not limited only to these compounds.

As a benzotriazole type compound, what is represented by General formula (101) is used suitably as a wavelength dispersion regulator of this invention.

Q ¹¹ -Q ¹² -OH

(Wherein Q ¹¹ represents a nitrogen-containing aromatic hetero ring, Q ¹² represents an aromatic ring),

Q ¹¹ represents a nitrogen containing aromatic hetero ring, preferably a 5 to 7 membered nitrogen containing aromatic hetero ring, more preferably a 5 to 6 membered nitrogen containing aromatic hetero ring, for example, imidazole, pyrazole , Triazole, tetrazole, thiazole, oxazole, serenazol, benzotriazole, benzothiazole, benzoxazole, benzo serenazol, thiadiazole, oxadiazole, naphthothiazole, naphthooxazole, azabenz Imidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, triazadene, tetrazaindene, and the like, more preferably a 5-membered nitrogen-containing aromatic heterocyclic ring, specifically imidazole , Pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadiazole and oxadiazole are preferred, particularly preferably benzotriazole.

The nitrogen-containing aromatic hetero ring represented by Q ¹¹ may further have a substituent, and the substituent T described above can be applied as the substituent. Moreover, when there are a plurality of substituents, each may be condensed to further form a ring.

The aromatic ring represented by Q ¹² may be an aromatic hydrocarbon ring or an aromatic hetero ring. Moreover, these may be monocyclic and may also form a condensed ring with another ring.

The aromatic hydrocarbon ring is preferably (preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.), and more preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. Hydrocarbon rings, more preferably aromatic hydrocarbon rings having 6 to 12 carbon atoms), and more preferably benzene rings.

As an aromatic hetero ring, it is preferably an aromatic hetero ring containing a nitrogen atom or a sulfur atom. Specific examples of the hetero ring include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole, Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole , Benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic hetero ring, pyridine, triazine, quinoline are preferable.

As an aromatic ring represented by Q ¹² , Preferably it is an aromatic hydrocarbon ring, More preferably, it is a naphthalene ring, a benzene ring, Especially preferably, it is a benzene ring. Q ¹² may further have a substituent, and the substituent T described above is preferable.

As Formula (101), it is preferably a compound represented by the following Formula (101a).

(Wherein R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represent a hydrogen atom or a substituent. The substituent T described above may be applied as the substituent). In addition, these substituents may be further substituted by another substituent, and the substituents may be condensed to form a ring structure.)

R ²⁰¹ and R ²⁰³ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom, It is an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, and a halogen atom, More preferably, it is a hydrogen atom and a C1-C12 alkyl group, Especially preferably, it is a C1-C12 alkyl group (preferably C4-C12) to be.

R ²⁰² and R ²⁰⁴ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, a halogen atom, more preferably a hydrogen atom, a carbon 1-12 alkyl group, particularly preferably a hydrogen atom, a methyl group, and most preferably a hydrogen atom.

R ²⁰⁶ and R ²⁰⁸ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, and more preferably a hydrogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, a halogen atom, more preferably a hydrogen atom, a carbon 1-12 alkyl group, particularly preferably a hydrogen atom, a methyl group, and most preferably a hydrogen atom.

R ²⁰⁶ and R ²⁰⁷ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom, and more preferably a hydrogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, a halogen atom, more preferably a hydrogen atom or a halogen atom, particularly preferably a hydrogen atom or a chlorine atom.)

As Formula 101, it is more preferably a compound represented by Formula 101b.                     

(Wherein, R ²⁰¹ , R ²⁰³ , R ²⁰⁵ and R ²⁰⁷ have the same meaning as that in the general formula 101a, and the preferred range is also the same.)

Although the specific example of a compound represented by General formula (101) is given to the following, this invention is not limited to the following specific example at all.

Among the benzotriazole-based compounds mentioned above, when the cellulose acylate film of the present invention was produced without containing one having a molecular weight of 320 or less, it was confirmed that it was advantageous in terms of retention.                     

Moreover, as a benzophenone type compound which is one of the wavelength dispersion regulators used for this invention, what is represented by General formula (102) is used preferably.

(Wherein Q ¹¹ and Q ¹² each independently represent an aromatic ring. X ¹⁰¹ represents NR ²¹⁰ (R ²¹⁰ represents a hydrogen atom or a substituent), an oxygen atom or a sulfur atom)

The aromatic ring represented by Q ¹¹ and Q ¹² may be an aromatic hydrocarbon ring or an aromatic hetero ring. Moreover, these may be monocyclic and may form a condensed ring with another ring.

The aromatic hydrocarbon ring represented by Q ¹¹ and Q ¹² is preferably (preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (eg, a benzene ring, a naphthalene ring, etc.), and more preferably. Is an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and more preferably a benzene ring.

The aromatic hetero ring represented by Q ¹¹ and Q ¹² is preferably an aromatic hetero ring containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom. As specific examples of the hetero ring, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole , Thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phena Gin, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, etc. are mentioned. As an aromatic hetero ring, Preferably, they are pyridine, triazine, quinoline.

The aromatic ring represented by Q ¹¹ and Q ¹² is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, still more preferably a substituted or unsubstituted benzene ring.

Q ¹¹ and Q ¹² may further have a substituent, and the substituent T described above is preferable, but the carboxylic acid, sulfonic acid, and quaternary ammonium salt are not contained in the substituent. If possible, substituents may be linked to each other to form a ring structure.

X ¹⁰¹ is NR ²¹⁰ (R ²¹⁰ represents a hydrogen atom or a substituent; substituent can be applied to a substituent group T described stores), represents an oxygen atom or a sulfur atom, preferably an X ¹⁰¹ is NR ²¹⁰ (as R ²¹⁰ Preferably they are an acyl group and a sulfonyl group, These substituents may further substitute), or O, Especially preferably, it is O.

Formula (102) is preferably a compound represented by the following Formula (102a).                     

(Wherein, R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ and R ²¹⁹ each independently represent a hydrogen atom or a substituent.)

R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁷ , R ²¹⁸ and R ²¹⁹ each independently represent a hydrogen atom or a substituent, and the substituent T described above can be applied as a substituent. . In addition, these substituents may be further substituted by other substituents, and the substituents may be condensed to form a ring structure.

R ²¹¹ , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²¹⁸ and R ²¹⁹ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted or unsubstituted amino groups, alkoxy groups, aryloxy groups , A hydroxy group, a halogen atom, more preferably a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, a halogen atom, still more preferably a hydrogen atom, a carbon 1-12 alkyl group, and particularly preferably hydrogen It is an atom and a methyl group, Most preferably, it is a hydrogen atom.

R ²¹² is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, having 1 to 20 carbon atoms. It is an alkyl group, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, a hydroxy group, More preferably, it is a C1-C20 alkoxy group, Especially preferably, it is a C1-C12 It is an alkoxy group.

R ²¹⁷ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, more preferably a hydrogen atom, having 1 to 20 carbon atoms. It is an alkyl group, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxy group, More preferably, it is a hydrogen atom, a C1-C20 alkyl group (preferably C1-C12, More preferably, they are C1-C8, More preferably, they are a methyl group, Especially preferably, they are a methyl group and a hydrogen atom.)

Formula (102) is preferably a compound represented by the following Formula (102b).

(Wherein, R ²²⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group.)

R ²²⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and the substituent T described above can be applied as the substituent.

R ²²⁰ is preferably a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted alkyl group having 5 to 20 carbon atoms, and still more preferably a substituted or unsubstituted alkyl group having 5 to 12 carbon atoms (n-hexyl group, 2). -Ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, benzyl group, etc. are mentioned, Especially preferably, a C6-C12 substituted or unsubstituted alkyl group (2-ethylhexyl group) is mentioned. , n-octyl group, n-decyl group, n-dodecyl group, benzyl group).

The compound represented by General formula (102) can be synthesize | combined by the well-known method of Unexamined-Japanese-Patent No. 11-12219.

Although the specific example of a compound represented by General formula (102) is given to the following, this invention is not limited to the following specific example at all.                     

Moreover, as a compound containing the cyano group which is one of the wavelength dispersion regulators used for this invention, what is represented by General formula (103) is used preferably.

In the formula, Q ²¹ and Q ²² each independently represent an aromatic ring. X ³¹ and X ³² represent a hydrogen atom or a substituent, and at least one represents a cyano group, a carbonyl group, a sulfonyl group, or an aromatic hetero ring. The aromatic ring represented by Q ²¹ and Q ²² may be an aromatic hydrocarbon ring or an aromatic hetero ring. In addition, they may be monocyclic and may further form a condensed ring with another ring.

The aromatic hydrocarbon ring is preferably (preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.), and more preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. Hydrocarbon rings, more preferably aromatic hydrocarbon rings having 6 to 12 carbon atoms), and more preferably benzene rings.

As an aromatic hetero ring, it is preferably an aromatic hetero ring containing a nitrogen atom or a sulfur atom. Specific examples of the hetero ring include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazolin, thiazole, thiadiazole, Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, Benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, etc. are mentioned. As an aromatic hetero ring, Preferably, they are pyridine, triazine, quinoline.

As an aromatic ring represented by Q ²¹ and Q ²² , Preferably it is an aromatic hydrocarbon ring, More preferably, it is a benzene ring.

Q ²¹ and Q ²² may further have a substituent, and the substituent T described above is preferable.

X ³¹ and X ³² represent a hydrogen atom or a substituent, and at least one represents a cyano group, a carbonyl group, a sulfonyl group, or an aromatic hetero ring. The substituent represented by X ³¹ and X ³² may be applied to the above-described substituent T. Further, X ³¹ and X ³² is a substituent represented by may be further substituted by other substituent, X ³¹ and X ³² are each chukhwan may form a ring structure.

X ³¹ and X ³² are preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic hetero ring, and more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic hetero ring. , more preferably a cyano group, a carbonyl group, and particularly preferably a cyano group, an alkoxycarbonyl group ^{(-C (= O) OR 100} (R 100 is: 1 to 20 carbon atoms group, a 6 to 12 carbon atoms, an aryl group and a combination of them One).

As general formula (103), it is preferably a compound represented by the following general formula (103a).                     

^Wherein R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ and R ²³⁰ each independently represent a hydrogen atom or a substituent. X ³¹ and X ³² represent a chemical formula The same meaning as those in 103, and the preferred range is also the same.)

R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ and R ²³⁰ each independently represent a hydrogen atom or a substituent, and as the substituent, the above-mentioned substituent T is applied. can do. In addition, these substituents may be further substituted by other substituents, and the substituents may be condensed to form a ring structure.

R ²²¹ , R ²²² , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁹ and R ²³⁰ are preferably hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted or unsubstituted amino groups, alkoxy groups, It is an aryloxy group, a hydroxyl group, a halogen atom, More preferably, it is a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, a halogen atom, More preferably, it is a hydrogen atom and a C1-C12 alkyl group, Especially Preferably they are a hydrogen atom and a methyl group, Most preferably, they are a hydrogen atom.

R ²²³ and R ²²⁸ are preferably hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, substituted or unsubstituted amino group, alkoxy group, aryloxy group, hydroxy group, halogen atom, more preferably hydrogen atom, carbon number 1 It is an alkyl group of -20, a C0-20 amino group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, and a hydroxyl group, More preferably, it is a hydrogen atom, a C1-C12 alkyl group, and a C1-C12 It is an alkoxy group, Especially preferably, it is a hydrogen atom.

More preferable formula (103) is a compound represented by the following formula (103b).

(Wherein, R ²²³ and R ²²⁸ have the same meaning as those in the formula 103a, and the preferred range is also the same. X ³³ represents a hydrogen atom or a substituent.)

X <^33> represents a hydrogen atom or a substituent, The substituent T mentioned above can be applied as a substituent, and if possible, it may further substitute by another substituent. X ³³ is preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, an aromatic hetero ring, more preferably a cyano group, a carbonyl group, a sulfonyl group, an aromatic hetero ring, and more preferably Is a cyano group and a carbonyl group, and particularly preferably a cyano group and an alkoxycarbonyl group (-C (= O) OR ¹⁰⁰ (R ¹⁰⁰ is: a C1-C20 alkyl group, a C6-C12 aryl group, and a combination thereof) .

More preferably, it is a compound represented by general formula (103c).

(Wherein, R ²²³ and R ²²⁸ have the same meaning as those in the general formula (103-A), and the preferred range is also the same. R ²³¹ represents an alkyl group having 1 to 20 carbon atoms.)

As R ²³¹ , Preferably, when R ²²³ and R ²²⁸ are both hydrogen, it is a C2-C12 alkyl group, More preferably, it is a C4-C12 alkyl group, More preferably, it is a C6-C12 alkyl group, Especially preferably, they are n-octyl group, tert-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, Most preferably, they are 2-ethylhexyl group.

As R ²³¹ , Preferably, when R ²²³ and R ²²⁸ are other than hydrogen, the molecular weight of the compound represented by general formula (103-C) becomes 300 or more, and the C20 or less carbon alkyl group is preferable.

The compound represented by the general formula (103) of the present invention can be synthesized by the method described in Journal of American Chemical Society, Vol. 63, Page 3452 (1941).

Although the specific example of a compound represented by General formula (103) below is given, this invention is not limited to the following specific example at all.

[Matt Particulates]

It is preferable to add microparticles | fine-particles to a cellulose acylate film of this invention as a mat agent. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, calcium silicate hydrate, aluminum silicate, magnesium silicate and calcium phosphate. have. It is preferable that the fine particles contain silicon in terms of low turbidity, and silicon dioxide is particularly preferable. The fine particles of silicon dioxide preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more. It is more preferable that the average particle diameter of primary particles being 5-16 nm can lower the haze of a film. 90-200 g / liter or more is preferable, and, as for apparent specific gravity, 100-200 g / liter or more is more preferable. The larger the apparent specific gravity, the higher the concentration dispersion liquid can be made, and the haze and aggregates are better, which is preferable.

These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 µm, and these fine particles exist as aggregates of primary particles in the film, and form irregularities of 0.1 to 3.0 µm on the film surface. The secondary average particle diameter is preferably 0.2 µm or more and 1.5 µm or less, more preferably 0.4 µm or more and 1.2 µm or less, and most preferably 0.6 µm or more and 1.1 µm or less. The primary and secondary particle diameters were made by observing the particles in the film with a scanning electron microscope to make the diameter of the circle circumscribed to the particles a particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle diameter.

As microparticles | fine-particles of silicon dioxide, a commercial item, such as aerodyl R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nihon Aerodil Co., Ltd. product) can be used, for example. have. The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerodyl R976 and R811 (above Nihon Aerodyl Co., Ltd.), and can be used.

Among them, aerodyl 200V and aerodyl R972V are silicon dioxide fine particles having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and lower the coefficient of friction while keeping the turbidity of the optical film low. It is especially preferable because the effect is large.

In the present invention, in order to obtain a cellulose acylate film having particles having a small secondary average particle diameter, several methods can be considered when preparing a dispersion of fine particles. For example, a method of preparing a fine particle dispersion obtained by stirring and mixing a solvent and fine particles in advance, adding the fine particle dispersion to a small amount of cellulose acylate solution prepared separately, stirring and dissolving it, and then mixing with the main cellulose acylate dope solution have. This method is a preferable preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, a small amount of cellulose ester is added to the solvent, followed by stirring and dissolving. Thereafter, fine particles are added thereto and dispersed in a disperser to form a fine particle addition liquid, and the fine particle addition liquid is sufficiently mixed with the dope liquid in an in-line mixer. Although this invention is not limited to these methods, 5-30 mass% is preferable, as for the density | concentration of silicon dioxide at the time of disperse | distributing a silicon dioxide microparticles | fine-particles in a solvent etc., 10-25 mass% is more preferable, 15-20 mass % Is most preferred. The higher the dispersion concentration, the lower the liquid turbidity relative to the added amount, and the better the haze and aggregates. 0.01-1.0g per 1m <2> is preferable, as for the addition amount of the mat agent in the dope solution of the final cellulose acylate, 0.03-0.3g is more preferable, 0.08-0.16g is the most preferable.

As the lower alcohols, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, etc. are preferably used. Although it does not specifically limit as solvent other than lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

[Plasticizer, deterioration inhibitor, release agent]

In addition to the aforementioned optically anisotropically decomposing compounds and wavelength dispersion regulators, the cellulose acylate film of the present invention includes various additives depending on the use in each preparation step (for example, plasticizers, UV inhibitors, antidegradants, release agents, infrared absorbers, etc.). ) May be added, and they may be solid or may be an oily substance. That is, it is not specifically limited at the melting point or boiling point. For example, it is mixing of the ultraviolet absorbing material of 20 degrees C or less and 20 degrees C or more, similarly mixing of a plasticizer, etc., and are described in Unexamined-Japanese-Patent No. 2001-151901 etc., for example. Moreover, as an infrared absorption dye, it is described in Unexamined-Japanese-Patent No. 2001-194522, for example. In addition, although the addition time may be added at any time in a dope preparation process, you may perform the process of adding and preparing an additive to the last preparation process of a dope preparation process. In addition, the addition amount of each raw material is not specifically limited as long as a function is expressed. Moreover, when a cellulose acylate film is formed in multiple layers, the kind and addition amount of the additive of each layer may differ. For example, although it is described in Unexamined-Japanese-Patent No. 2001-151902 etc., these are the techniques known conventionally. For details, the materials described in detail on pages 16 to 22 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association) are preferably used.

[Ratio of Compound Addition]                     

In the cellulose acylate film of this invention, it is preferable that the total amount of the compound whose molecular weight is 3000 or less is 5 to 45% with respect to the cellulose acylate weight. More preferably, it is 10 to 40%, More preferably, it is 15 to 30%. As these compounds, as mentioned above, the compound which lowers optical anisotropy, a wavelength-dispersion regulator, a ultraviolet inhibitor, a plasticizer, a deterioration inhibitor, a microparticle, a peeling agent, an infrared absorber, etc. are preferable as a molecular weight, 3000 or less are preferable, 2000 or less are more preferable. And 1000 or less are more preferable. If the total amount of these compounds is 5% or less, the properties of the cellulose acylate alone appear easily, for example, there is a problem that the optical performance and physical strength tend to fluctuate with a change in temperature and humidity. In addition, when the total amount of these compounds is 45% or more, problems such as clouding out of the film due to precipitation over the surface of the film exceeding the limit of compound compatibility in the cellulose acylate film are likely to occur.

[Organic Solvents in Cellulose Acylate Solution]

In this invention, it is preferable to manufacture a cellulose acylate film by the solvent cast method, and a film is manufactured using the solution (dope) which melt | dissolved cellulose acylate in the organic solvent. The organic solvent preferably used as the main solvent of the present invention is preferably a solvent selected from esters having 3 to 12 carbon atoms, ketones, ethers and halogenated hydrocarbons having 1 to 7 carbon atoms. Esters, ketones and ethers may have a cyclic structure. Compounds having two or more functional groups of esters, ketones and ethers (ie, -O-, -CO- and -COO-) can also be used as the main solvent, and other functional groups such as, for example, alcoholic hydroxyl groups. May have In the case of the main solvent which has two or more types of functional groups, the carbon atom number should just be in the defined range of the compound which has any one functional group.

As for the cellulose acylate film of the present invention, a chlorinated halogenated hydrocarbon may be used as the main solvent, or a non-chlorine solvent may be used as the main solvent, as described in Korean Patent Publication No. 2001-1745 (pages 12 to 16). It does not specifically limit about the cellulose acylate film of this invention.

In addition, the solvent for the cellulose acylate solution and the film of the present invention is disclosed in the following patents, including the dissolution method thereof, and is a preferred embodiment. These are, for example, Japanese Unexamined Patent Application Publication No. 2000-95876, Japanese Unexamined Patent Publication No. Hei 12-95877, Japanese Unexamined Patent Application Publication No. Hei 10-324774, Japanese Unexamined Patent Application Publication No. Hei 8-152514, 330538, Japanese Patent Laid-Open No. 9-95538, Japanese Patent Laid-Open No. 9-95557, Japanese Patent Laid-Open No. 10-235664, Japanese Patent Laid-Open No. 12-63534, Japanese Patent Laid-Open No. 11- 21379, Japanese Patent Application Laid-Open No. Hei 10-182853, Japanese Patent Application Laid-open No. Hei 10-278056, Japanese Patent Application Laid-open No. Hei 10-279702, Japanese Patent Application Laid-open No. Hei 10-323853, and Japanese Patent Application Laid-Open No. 237186, Unexamined-Japanese-Patent No. 11-60807, Unexamined-Japanese-Patent No. 11-152342, Unexamined-Japanese-Patent No. 11-292988, Unexamined-Japanese-Patent No. 11-60752, etc. are described. According to these patents, not only the preferred solvent for the cellulose acylate of the present invention, but also the physical properties of the solution and coexisting materials to coexist, are also preferred embodiments of the present invention.                     

[Manufacturing process of cellulose acylate film]

[Dissolution Process]

The dissolution method of the cellulose acylate solution (dope) of the present invention is not particularly limited, and may be room temperature, or may be performed by a cooling dissolution method or a high temperature dissolution method, or a combination thereof. For the preparation of the cellulose acylate solution in the present invention, and the solution concentration and filtration according to the dissolution step, the publication of the Invention Association Publication No. 2001-1745, issued March 15, 2001, invented by the Invention Association The manufacturing process described in detail on pages 25 to 25 is preferably used.

(Transparency of dope solution)

It is preferable that the dope transparency of the cellulose acylate solution of this invention is 85% or more. More preferably, it is 88% or more, More preferably, it is 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose acylate dope solution. As a specific method of calculating the dope transparency, the dope solution was injected into a glass cell of 1 cm × 1 cm, and the absorbance at 550 nm was measured with a spectrophotometer (UV-3150, Shimadzu Corporation). Only the solvent was previously measured as a blank, and the transparency of the cellulose acylate solution was calculated from the ratio with the absorbance of the blank.

[Flexible, Drying, Winding Process]

Next, the manufacturing method of the film using the cellulose acylate solution of this invention is described. As a method and apparatus for producing a cellulose acylate film of the present invention, a solution casting film forming method and a solution casting film forming apparatus conventionally provided for producing a cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolver (pot) is once stored in a storage pot, and air bubbles contained in the dope are removed and finally prepared. The dope is sent from the dope outlet to a pressurized die via a pressurized metering gear pump capable of metering fluid with high precision, for example, by rotation speed, and the dope is running endlessly from the slit of the pressurized die. It is made to be uniformly cast on the metal support of the flexible part, so that a less dry dope film (also called a web) is peeled from the metal support at the peeling point at which the metal support is almost round. Both ends of the web to be obtained are clipped and dried in a tenter while maintaining their width, followed by a roll group of a drying apparatus to finish drying, and then wound to a predetermined length with a winder. The combination of the tenter and the drying apparatus of the roll group varies depending on the purpose. In the solution casting film forming method used for the functional protective film which is an optical member for electronic displays, or a silver halide photographic photosensitive material which is the main use of the cellulose acylate film of this invention, a lower coating layer, an antistatic layer, an antihalation layer, The coating device is often added due to the surface treatment of the film such as the protective layer. These are described in detail on pages 25 to 30 of the Publication of the Invention Association (Publication No. 2001-1745, published March 15, 2001, Invention Association), and include flexible (including covalent lead), metal supports, It is classified into drying, peeling, and the like, and can be preferably used in the present invention.

Moreover, 10-120 micrometers is preferable, as for the thickness of a cellulose acylate film, 20-100 micrometers is more preferable, 30-90 micrometers is still more preferable.                     

[Optical Performance Change of Film After High Humidity Treatment]

[Cellulose Acylate Film Property Evaluation]

About the change of the optical performance by the environmental change of the cellulose acylate film of this invention, it is preferable that the amount of changes of Re and Rth of the film which processed at 60 degreeC 90% RH for 240 hours is 15 nm or less. More preferably, it is 12 nm or less, and it is still more preferable that it is 10 nm or less.

[Optical Performance Change of Film After High Temperature Treatment]

Moreover, it is preferable that the amount of changes of Re and Rth of the film processed at 80 degreeC 240 hours is 15 nm or less. More preferably, it is 12 nm or less, and it is still more preferable that it is 10 nm or less.

[Compound Volatilization after Film Heating Treatment]

It is preferable that the compound which reduces Rth and the compound which decreases (DELTA) Rth which can be used suitably for the cellulose acylate film of this invention is 30% or less of the volatilization amount of the compound from the film which processed 80 degreeC 240 hours. More preferably, it is 25% or less, and it is more preferable that it is 20% or less.

In addition, the amount of volatilization from a film starts to melt | dissolve the film and untreated film which were processed at 80 degreeC 240 hours, respectively, in a solvent, detects a compound by liquid high-speed chromatography, and makes the peak area of a compound into the amount of the compound which remained in the film, Calculated by

% Of volatilization = {(amount of residual compounds in untreated)-(amount of remaining compounds in untreated)} / (amount of remaining compounds in untreated) × 100

[Glass Transition Temperature Tg]

The glass transition temperature Tg of the cellulose acylate film of this invention is 80-165 degreeC. It is more preferable that Tg is 100-160 degreeC from a heat resistant viewpoint, and it is especially preferable that it is 110-150 degreeC. The glass transition temperature Tg was measured by calorie measurement using a differential scanning calorimeter (DSC2910, TA instrument) at a temperature of 5 ° C./min at a heating and lowering rate of 5 ° C./minute from the sample of the cellulose acylate film of the present invention at room temperature to 200 ° C. Was calculated.

[Haze of film]

It is preferable that the haze of the cellulose acylate film of this invention is 0.01 to 2.0%. More preferably, it is 0.05 to 1.5%, and it is still more preferable that it is 0.1 to 1.0%. As the optical film, the transparency of the film is important. The haze was measured according to JIS K-6714 with a haze meter (HGM-2DP, Suga Tester) at 25 ° C. and 60% RH of a 40 mm × 80 mm sample of cellulose acylate film of the present invention.

[Humidity dependence of Re, Rth of film]

It is preferable that both the in-plane retardation Re and the retardation Rth of a film thickness direction of the cellulose acylate film of this invention are small in change by humidity. Specifically, the difference between Rth value at 25 ° C 10% RH and Rth value at 25 ° C 80% RH {= (Rth value at 10% RH)-(Rth value at 80% RH)} is 0 to It is preferable that it is 50 nm. More preferably, it is 0-40 nm, More preferably, it is 0-35 nm.                     

[Equilibrium moisture content of film]

The equilibrium moisture content of the cellulose acylate film of the present invention is equal to the equilibrium moisture content at 25 ° C. and 80% RH regardless of the film thickness, so as not to impair the adhesion to water-soluble polymers such as polyvinyl alcohol when used as a protective film of the polarizing plate. It is preferable that it is 0 to 4%. It is more preferable that it is 0.1 to 3.5%, and it is especially preferable that it is 1 to 3%. If the equilibrium moisture content is 4% or more, the dependence of humidity on the retardation when used as a support for the optical compensation film is too large, which is not preferable.

The measurement method of the water content measured 7 mm x 35 mm of the cellulose acylate film samples of this invention by the Karl Fischer method with a moisture meter and a sample drying apparatus (CA-03, VA-05, Mitsubishi Chemical Corporation). The moisture content (g) was calculated by dividing by the sample weight (g).

[Film moisture permeability]

The water vapor transmission rate of the cellulose acylate film used for the optical compensation sheet of the present invention was measured under conditions of a temperature of 60 ° C. and a humidity of 95% RH based on JIS standard JISZ0208, and was converted into a film thickness of 80 μm in terms of 400 to 2000 g / m 2 · 24h. Is preferably. It is more preferable that it is 500-1800 g / m <2> * 24h, and it is especially preferable that it is 600-1600g / m <2> * 24h. When it exceeds 2000 g / m <2> * 24h, the tendency which the absolute value of the humidity dependence of Re value and Rth value of a film exceeds 0.5 nm /% RH becomes strong. Moreover, even when the optically anisotropic layer is laminated | stacked on the cellulose acylate film of this invention and it is set as an optical compensation film, the tendency for the absolute value of humidity dependence of Re value and Rth value to exceed 0.5 nm /% RH becomes unpreferable, and is not preferable. . When this optical compensation sheet or polarizing plate is mounted on a liquid crystal display device, color change and a viewing angle fall are caused. In addition, when the moisture permeability of the cellulose acylate film is less than 400 g / m 2 · 24h, when bonding to both surfaces of the polarizing film to produce a polarizing plate, drying of the adhesive is hindered by the cellulose acylate film, resulting in poor adhesion.

If the film thickness of the cellulose acylate film is thick, the water vapor transmission rate becomes small. If the film thickness is thin, the water vapor transmission rate increases. Therefore, it is necessary to convert the sample of any film thickness into 80 micrometers of reference | standards. The film thickness conversion was calculated | required as (80 micrometers reduced water vapor transmission rate = actual water vapor transmission rate x actual film thickness micrometer / 80 micrometers).

As for the method of measuring the moisture permeability, the method described in pages 285 to 294: Measurement of vapor permeability (mass method, thermometer method, vapor pressure method, and adsorption amount method) of "Physical Properties II" (Polymer Experiment Lecture 4 Gyoritsu Publication) can be applied. , 70mmΦ of the cellulose acylate film sample of the present invention at 25 ° C., 90% RH, 60 ° C., and 95% RH for 24 hours, respectively, to control moisture permeability test apparatus (KK-709007, Toyosei Seiki Co., Ltd.) According to Z-0208, the amount of water per unit area was calculated (g / m 2), and the water vapor permeability = the weight after humidity control and the weight before humidity control.

[Change of Dimension of Film]

The dimensional stability of the cellulose acylate film of the present invention is settled for 24 hours under the condition of dimensional change (high humidity) when left to stand for 24 hours under conditions of 60 ° C and 90% RH (high temperature). It is preferable that all the dimensional change rates of are 0.5% or less. More preferably, it is 0.3% or less, More preferably, it is 0.15% or less.

As a specific measuring method, two 30-mm x 120-mm samples of cellulose acylate film were prepared, and humidity was adjusted at 25 ° C. and 60% RH for 24 hours, and automatic pin gauge (Shinto Science Co., Ltd.) Holes were drilled at intervals of 100 mm to make the original dimension (L0) of the punch interval. After measuring one sample at 60 ° C and 90% RH for 24 hours, measure the punch interval (L1) and measure the other one sample at 90 ° C and 5% RH for 24 hours, and then measure the punch interval (L2). Was measured. In the measurement of all the intervals it was measured to the minimum unit 1 / 1000mm. Dimensional rate of change of 60 ° C at 90% RH (high humidity) = {| L0-L1 | / L0} x 100, Dimensional rate of change of 90 ° C at 5% RH (high temperature) = {| L0-L2 | / L0} × 100 So

The rate of dimensional change was obtained.

[Elastic modulus of film]

(Elastic modulus)

It is preferable that the elasticity modulus of the cellulose acylate film of this invention is 200-500 kgf / Pa, More preferably, it is 240-470 kgf / Pa, More preferably, it is 270-440 kgf / Pa. As a specific measuring method, the elastic modulus was determined by measuring the stress at 0.5% elongation at a tensile rate of 10% / min in a 23 ° C.-70% atmosphere using a universal tensile tester STM T50BP manufactured by Toyoboldwin.

[Photoelastic coefficient of film]

(Photoelastic coefficient)

It is preferable that the photoelastic coefficient of the cellulose acylate film of this invention is 50x10 <^13> cm <2> / dyne or less. It is more preferable that it is 30 * 10 <-1> ^{-cm <} 2> / dyne or less, and it is still more preferable that it is 20 * 10 <^13> -cm <2> / dyne or less. As a specific measuring method, a tensile stress was applied in the major axis direction of the cellulose acylate film sample 12 mm x 120 mm, and the retardation at that time was measured with an ellipsometer (M150, Nihon Bunco Co., Ltd.) The photoelastic coefficient was calculated from the change amount of retardation.

[Evaluation Method of Cellulose Acylate Film of the Present Invention]

When the cellulose acylate film of this invention was evaluated, it measured and performed by the following method.

(In-plane retardation Re, retardation Rth of film thickness direction)

Humidity control of sample 30 mm x 40 mm at 25 degreeC and 60% RH for 2 hours, Re ((lambda)) Was measured by injecting light having a wavelength of λ nm in the direction of the film normal with an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Meter Instruments Co., Ltd.). Rth (λ) Is a film having a retardation value measured by injecting light having a wavelength of λ nm in a direction inclined at + 40 ° with respect to the film normal direction using the Re (λ) and an in-plane slow axis as the inclination axis, and an in-plane slow axis as the inclination axis. Input the average refractive index 1.48 and the film thickness based on the retardation values measured in three directions of the total retardation values measured by incidence of light having a wavelength of λ nm in a direction inclined at -40 ° with respect to the normal direction. Calculated by

(Wavelength dispersion measurement of Re, Rth)

Humidity was adjusted at 25 ° C. and 60% RH for 2 hours at a sample of 30 mm × 40 mm to inject light having a wavelength of 780 nm to 380 nm in an ellipsometer M-150 (manufactured by Nihon Bunco Co., Ltd.) in the film normal direction. Re at wavelength was calculated | required and the wavelength dispersion of Re was measured. In addition, about wavelength dispersion of Rth, the retardation value and surface which measured by injecting the light of wavelength 780-380 nm in the direction inclined +40 degree with respect to the film normal line direction using said Re and the in-plane slow axis as inclination axis | shafts Average refractive index based on the retardation value measured in three directions of the total retardation value measured by injecting light of wavelength 780-380 nm in the direction inclined at -40 degrees with respect to the film normal direction using the slow axis inside as an inclination axis. It was calculated by inputting 1.48 and the film thickness.

Molecular orientation axis

Molecular orientation axis was calculated from the phase difference when the incident angle at vertical incidence was changed by an automatic birefringence meter (KOBRA 21DH, Oji measurement Co., Ltd.) by adjusting the sample 70mm × 100mm at 25 ° C and 65% RH for 2 hours. .

(Axis shift)

Moreover, the axis shift angle was measured with the automatic birefringence meter (KOBRA-21ADH, an oji measuring apparatus Co., Ltd.). 20 points were measured at equal intervals over the entire width in the width direction to obtain an average value of the absolute values. In addition, the range of slow-axis angle (axis shift | offset | difference) measures 20 points at equal intervals over the whole width direction, and takes the difference of the average of four points in the one where the absolute value of axle shift | offset is larger, and the average of four points in the smaller one.

(Transmittance)

The transmittance | permeability of visible light (615 nm) was measured for 20 mm x 70 mm of samples at 25 degreeC and 60% RH with a transparency measuring instrument (AKA phototube colorimeter, KOTAKI Corporation).                     

(Spectral characteristics)

The transmittance | permeability in the wavelength of 300-450 nm was measured with the spectrophotometer (U-3210, Hitachi, Ltd.) at 25 degreeC and 60% RH of sample 13 mm x 40 mm. The inclination width was calculated with a wavelength of 72% and a wavelength of -5%. The marginal wavelength is shown as a (slope width / 2) + 5% wavelength. The absorption edge is represented by a wavelength of 0.4% transmittance. This evaluated the transmittance | permeability of 380 nm and 350 nm.

[Characteristic of Film Surface]

As for the surface of the cellulose acylate film of this invention, it is preferable that the arithmetic mean roughness Ra of the surface asperity of the film | membrane based on JISBO601-1994 is 0.1 micrometer or less, and the maximum height Ry is 0.5 micrometer or less. Preferably, the arithmetic mean roughness Ra is 0.05 µm or less and the maximum height Ry is 0.2 µm or less. The concave and convex shapes of the film surface can be evaluated by atomic force microscope (AFM).

[In-plane Variation of Retardation of Cellulose Acylate Film]

It is preferable that the cellulose acylate film of this invention satisfy | fills following Formula.

| Re (MAX) -Re (MIN) | ≤3 Or | Rth (MAX) -Rth (MIN) | ≤5

[In formula, Re (MAX) and Rth (MAX)-are the maximum retardation values of the film cut out arbitrarily 1m, Re (MIN), Rth (MIN) is the minimum value.]

[Film retention]

In the cellulose acylate film of this invention, the retention property of the various compounds added to the film is calculated | required. Specifically, the mass change of the film when the cellulose acylate film of the present invention is allowed to stand for 48 hours under the condition of 80 ° C / 90% RH is preferably 0 to 5%. More preferably, it is 0 to 3%, More preferably, it is 0 to 2%.

<Evaluation method of retention>

The sample was cut out to a size of 10 cm × 10 cm, and the mass after standing for 24 hours in an atmosphere of 23 ° C. and 55% RH was measured and left for 48 hours under conditions of 80 ± 5 ° C. and 90 ± 10% RH. After the treatment, the surface of the sample was lightly wiped, and the mass after 1 day standing at 23 ° C. and 55% RH was measured, and the retention was calculated by the following method.

Retention (mass%) = {(mass before standing-mass after standing) / mass before standing} × 100

[Film Dynamics]

(curl)

It is preferable that the curl value of the width direction of the cellulose acylate film of this invention is -10 / m-+ 10 / m. Cellulose Acylate Film of the Invention The cellulose acylate film of the present invention is subjected to a rubbing treatment at the time of coating and forming the optically anisotropic layer described later, and to forming or bonding the alignment film and the optically anisotropic layer at a long time. When the cultivation in the width direction of the acylate film is outside the above-mentioned range, the handling of the film may be hindered and the cutting of the film may occur. In addition, since the film is strongly in contact with the conveying roll at the edge or the center of the film, dust is likely to occur, and foreign matter adhesion on the film increases, and the frequency of spot defects and coating streaks of the optical compensation film may exceed the allowable value. . In addition, since curling is within the above-described range, color staining problems that are likely to occur when the optically anisotropic layer is installed can be reduced, and bubbles can be prevented from entering when the polarizing film is attached.

Culches can be measured according to the measurement method specified by the American National Standards Institute (ANSI / ASCPH 1. 29-1985).

(Tear strength)

The tear strength (Elmendorf tear method) based on the tear test method of JISK7128-2: 1998 is 2 g or more in the range whose film thickness of the cellulose acylate film of this invention is 20-80 micrometers. More preferably, it is 5-25 g, Furthermore, it is 6-25 g. Moreover, 8 g or more is preferable in conversion of 60 micrometers, More preferably, it is 8-15 g. Specifically, after adjusting 50 mm x 64 mm of sample pieces for 2 hours and humidity at 25 degreeC and 65% RH conditions, it can measure using a light load tear strength tester.

[Residual Solvent Amount of Film]

It is preferable to dry on the conditions which become the range of 0.01-1.5 mass% of residual solvent amount with respect to the cellulose acylate film of this invention. More preferably, it is 0.01-1.0 mass%. Curling can be suppressed by making the residual solvent amount of the transparent support body used for this invention into 1.5% or less. It is more preferable that it is 1.0% or less. This is considered to be an important effect factor because the free deposition is reduced by reducing the amount of residual solvent during film formation by the solventcasting method described above.

[Hygroscopic Expansion Coefficient of Film]                     

It is preferable that the moisture absorption expansion coefficient of the cellulose acylate film of this invention shall be 30x10 <^-5> /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ^-5 /% RH or less, more preferably 10 × 10 ^-5 /% RH or less. Moreover, although the moisture absorption expansion coefficient is preferable, it is a value normally 1.0x10 <^-5> /% RH or more. The hygroscopic expansion coefficient represents the amount of change in the length of the sample when the relative humidity is changed under a constant temperature. By adjusting the hygroscopic expansion coefficient, when the cellulose acylate film of the present invention is used as the optical compensation film support, it is possible to prevent the light leakage due to the increase in the frame-type transmittance, that is, the deformation, while maintaining the optical compensation function of the optical compensation film. .

[Surface treatment]

The cellulose acylate film can be surface-treated in some cases, and can improve the adhesion of a cellulose acylate film and each functional layer (for example, the undercoat layer and a white layer). For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment herein may be a low temperature plasma generated under a low pressure gas of 10 ^{−3 to 20} Torr, and also preferably a plasma treatment under atmospheric pressure. The plasma excited gas refers to a gas that is plasma excited under the conditions described above, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, freons such as tetrafluoromethane, and mixtures thereof. The details are described in detail in pages 30 to 32 of the Invention Association Publication (Publication No. 2001-1745, published March 15, 2001, Invention Association), and can be preferably used in the present invention. have.

Alkali saponification treatment is mentioned as one of the effective means of surface treatment at the time of using the cellulose acylate film of this invention as a transparent protective film of a polarizing plate. In this case, it is preferable that the contact angle of the film surface after alkali saponification process is 55 degrees or less. More preferably, it is 50 degrees or less, and it is still more preferable that it is 45 degrees or less. The evaluation method of a contact angle can be used as evaluation of hydrophilicity by the conventional method which drops the water droplet of diameter 3mm on the film surface after alkali saponification process, and calculates the angle which a film surface and water droplet make | form.

(Light resistance)

As an index of the light durability of the cellulose acylate of the present invention, the color difference ΔE * ab of the film irradiated with super xenon light for 240 hours is preferably 20 or less. More preferably, it is 18 or less, and it is still more preferable that it is 15 or less. The measurement of the color difference used UV3100 (made by Shimadzu Corporation). In the measuring method, after adjusting a film to 25 degreeC 60% RH for 2 hours or more, the color before xenon irradiation was color-measured and the initial value (L0 ^* , a0 ^* , b0 ^* ) was calculated | required. Then, xenon light was irradiated for 240 hours by 150 x / m <2> and 60 degreeC 50% RH conditions by the super Xenon weather meter SX-75 (made by Suga Test Machine Co., Ltd.) by the film single member. After the lapse of the predetermined time, the film was taken out of the thermostat, the humidity was adjusted to 25 ° C. 60% RH for 2 hours, and color measurement was performed again to obtain values (L1 ^* , a1 ^* , b1 ^* ) after irradiation. From these, color difference (DELTA) E ^* ab = ((L0 ^* -L1 ^* ) ^ 2+ (a0 ^* -a1 ^* ) ^ 2+ (b0 ^* -b1 ^* ) ^ 2) ^ 0.5 was calculated | required.

[Functional layer]

The cellulose acylate film of this invention is applied to optical uses and a photosensitive material as the use. It is particularly preferable that the optical use is a liquid crystal display device, the liquid crystal cell comprising a liquid crystal display device holding two liquid crystals between two electrode substrates, at least two polarizing elements arranged on both sides thereof, and at least between the liquid crystal cell and the polarizing element. It is more preferable that it is the structure which arrange | positioned one sheet of optical compensation sheet. As these liquid crystal display devices, TN, IPS, FLC, AFLC, OCB, STN, ECB, VA, and HAN are preferable.

In that case, when using the cellulose acylate film of this invention for the optical uses mentioned above, various functional layers will be provided. These are, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal layer, and the like. These functional layers and materials thereof that can use the cellulose acylate film of the present invention include surfactants, lubricants, matting agents, antistatic layers, hard coat layers, and the like. , Issued on March 15, 2001, on pages 32 to 45 of the Invention Association), and can be preferably used in the present invention.

[Application (Polarizing Plate)]

The use of the cellulose acylate film of this invention is demonstrated.

The optical film of the present invention is particularly useful for polarizing plate protective films. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained cellulose acylate film is alkali treated and the polyvinyl alcohol film is immersed and stretched in an iodine solution to be bonded to both surfaces of a polarizer produced using a fully saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.

As an adhesive agent used for bonding a protective film process surface and a polarizer, polyvinyl alcohol adhesives, such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes, such as butyl acrylate, etc. are mentioned, for example.

The polarizing plate is composed of a polarizer and a protective film for protecting both surfaces thereof, and is further formed by bonding a protective film on one side of the polarizing plate and a separate film on the opposite side. The protective film and the separation film are used for the purpose of protecting the polarizing plate at the time of shipment of the polarizing plate and at the time of product inspection. In this case, a protective film is bonded in order to protect the surface of a polarizing plate, and is used for the opposite surface side of the surface which bonds a polarizing plate to a liquid crystal plate. Moreover, a separation film is used for the purpose of covering the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.

In a liquid crystal display device, although the board | substrate containing a liquid crystal is normally arrange | positioned between two polarizing plates, the outstanding display property is acquired even if it arrange | positions in what site the polarizing plate protective film which applied the optical film of this invention. In particular, since a transparent hard coat layer, an antiglare layer, an antireflection layer, etc. are formed in the polarizing plate protective film of the display side outermost surface of a liquid crystal display device, it is especially preferable to use this polarizing plate protective film in this part.

[Applications (Optical Compensation Film)]

The cellulose acylate film of the present invention can be used for various purposes, and it is particularly effective when used as an optical compensation film of a liquid crystal display device. In addition, an optical compensation film generally refers to an optical material used in a liquid crystal display device to compensate for a phase difference, and has the same meaning as a retardation plate, an optical compensation sheet, and the like. The optical compensation film is birefringent and is used for the purpose of removing coloration of the display screen of the liquid crystal display device or improving viewing angle characteristics. The cellulose acylate film of the present invention has a low optical anisotropy with Re and Rth of 0 ≤ Re ≤ 10 nm and | Rth | ≤ 25 nm, and | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤ 10 and | Rth ₍₄₀₀₎ Since the wavelength dispersion is small at -Rth ₍₇₀₀₎ | ≤ 35, unnecessary anisotropy is not generated, and when the optical anisotropic layer having birefringence is used together, only the optical performance of the optical anisotropic layer can be expressed.

Therefore, when using the cellulose acylate film of this invention as an optical compensation film of a liquid crystal display device, it is preferable that Re and Rth of the optically anisotropic layer used together are Re = 0-200nm and | Rth | = 0-400nm, If it is this range, any optically anisotropic layer may be sufficient. The optical performance and driving method of the liquid crystal cell of the liquid crystal display device in which the cellulose acylate film of the present invention is used are not limited, and any optically anisotropic layer required as the optical compensation film can be used in combination. As an optically anisotropic layer used together, you may form with the composition containing a liquid crystalline compound, and you may form with the polymer film which has birefringence.

As said liquid crystalline compound, a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound is preferable.

(Discotic liquid crystalline compound)

Examples of discotic liquid crystalline compounds that can be used in the present invention include various documents (C. Destrade et al., Mol. Crysr, Liq. Cryst., Vol. 71, page 111 (1981); Summary, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994)).

In the optically anisotropic layer, the discotic liquid crystalline molecules are preferably fixed in an aligned state, and most preferably fixed by a polymerization reaction. Polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284. In order to fix a discotic liquid crystalline molecule by superposition | polymerization, it is necessary to couple a polymeric group as a substituent to the disk-shaped core of a discotic liquid crystalline molecule. However, if the polymerizable group is directly linked to the disk-shaped core, it becomes difficult to maintain the alignment state in the polymerization reaction. Thus, a linking group is introduced between the discotic core and the polymerizable group. Discotic liquid crystalline molecules having a polymerizable group are disclosed in Japanese Patent Laid-Open No. 2001-4387.

(Bar type liquid crystalline compound)

In the present invention, examples of rod-like liquid crystalline compounds that can be used include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, and cyanophenylcyclohexane. And cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitriles. Not only the low molecular liquid crystalline compounds mentioned above but a high molecular liquid crystalline compound can also be used.

In the optically anisotropic layer, the rod-like liquid crystalline molecules are preferably fixed in an alignment state, and most preferably fixed by a polymerization reaction. Examples of the polymerizable rod-like liquid crystalline compound which can be used in the present invention include Makromol. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Patent 4683327, U.5622648, U.5770107, International Patent (WO) 95/22586, U.95 / 24455, 97/00600, 98/23580, 98/52905, JP-A-272551, 6-16616, 7-110469, 11-80081 and The compound described in Unexamined-Japanese-Patent No. 2001-328973 etc. is contained.

(Optically anisotropic layer made of a polymer film)

As described above, the optically anisotropic layer may be formed of a polymer film. The polymer film is formed of a polymer capable of expressing optical anisotropy. Examples of such polymers include polyolefins (e.g. polyethylene, polypropylene, norbornene-based polymers), polycarbonates, polyallylates, polysulfones, polyvinyl alcohols, polymethacrylic acid esters, polyacrylic acid esters and cellulose esters (e.g. Cellulose triacetate, cellulose diacetate). Moreover, you may use the copolymer or polymer mixture of these polymers.

It is preferable to obtain the optical anisotropy of a polymer film by extending | stretching. It is preferable that extending | stretching is uniaxial stretching or biaxial stretching. Specifically, longitudinal uniaxial stretching using the circumferential speed difference of two or more rolls, or tenter stretching in which both sides of the polymer film are held and stretched in the width direction, and biaxial stretching in combination thereof are preferable. Moreover, the optical property of the 2 or more sheets whole film may satisfy | fill the above conditions using 2 or more sheets of polymer films. It is preferable to manufacture a polymer film by the solvent cast method in order to reduce the birefringence nonuniformity. It is preferable that it is 20-500 micrometers, and, as for the thickness of a polymer film, it is most preferable that it is 40-100 micrometers.

As the polymer film forming the optically anisotropic layer, at least one polymer material selected from the group consisting of polyamide, polyimide, polyester, polyether ketone, polyamideimide polyesterimide and polyaryl ether ketone is used. And the method of apply | coating the solution which melt | dissolved this in the solvent to a base material, drying a solvent, and forming into a film can also be used preferably. At this time, the method of extending | stretching the said polymer film and a base material, and expressing optical anisotropy and using as an optically anisotropic layer can also be used preferably, The cellulose acylate film of this invention can be used suitably as said base material. Moreover, it is also preferable to produce the said polymer film on another base material, to peel a polymer film from a base material, and to bond with the cellulose acylate film of this invention, and to use it as an optically anisotropic layer. In this method, the thickness of the polymer film can be made thin, preferably 50 µm or less, more preferably 1-20 µm.

(Composition of General Liquid Crystal Display Device)

When using a cellulose acylate film as an optical compensation film, you may arrange | position the slow axis of the optical compensation film which consists of a transmission axis of a polarizing element and a cellulose acylate film at any angle. The liquid crystal display device has a configuration in which a liquid crystal cell formed by supporting liquid crystal between two electrode substrates, two polarizing elements arranged on both sides thereof, and at least one optical compensation film disposed between the liquid crystal cell and the polarizing element. have.

The liquid crystal layer of the liquid crystal cell is usually formed by sealing a liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive material. In the liquid crystal cell, a gas barrier layer, a hard coat layer or an undercoat layer (undercoat layer) (used for bonding the transparent electrode layer) may be further formed. These layers are usually formed on a substrate. The substrate of the liquid crystal cell generally has a thickness of 50 µm to 2 mm.

(Types of liquid crystal display device)

The cellulose acylate film of this invention can be used for the liquid crystal cell of various display modes. Twisted Nematic (TN), In-plane Switching (IPS), Ferroelectric Liquid Crystal (FLC), Anti-ferroelectric Liquid Crystal (AFLC), Optimal Compensatory Bend (OCB), Super Twisted Nematic (STN), Vertically Aligned (VA), Various display modes have been proposed, such as Electrically Controlled Birefringence (ECB) and Hybrid Aligned Nematic (HAN). Moreover, the display mode which orientation-divided the said display mode is also proposed. The cellulose acylate film of this invention is effective also in the liquid crystal display device of any display mode. It is also effective in any type of transmissive, reflective or transflective liquid crystal display device.

(TN type liquid crystal display device)

You may use the cellulose acylate film of this invention as a support body of the optical compensation sheet of a TN type liquid crystal display device which has a liquid crystal cell of TN mode. The liquid crystal cell of the TN mode and the TN type liquid crystal display are well known from the past. As for the optical compensation sheet used in the TN type liquid crystal display device, Japanese Patent Laid-Open No. Hei 3-9325, Japanese Patent Laid-Open No. Hei 6-148429, Japanese Patent Laid-Open No. Hei 8-50206, and Japanese Patent Laid-Open No. 9 Each publication of -26572 is described. Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 and Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068).

(STN type liquid crystal display device)

You may use the cellulose acylate film of this invention as a support body of the optical compensation sheet of STN type liquid crystal display device which has a liquid crystal cell of STN mode. Generally, in the STN type liquid crystal display, the bar liquid crystal molecules in the liquid crystal cell are twisted in the range of 90 to 360 degrees, and the product of the refractive index anisotropy (Δn) and the cell gap (d) of the bar liquid crystal molecules is 300 It is in the range of ˜1500 nm. The optical compensation sheet used for STN type liquid crystal display device is described in Unexamined-Japanese-Patent No. 2000-105316.                     

(VA type liquid crystal display device)

The cellulose acylate film of this invention is used especially advantageously as a support body of the optical compensation sheet of VA type liquid crystal display device which has a liquid crystal cell of VA mode. It is preferable to set Re-retardation value of the optical compensation sheet used for VA type liquid crystal display device to 0-150 nm, and to set Rth retardation value to 70-400 nm. The Re retardation value is more preferably 20 to 70 nm. When using two optically anisotropic polymer films for VA type liquid crystal display devices, it is preferable that the Rth retardation value of a film is 70-250 nm. When using one optically anisotropic polymer film for VA type liquid crystal display devices, it is preferable that the Rth retardation value of a film is 150-400 nm. The VA type liquid crystal display device may be, for example, an orientation-divided method described in JP-A-10-123576.

(IPS type liquid crystal display device and ECB type liquid crystal display device)

The cellulose acylate film of the present invention is particularly advantageously used as a support for an optical compensation sheet of an IPS type liquid crystal display device and an ECB type liquid crystal display device having a liquid crystal cell in IPS mode and ECB mode, or as a protective film for a polarizing plate. In these modes, the liquid crystal material is oriented substantially in parallel when displaying black, and the liquid crystal molecules are aligned in parallel with the substrate surface in a state where no voltage is applied and displayed in black. In these embodiments, the polarizing plate using the cellulose acylate film of the present invention contributes to improvement of color, enlarged viewing angle, and improvement of contrast. In this aspect, it is preferable to use at least one polarizing plate using the cellulose acylate film of this invention for the protective film (cell side protective film) arrange | positioned between a liquid crystal cell and a polarizing plate among the protective films of the said polarizing plate above and below a liquid crystal cell. More preferably, it is preferable to arrange | position an optically anisotropic layer between the protective film of a polarizing plate, and a liquid crystal cell, and to set the retardation value of the arranged optically anisotropic layer to 2 times or less of the value of (DELTA) n * d of a liquid crystal layer.

(OCB type liquid crystal display device and HAN type liquid crystal display device)

The cellulose acylate film of the present invention is advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having a liquid crystal cell of OCB mode or an HAN type liquid crystal display device having a liquid crystal cell of HAN mode. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of the retardation is minimized does not exist in the plane of the optical compensation sheet nor in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also determined by the optical properties of the optically anisotropic layer, the optical properties of the support, and the arrangement of the optically anisotropic layer and the support. The optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device is described in Unexamined-Japanese-Patent No. 9-197397. See also, Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)

The cellulose acylate film of the present invention is advantageously used as an optical compensation sheet of a reflective liquid crystal display device of TN type, STN type, HAN type, and GH (Guest-Host) type. These display modes are well known from the past. Regarding the TN type reflective liquid crystal display device, there is a description in Japanese Patent Laid-Open Nos. 10-123478, WO9848320, and Japanese Patent No. 3024277. An optical compensation sheet for use in a reflective liquid crystal display device is described in WO00-65384.

(Other liquid crystal display device)

The cellulose acylate film of this invention is advantageously used also as a support body of the optical compensation sheet of an ASM type liquid crystal display device which has a liquid crystal cell of ASM (Axially Symmetric Aligned Microcell) mode. The liquid crystal cell of ASM mode has the characteristic that the thickness of a cell is hold | maintained by the resin spacer which can be adjusted. Other properties are the same as those of the liquid crystal cell of the TN mode. The liquid crystal cell of the ASM mode and the ASM type liquid crystal display are described in Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).

(Hard Coat Film, Anti-glare Film, Anti-reflection Film)

The cellulose acylate film of the present invention can further preferably be applied to a hard coat film, an antiglare film, and an antireflection film. One or both of a heart coat layer, an antiglare layer, and an antireflection layer may be provided on one or both surfaces of the cellulose acylate film of the present invention for the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, and EL. have. Preferred embodiments as such anti-glare films and anti-reflective films are described in detail on pages 54 to 57 of the Invention Association Publication (Publication No. 2001-1745, issued March 15, 2001, Invention Association), and the present invention. Cellulose acylate film can be preferably used.                     

(Photo film support)

Moreover, in the case of the cellulose acylate film of this invention, it can apply also as a support body of a silver halide photographic photosensitive material, and can apply the various material, prescription, and processing method which are described in the patent. About these techniques, the description about color negative is described in detail in Unexamined-Japanese-Patent No. 2000-105445, The cellulose acylate film of this invention is used preferably. Moreover, application of the color inversion silver halide photographic photosensitive material as a support is also preferable, and various materials, prescriptions, and treatment methods described in JP-A-11-282119 can be applied.

Transparent board

In the case of the cellulose acylate film of the present invention, since the optical anisotropy is close to zero and has transparency, the cellulose acylate film can be used as a substitute for the liquid crystal cell glass substrate of the liquid crystal display device, that is, as a transparent substrate for encapsulating the driving liquid crystal.

Since the transparent substrate encapsulating the liquid crystal should have excellent gas barrier properties, a gas barrier layer may be formed on the surface of the cellulose acylate film of the present invention as necessary. The form and material of the gas barrier layer is not particularly limited, on at least one surface of the cellulose acylate film of the present invention deposit a SiO _2, etc., or vinylidene polymer or a vinyl alcohol-based polymer, such as relatively high gas barrier property chloride The method of forming the coat layer of a polymer can be considered, These can be used suitably.

Moreover, in order to use as a transparent substrate which encloses a liquid crystal, the transparent electrode for driving a liquid crystal can also be formed by voltage application. Although it does not specifically limit as a transparent electrode, A transparent electrode can be formed by laminating | stacking a metal film, a metal oxide film, etc. on at least one surface of the cellulose acylate film of this invention. Especially, a metal oxide film is preferable from a viewpoint of transparency, electroconductivity, and a mechanical characteristic, and the thin film of indium oxide containing 2-15% of zinc oxide mainly using tin oxide can be used preferably. Details of these techniques are disclosed in, for example, Japanese Patent Laid-Open No. 2001-125079, Japanese Patent Laid-Open No. 2000-227603, and the like.

Example

Although the Example of this invention is given to the following, it is not limited to these.

Example 1

(Production of cellulose acylate film)

The following composition was thrown into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acylate solution A was prepared.

<Cellulose Acylate Solution A Composition>

100 parts by mass of cellulose acetate having a degree of substitution of 2.86

Triphenyl phosphate (plasticizer) 7.8 parts by mass

3.9 parts by mass of biphenyldiphenyl phosphate (plasticizer)

300 parts by mass of methylene chloride (first solvent)

54 parts by mass of methanol (second solvent)                     

11 parts by mass of 1-butanol

The following composition was thrown into another mixing tank, it stirred while heating, each component was melt | dissolved, and the additive solution B-1-B-6 were prepared.

<Production of Cellulose Acetate Film Sample 001>

40 mass parts of additive solution B-1 was added to 477 mass parts of cellulose acylate solution A, and it fully stirred, and dope was prepared. The dope was cast on a drum cooled to 0 ° C. from oil studies. Peel off at the outside of 70 mass% of solvent content and fix both ends of the film width direction with a pin tenter (the pin tenter as described in FIG. 3 of Unexamined-Japanese-Patent No. 4-1009), and the solvent content is 3-5 mass%. It dried while maintaining the space | interval which the elongation of a horizontal direction (direction perpendicular | vertical to a machine direction) becomes 3%. Then, it conveyed between the rolls of the heat processing apparatus, and dried again, and produced the cellulose acetate film sample 001 of thickness 80micrometer.

<Production of Cellulose Acetate Film Samples 002 to 003, 101 to 105>

Cellulose acetate film samples 002 to 003 and 101 to 105 were produced in the same manner as for cellulose acetate film sample 001 except that the additive solution and thickness were changed as shown in Table 2 in the production of cellulose acetate film 001. The spectral transmittances at wavelengths of 380 nm and 350 nm of these samples were measured. As a result, the transmittance at wavelength 380 nm was 45% or more and 95% or less. It turned out that this is 10% or less.

[Example 2]

(Production of cellulose acylate film)

The following composition was thrown into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acylate solution C was prepared.

<Cellulose Acylate Solution C Composition>

100 parts by mass of cellulose acetate having a degree of substitution of 2.86

300 parts by mass of methylene chloride (first solvent)                     

54 parts by mass of methanol (second solvent)

11 parts by mass of 1-butanol

The composition of Table 3 was added to another mixing tank, stirred while heating, and each component was dissolved to prepare additive solutions B-7 to B-19. 40 mass parts of additive solutions B-7-19 were added to 465 mass parts of cellulose acylate solution C, and the samples 004-007 and 106-114 of the cellulose acetate film of thickness 80micrometer were produced. The transparency of the dope solutions of these samples was all 85% or more, and it confirmed that the compound and wavelength dispersion regulator which reduce optical anisotropy are fully compatible with the dope solution of a cellulose acylate. Moreover, the haze of these samples confirmed that transparency was sufficient also when it made into a film in 0.01 to 2% of range. Moreover, when the glass transition temperature Tg of these samples was measured, it confirmed that it was 80-165 degreeC except for the comparative sample 004 which did not add the optical anisotropy reducing agent and wavelength dispersion regulator of this invention.                     

[Example 3]

(Preparation of cellulose acetate solution)

The following composition was thrown into the mixing tank, it stirred, each component was melt | dissolved, and the cellulose acetate solution D was prepared.

(Cellulose acetate solution D composition)

100.0 parts by mass of cellulose acetate having an acetylation degree of 2.86

Methylene chloride (first solvent) 402.0 parts by mass

60.0 parts by mass of methanol (second solvent)

(Preparation of Matte Solution)

20 mass parts and 80 mass parts of methanol were stirred for 30 minutes, and it mixed as the silica particle dispersion liquid with the silica particle (AEROSIL R972, Nippon Aerosil Co., Ltd. make) of average particle diameter 16nm well for 30 minutes. This dispersion was added to the disperser together with the following composition, stirred for 30 minutes or more, and each component was dissolved to prepare a mat solution.

(Mat agent solution composition)

10.0 parts by mass of silica particle dispersion having an average particle diameter of 16 nm

Methylene chloride (first solvent) 76.3 parts by mass

3.4 parts by mass of methanol (second solvent)

Cellulose acetate solution D 10.3 parts by mass

(Preparation of additive solution)

The following composition was put into a mixing tank, stirred while heating, and each component was dissolved to prepare a cellulose acetate solution. About the compound and wavelength dispersion regulator which reduce optical anisotropy, what was shown in following Table 4 was used.

(Composition of additive solution)

49.3 parts by mass of compound which lowers optical anisotropy

7.6 parts by mass of wavelength dispersion regulator

Methylene chloride (first solvent) 58.4 parts by mass

8.7 parts by mass of methanol (second solvent)

Cellulose acetate solution D 12.8 parts by mass

(Production of Cellulose Acetate Film Sample 115)

94.6 parts by mass of the cellulose acetate solution D, 1.3 parts by mass of the mat agent solution, and 4.1 parts by mass of the additive solution were respectively filtered and mixed, and the mixture was cast using a band softener. In the above composition, the mass ratios of the compound which lowered the optical anisotropy and the wavelength dispersion regulator to the cellulose acetate were 12% and 1.8%, respectively. The cellulose acetate film was manufactured by peeling a film from a band with 30% of the residual solvent volume, and drying at 140 degreeC for 40 minutes. The amount of residual solvent of the completed cellulose acetate film was 0.2%, and the film thickness was 40 micrometers.

(Production of Cellulose Acetate Film Samples 008 to 011 and 116 to 128)

Cellulose acylate film samples 008-011 and 116-128 were produced similarly except having changed the kind and quantity of the compound and wavelength dispersion regulator which reduce the optical anisotropy in an additive solution to the content of Table 4. Table 4 also lists the solution composition of Sample 115 preparation. Difference of retardation in the film thickness direction at 10% relative humidity and 80% relative humidity of these samples ΔRth (= Rth 10% RH (Rth value at 10% RH)-Rth 80% RH (Rth at 80% RH) Value)) was measured, and ΔRth was 30 in Comparative Samples 008, 009 without adding the optically anisotropic reducing agent of the present invention, and Comparative Samples 010 and 011 in which the plasticizer biphenyldiphenylphosphate (BDP) was added instead of the optically anisotropic reducing agent. It did not become below nm, and the humidity anisotropy of optical anisotropy was large. On the other hand, in samples 115-128 containing the optically anisotropic reducing agent of this invention, it was confirmed that humidity dependence is falling in (DELTA) Rth in the range of 0-30 nm. Moreover, when the equilibrium moisture content of these samples was measured at 80 degreeC of 25 degreeC, it was 4% or less except for the comparative sample 008, and the cellulose acylate film is hydrophobized by addition of the optically anisotropic lowering agent or wavelength dispersion regulator of this invention. I could confirm that. In addition, the moisture permeability (in terms of 80 µm) at 60 ° C., 95% RH, and 24 hr of these samples was measured. Compared with the above, it was confirmed that all of the samples 115 to 128 to which the optically anisotropic lowering agent and the wavelength dispersion adjusting agent of the present invention were added had improved moisture permeability. In addition, in all samples except Comparative Sample 011, there was no clouding of the film, so that a sufficiently transparent film could be prepared. In this case, the film became cloudy and the compound precipitated (leaked), which could not be evaluated as a cellulose acylate film having transparency.                     

Moreover, in the samples 126 and 127, the mass change when it was left to stand on 80 degreeC and 90% RH for 48 hours was measured, and the sample 126 was -0.12% and the sample 127 was -0.02%. As a wavelength dispersion regulator, the sample 127 which used the benzotriazole type compound UV-21, UV-22, and UV-23 but does not contain UV-23 (molecular weight 315.5) whose molecular weight is 320 or less is more advantageous than the sample 126 from the standstill viewpoint. I could confirm it.                     

Example 4                     

(Production of cellulose acylate film)

The following composition was thrown into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acylate solution E was prepared. At this time, three cellulose acylates having substitution degrees of 2.49, 2.86, and 2.92 were used (Table 5).

<Cellulose Acylate Solution E Composition>

100 parts by mass of cellulose acetate

300 parts by mass of methylene chloride (first solvent)

54 parts by mass of methanol (second solvent)

11 parts by mass of 1-butanol

The composition of Table 5 was added to another mixing tank, stirred while heating, and each component was dissolved to prepare additive solutions B-20 to B-25. 40 mass parts of additive solutions B-20-25 were added to 465 mass parts of cellulose acylate solution E, and the cellulose acetate film samples 129-132 of thickness 40micrometer, and the comparative samples 012-013 were produced. Similarly to Example 3, the difference between the retardation in the film thickness direction at the relative humidity of 10% and the relative humidity of 80% for these samples was ΔRth (= Rth 10% RH-Rth 80% RH) at 25 ° C and 80% RH. Equilibrium moisture content, 60 ℃ 95% RH, moisture permeability of 24hr (equivalent to 80㎛), 80 ℃ 90% RH, mass change after 48 hours, 60 ℃ 95% RH, dimensional change and elastic modulus after 24 hours was measured, the present invention It was confirmed that all of the samples 129 to 132 using a cellulose acylate film having a total substitution degree of 2.92 and containing an optically anisotropic lowering agent and a wavelength dispersion regulator were all better than the comparative sample 012 having a substitution degree of 2.49.

[Example 5]

(Production of cellulose acylate film)

The following composition was put into the mixing tank, it stirred while heating, each component was dissolved, and the cellulose acylate solution F was prepared. At this time, two types of cellulose acylate films of total substitution degree 2.85 (acetyl substitution degree 2.06 + propynyl substitution degree 0.79) and total substitution degree 2.70 (acetyl substitution degree 1.93 + propynyl substitution degree 0.77) were used.

<Cellulose Acylate Solution F Composition>

100 parts by mass of cellulose acylate

300 parts by mass of methylene chloride (first solvent)

54 parts by mass of methanol (second solvent)

11 parts by mass of 1-butanol

The composition shown in Table 6 below was added to another mixing tank, stirred while heating, and each component was dissolved to prepare additive solutions B-26 to B-31. 40 mass parts of additive solutions B-26-B-31 were added to 465 mass parts of cellulose acylate solution F, and 133-139 of cellulose acylate film samples of thickness 40micrometer were produced. In these samples, the retardation difference ΔRth (= Rth 10% RH-Rth 80% RH) at 25% and 80% RH in the same manner as in Example 3 in the film thickness direction at 10% relative humidity and 80% relative humidity. Equilibrium moisture content and moisture permeability (in terms of 80 μm) of 60 ° C., 95% RH and 24 hr were measured, and an optical anisotropy lowering agent, wavelength dispersion, It was confirmed that all of the samples 133 to 139 containing the adjusting agent were better than the comparative samples 008 to 010 of Example 3.                     

[Example 6]                     

(Production of cellulose acylate film)

Except for using the cellulose acylate of acetyl substitution degree 2.92 and using the composition of Table 7 below, samples 140 to 145 having a thickness of 80 or 40 µm were prepared in the same manner as in Example 3 (Table 7).

[Example 7]

(Production of cellulose acylate film)

A cellulose acetate film sample having a thickness of 80 or 40 µm in the same manner as in Example 3 except for using the cellulose acylate having a total substitution degree of 2.70 (acetyl substitution degree 1.0 + butyryl substitution degree 1.7) and the composition of Table 8 below. 146-150 was produced (Table 8).                     

The evaluation results of the optical characteristics of the cellulose acylate film samples 101 to 150 and comparative samples 001 to 011 of the present invention obtained in Examples 1 to 7 are shown in Tables 9 to 12. Samples 101 to 150 using compounds which lower the optical anisotropy of the present invention are comparative samples 001 to 006, 008 to 009 which do not use these compounds, and general plasticizers, and biphenyl-diphenyl phosphate having a LogP of 7.3, which is unexpected in the present invention ( Compared with Comparative Samples 007 and 010 using BDP), both Re ₍₆₃₀₎ and Rth ₍₆₃₀₎ exhibited sufficient degradation, and are almost optically isotropic. In addition, in the sample using the compound for adjusting the wavelength dispersion of the present invention, all of the samples with respect to the comparative sample were sufficiently reduced in the amount of Re ₍₄₀₀₎ -Rth ₍₇₀₀₎ |, | Rth ₍₄₀₀₎ -Re ₍₇₀₀₎ | Visible wavelength dispersion is approaching zero.

[Example 8]                     

(Production of polarizing plate)

The cellulose acetate film sample 101 of the present invention obtained in Example 1 was immersed in a 1.5 N sodium hydroxide aqueous solution at 55 ° C. for 2 minutes. It was washed in a water bath at room temperature and neutralized at 30 DEG C with 0.1 sulfuric acid. Again, it wash | cleaned in the water washing bath of room temperature, and dried again by the warm air of 100 degreeC. In this way, the surface of the cellulose acylate film was saponified.

Subsequently, a rolled polyvinyl alcohol film having a thickness of 80 µm was continuously stretched and dried five times in an aqueous solution of iodine to obtain a polarizing film. Polyvinyl alcohol (PVA-117H manufactured by Kuraray) prepared two alkaline cellulose acylate film samples 101 treated with 3% aqueous solution as an adhesive and bonded with a polarizing film interposed therebetween, thereby protecting both sides with a cellulose acylate film 101. Obtained polarizing plate. At this time, it bonded together so that the slow axis of the cellulose acylate film sample 101 of both sides may become parallel to the transmission axis of a polarizing film. Similarly, the polarizing plate was produced also about the samples 102-150 of Examples 1-7 of this invention, and the comparative sample 004 of Example 2. The cellulose acylate film samples 101 to 150 and the comparative sample 004 of the present invention all had sufficient bonding properties with the stretched polyvinyl alcohol and had excellent polarizing plate workability. This polarizing plate is referred to below as polarizing plates 101 to 150 and polarizing plate 004.

(Comparative Example)

In Example 8, instead of performing protection of a polarizing film with two cellulose acylate films of this invention, a polarizing plate was produced by the same operation using two commercially available polycarbonate films "Panlite C1400" (made by the day jinagasei) It was. However, since the adhesiveness with extending | stretching polyvinyl alcohol is inadequate, a polycarbonate film cannot function as a protective film of a polarizing film, and there existed a problem in aptitude for processing a polarizing plate.

(Comparative Example)

In Example 8, instead of performing protection of a polarizing film with two sheets of the cellulose acylate film of this invention, the polarizing plate was produced by the same operation using two sheets of 80-micrometer-thick aton films (made by JSR). However, since the adhesiveness with extending | stretching polyvinyl alcohol was inadequate, an aton film could not function as a protective film of a polarizing film, and there existed a problem in aptitude for processing a polarizing plate.

(Polarizing plate durability)

The polarization degree after leaving the polarizing plate using the cellulose acylate film samples 101-150 and comparative sample 004 of this invention produced in Example 8 for 500 hours on 60 degreeC 95% RH conditions was evaluated, and the samples 101-150 were used. The polarizing properties of the polarizing plate were all excellent with respect to the polarizing plate using the comparative sample 004, and the polarizing plate processing of the cellulose acylate film was performed by the addition of a compound or a wavelength dispersion adjusting agent (all of the comparative samples 004 were added) which lower the optical anisotropy of the present invention. It was confirmed that the durability at the time was improved.

Example 9 (Evaluation of mounting on IPS type liquid crystal display device)

Using the cellulose acylate film obtained in Examples 1 to 7 and the polarizing plate obtained in Example 8, the mounting on the liquid crystal display device was evaluated to confirm whether the optical performance was sufficient. In this embodiment, an IPS type liquid crystal cell and a VA type and an OCB type liquid crystal cell are used in the following examples, but the use of a polarizing plate or an optical compensation film using the cellulose acylate film of the present invention is not limited to the operation mode of the liquid crystal display device. It is not limited.

Aton film with respect to polarizing plates 115-150 and polarizing plates 008-010 (polarizing plates produced by the cellulose acylate film samples 115-150 and comparative samples 008-010 produced in Examples 3-7) among the polarizing plates produced in Example 8. (Compared to JSR Co., Ltd.), the optical compensation film was uniaxially stretched to give an optical compensation function. At this time, the visual characteristics can be improved without changing the frontal characteristics by making the slow axis of the in-plane retardation of the optical compensation film perpendicular to the transmission axis of the polarizing plate. The in-plane retardation Re of the optical compensation film used was 270 nm, the retardation Rth of the thickness direction was 0 nm, and the Nz factor was 0.5.

Two sets of laminates of the polarizing plate 115 and the optical compensation film are prepared so that the optical compensation film is the liquid crystal cell side, respectively, `` (Lamination of the polarizing plate 115 and the optical compensation film) + (IPS type liquid crystal cell) + (Polarization plate 115 and the optical compensation). Display device) was fabricated. At this time, the transmission axis of the upper and lower polarizing plates was orthogonal, and the transmission axis of the upper polarizing plate was parallel to the molecular long axis direction of the liquid crystal cell (that is, the slow axis of the optical compensation layer and the molecular long axis direction of the liquid crystal cell were orthogonal). The liquid crystal cell, the electrode, and the board | substrate can use what is conventionally used as IPS as it is. The alignment of the liquid crystal cell is a horizontal alignment, and the liquid crystal has positive dielectric anisotropy, and those developed and marketed for IPS liquid crystal can be used. The physical properties of the liquid crystal cell were Δn: 0.099 of the liquid crystal, the cell gap of the liquid crystal layer: 3.0 µm, the pretilt angle: 5 degrees, and the rubbing direction: 75 degrees both above and below the substrate.

In the same manner, two sets of laminated bodies obtained by laminating an optical compensation film were also prepared for the polarizing plates 116 to 127, 138 to 139, 140 to 150, and the polarizing plates 008 to 010 to prepare a display device mounted with an IPS liquid crystal cell.

In the liquid crystal display device produced as described above, the results of measuring the light leakage rate at the time of black display at 45 degrees in the azimuth direction and 70 degrees in the polar direction from the front of the device are shown in Tables 13 and 14. .

The smaller this value, the less optical leakage in the inclination 45 degree direction and the better the contrast of the display device, and the viewing angle characteristic of the liquid crystal display device can be evaluated. When the polarizing plates 115-127, 138-139, 140-150 which consist of the cellulose acylate film of this invention were used, compared with the case where the polarizing plates 008-010 which consist of a comparative sample were used, the light leakage rate is 1/50 at 1/50. It all went down to four. When the polarizing plates 115 to 127, 138 to 139, and 140 to 150 were used, the color change of the display device was smaller than that of the polarizing plates 008 to 010. This shows that the cellulose acylate film samples 115 to 127, 138 to 139 and 140 to 150 of the present invention have the same optical compensation performance at any wavelength because the wavelength dispersion of Re and Rth is excellent (the wavelength dependency is small). . As described above, it was found that the optical compensation film and the polarizing plate produced by the cellulose acylate film of the present invention are excellent in viewing angle characteristics and difficult to change the display color.                     

Example 10 (Evaluation of Packaging for VA Type and OCB Type Liquid Crystal Display Devices)

The liquid crystal display device of Example 1 of Unexamined-Japanese-Patent No. 10-48420, and the Example 1 of Unexamined-Japanese-Patent No. 9-26572 using the cellulose acylate film sample of this invention obtained in Examples 1-7. Optical anisotropic layer containing discotic liquid crystal molecules, alignment film coated with polyvinyl alcohol, VA type liquid crystal display device described in FIGS. 2 to 9 of JP 2000-154261, and FIG. 10 to JP 2000-154261 Evaluation in the OCB type liquid crystal display device described in 15 showed that, in all cases, good contrast viewing angles were obtained.

Example 11 (Optical Compensation Film Performance)                     

The optical compensation film sample was produced by the method of Example 1 of Unexamined-Japanese-Patent No. 7-333433 using the cellulose acylate film sample of this invention obtained in Examples 1-7. The obtained filter film had the right and left top and bottom excellent viewing angles. Therefore, it turned out that the cellulose triacetate film of this invention is excellent as an optical use.

[Example 12]

(Optical compensation film performance)

Using the cellulose acylate film sample of this invention, the optical compensation film sample was produced according to the method of Example 1 of Unexamined-Japanese-Patent No. 2003-315541. 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB Cellulose acylate film sample 140 (thickness: 80 μm) of a polyimide having a weight average molecular weight (Mw) of 70,000 and a polyimide having Δn of about 0.04, prepared at 25 wt% using cyclohexanone as a solvent. )). Thereafter, heat treatment was performed at 100 ° C. for 10 minutes, followed by 15% longitudinal uniaxial stretching at 160 ° C. to obtain an optical compensation film having a polyimide film having a thickness of 6 μm coated on the cellulose acylate film of the present invention. The optical properties of this optical compensation film were an optical compensation film having a birefringence layer having Re = 70 nm, Rth = 220 nm, and a deviation angle of an alignment axis within ± 0.3 degrees and having nx> ny> nz.

(Comparative Example)

A polyimide film having a thickness of 6 µm was coated on the cellulose acylate film of Comparative Sample 001 by the same operation except that Sample 140 of Example 12 was applied to Comparative Sample 001 (thickness: 80 µm) prepared in Example 1. An optical compensation film was obtained. The optical properties of this optical compensation film were Re = 75 nm and Rth = 280 nm.

(Evaluation of mounting on VA type liquid crystal display)

In the optical compensation films obtained in Examples 12 and Comparative Examples, the side without the polyimide film was subjected to alkali saponification and bonded to the polarizer by directly adhering the polarizer with a polyvinyl alcohol-based adhesive. At this time, the bonding was performed such that the nx direction of the optical compensation film and the absorption axis of the polarizing plate were perpendicular to each other. These optical compensation films were bonded to the VA liquid crystal panel with an adhesive so as to be the liquid crystal cell side. Moreover, only the polarizing plate was bonded to VA liquid crystal panel through an adhesive so that the absorption axes of a polarizing plate might orthogonally cross on the opposite side of a liquid crystal cell. When the viewing angle characteristics of the liquid crystal display device obtained as described above were measured, the optical compensation film obtained from the cellulose acylate film sample 140 of the present invention obtained in Example 12 had a better viewing angle than the optical compensation film obtained from the comparative sample 001. It was to have. Therefore, it turned out that it is excellent also when using the cellulose triacylate film of this invention as retardation film for VA.

Example 13 (Evaluation of optical performance after wet heat treatment, volatility of compound)

For the cellulose acylate film sample of the present invention produced in Examples 1 to 6, the amount of change in Re and Rth of the film treated at 60 ° C 90% RH for 240 hours and the amount of change in Re and Rth of the film treated at 80 ° C 240 hours And the total amount of volatilization of the compound which reduces Rth and the compound which reduces (DELTA) Rth in the film which processed at 80 degreeC 240 hours was measured. The results are shown in Table 15. Moreover, as the comparative example, the comparative sample 012 which added TPP (triphenyl phosphate) by the operation of Example 3 was produced. From the results of Table 15, it was found that the cellulose acylate film of the present invention had a small amount of change in Re and Rth even when subjected to high humidity treatment and high temperature treatment, and had a small amount of volatilization of the compound even at high temperature treatment.                     

Example 14                     

(Light Resistance of Cellulose Acylate Film)

Super zeolite light was irradiated for 240 hours with respect to the cellulose acylate film samples 103 and 144 of this invention produced by Example 1, 2, 6, and the comparative sample 007. The color difference ΔE * ab was calculated from the color measurement of the film before irradiation and the color measurement after irradiation. The film of the present invention was found to have a small color difference with respect to super xenon light irradiation, which is an accelerated test of light resistance to natural light. It was also confirmed that the same results were obtained even in the carbon arc irradiation, which was the same acceleration test.

Name of sample Optical anisotropy
Lowering agent Wavelength dispersion
Moderator ΔE * ab Comparative Sample 007 (BDP) 25 Invention 103 A-19 UV-102 11 Invention 144 FB-6 UV-102 0.8

Example 15 (Evaluation of Implementation for IPS Type Liquid Crystal Display)

<Production of IPS Mode Liquid Crystal Cell 1>

The electrodes were arranged on one glass substrate so that the distance between adjacent electrodes was 20 µm, and a polyimide film was formed thereon as an alignment film to perform a rubbing treatment. A polyimide film was formed on one surface of a separately prepared glass substrate and rubbed to obtain an alignment film. The two glass substrates are opposed to each other and the alignment films are opposed to each other, and the gaps (gaps; d) of the substrates are 3.9 µm, and the two glass substrates are overlapped so that the rubbing directions of the two glass substrates become parallel to each other. Then, the refractive index anisotropy (Δn) is 0.0769 and the dielectric anisotropy (Δε). ) This plus 4.5 nematic liquid crystal composition was encapsulated. The value of d · Δn of the liquid crystal layer was 300 nm.                     

<Production of Polarizer>

Iodine was adsorbed to the stretched polyvinyl alcohol film to produce a polarizing film, and the cellulose acylate film sample 103 of the present invention was bonded to one side of the polarizing film using a polyvinyl alcohol-based adhesive. Subsequently, a saponification process was carried out to the commercially available cellulose acetate film (Fuji Tak TF80UL, manufactured by Fujishashin Film Co., Ltd.), and it bonded to the opposite side of this polarizing film using the polyvinyl alcohol-type adhesive agent, and formed the 1st polarizing plate.

Moreover, in the manufacturing method of a 1st polarizing plate, the 2nd polarizing plate was produced similarly except having made both surfaces into the commercially available cellulose acetate film.

The cellulose acylate film 103 of the present invention was bonded to one side of the IPS mode accelerator produced above so that the absorption axis of the first polarizing plate was parallel to the rubbing direction of the liquid crystal cell. Subsequently, the second polarizing plate was bonded to the other side of the IPS mode liquid crystal cell in a cross nicol arrangement, and a liquid crystal display device was manufactured so that the backlight was arranged on the first polarizing plate side.

[Comparative Example]

In Example 15, the IPS liquid crystal display device was produced similarly except having made the polarizing plate of both surfaces of an IPS cell the 2nd polarizing plate.

<Measurement of leaked light of manufactured liquid crystal display device>

The change in the total azimuth direction (Δuv) at the polar angle of 60 degrees of the black color of the liquid crystal display device thus produced was measured. The results are summarized in Table 17. In Example 15 having a Δuv of 0.05 or less, almost no change in color was observed, but the comparative example having 0.05 or more exhibits a change in color. It was found that color change was improved by doing so.

Protective film used for polarizing plate Re Rth Black color change (Δuv) Example 15 Sample 103 of the Invention 1.9 14.9 0.03 Comparative example Fuji Tak TF80UL 3 45 0.09

According to the research of the present inventors, a cellulose acylate film having a small optical anisotropy and a small wavelength dispersion of Re and Rth can be produced. It has become possible to provide a liquid crystal display device using these.

The optical characteristics of a polarizing plate can be made good by using a cellulose acylate film with small optical anisotropy and small wavelength dispersion for a protective film of a polarizing plate. In addition, when used as a support of the optical compensation film can derive the optical performance of the optical compensation film itself. By using these polarizing plates and optical compensation films in liquid crystal displays, the contrast can be improved and the color can be improved.

By using the cellulose acylate film of the present invention having a small Re or Rth in the visible region having a wavelength of 400 to 800 nm and a small change in Re or Rth due to the wavelength, the wavelength dependence can be achieved by using a protective film of a polarizer, a support of an optical compensation film, or the like. It can be applied to the field of an image display apparatus which is small, that is, the display color is improved.

Claims (13)

Re _(λ) defined by the following formula (I) and Rth _(λ) defined by the following formula (II) satisfy the following formulas (III) and (IV) and lower Re _(λ) and Rth _(λ) 0.01-30% by weight of the compound having an octanol-water partition coefficient (LogP value) of 0 to 7 with respect to the cellulose acylate solid content, wherein the octanol-water partition coefficient (LogP value) is 0-7. The cellulose acylate film, wherein the compound is at least one selected from a polyhydric alcohol ester compound, a carboxylic acid ester compound, a polycyclic carboxylic acid compound, and a bisphenol derivative: (I) Re _(λ) = (nx-ny) × d (II) Rth _(λ) = {(nx + ny) / 2-nz} × d (III) 0 ≤ Re ₍₆₃₀₎ ≤ 2 and Rth ₍₆₃₀₎ ≤ 15 (IV) | Re ₍₄₀₀₎ -Re ₍₇₀₀₎ | ≤10 and | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | ≤35 [Wherein Re _(λ) is the front retardation value (unit: nm ₎ at wavelength _λ nm, and Rth _(λ) is the retardation value (unit: nm) in the film thickness direction at wavelength _λ nm. Nx is a refractive index in the slow axis direction in the film plane, ny is a refractive index in the fast axis direction in the film plane, nz is a refractive index in the thickness direction of the film, and d is the thickness of the film. delete The cellulose acylate film according to claim 1, which contains a compound which reduces the retardation Rth _(λ) in the film film thickness direction in a range satisfying the following formulas (i) and (iii): (Iii) (Rth (A) -Rth (O)) / A ≤-1.0 (Iii) 0.01 ≤ A ≤ 30 (From here, Rth (A): Rth (nm) of the film containing A% of the compound which reduces Rth _((lambda) ) Rth (O): Rth (nm) of the film which does not contain the compound which reduces Rth _((lambda) ) A: Weight (%) of the compound when the weight of the film raw material polymer is 100. to be). The acyl substitution degree of cellulose acylate is 2.85-3.00, 0.01-30 weight% of compounds which reduce Re _((lambda)) and Rth _((lambda)) with respect to cellulose acylate solid content are contained, The cellulose acylate film characterized by the above-mentioned. 5. The cellulose acylate film according to claim 4, wherein the acyl substituent of the cellulose acylate is substantially only an acetyl group, the total substitution degree is 2.85 to 3.00, and the average degree of polymerization of the cellulose acylate is 180 to 550. delete The compound according to claim 1, wherein the compound in which Re _(λ) and Rth _(λ) are lowered and the octanol-water partition coefficient (LogP value) is 0 to 7 is represented by any one of Formulas 1 to 6 and 8 to 19. Cellulose acylate film, characterized in that: [Formula 1]

(In formula, R <^101> -R <^103> represents a C1-C20 aliphatic group each independently.) [Formula 2]

(3)

(In the formula 2 and 3, Z is a carbon atom, an oxygen atom, a sulfur atom, or -NR ²⁰⁵ -. Represents a, R ²⁰⁵ represents a hydrogen atom or an alkyl group; Y ²⁰¹ -Y ²⁰² is an ester having the carbon number of 1 to 20 are each independently Group, alkoxycarbonyl group, amide group or carbamoyl group, m represents an integer of 1 to 5, n represents an integer of 1 to 6) [Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

In Formulas 4-6 and 8-12, Y ³¹ -Y ³⁹ and Y ⁴⁴ -Y ⁷⁰ each independently represent an ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. . an amide group, represents the number of carbon atoms is 1 to 20 is a carbamoyl group or a hydroxyl group, V ³¹ and V ³⁴ -V ⁴³ are respectively independently a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, each L ³¹ -L ³⁸ and L ⁴⁴ - L ⁸⁰ each independently represents a single bond or a divalent saturated linking group having 1 to 40 atoms and having 0 to 20 carbon atoms) [Chemical Formula 13]

In Formula 13, R ³¹ represents an alkyl group or an aryl group, and R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group or an aryl group. The total number of carbon atoms in R ³¹ , R ^32, and R ³³ is 10 or more, R ³¹ , R ³² and R ³³ may each have a substituent, and R ³¹ and R ³² may combine to form a ring) [Formula 14]

(In Formula 14, R ¹⁰⁴ and R ¹⁰⁵ each independently represent an alkyl group or an aryl group. The total number of carbon atoms of R ¹⁰⁴ and R ¹⁰⁵ is 10 or more, and R ¹⁰⁴ and R ¹⁰⁵ may each have a substituent.) [Formula 15]

In Formula 15, R ²¹ , R ^22, and R ²³ each independently represent a hydrogen atom or an alkyl group. X ²¹ represents a divalent linking group formed of at least one group selected from the following linking group group 1. Y ²¹ is A hydrogen atom, an alkyl group, an aryl group, or an aralkyl group is represented. (Coupler group 1) Single bond, -O-, -CO-, -NR ^24- , alkylene group and arylene group. R ²⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.) [Chemical Formula 16]

(In Formula 16, Q ¹ , Q ² and Q ³ each independently represent a 5 to 6 membered ring. X ⁶¹ represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, P = O) [Chemical Formula 17]

(In Formula 17, X ⁴² represents B, CR ⁷⁰ (R ⁷⁰ represents a hydrogen atom or a substituent.), N, P, P═O. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom or a substituent) [Chemical Formula 18]

(In Formula 18, R ¹¹¹ represents an alkyl group or an aryl group, and R ¹¹² and R ¹¹³ each independently represent a hydrogen atom, an alkyl group, or an aryl group.) [Formula 19]

(In Formula 19, R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ each independently represent an alkyl group or an aryl group.). delete The cellulose acylate film according to claim 1, wherein the compound which reduces ΔRth defined by the following formula (VII) is contained within a range satisfying the following formulas (VII) and (XI): (Ⅸ) ΔRth = | Rth ₍₄₀₀₎ -Rth ₍₇₀₀₎ | (Ⅹ) (ΔRth (B) -ΔRth (O)) / B ≤-2.0 (XI) 0.01 ≤B ≤30 (From here, Rth ₍₄₀₀₎ : Rth (nm) at 400 nm Rth ₍₇₀₀₎ : Rth (nm) at ₇₀₀ nm ΔRth (B): ΔRth (nm) of a film containing B% of a compound that reduces ΔRth ΔRth (O): ΔRth (nm) of the film containing no compound that lowers ΔRth B: Weight (%) of the compound when the weight of the film raw material polymer was 100. to be). An optical compensation film having a cellulose acylate film according to claim 1 and an optically anisotropic layer having a Re ₍₆₃₀₎ of 0 to 200 nm and a Rth ₍₆₃₀₎ of 0 to 400 nm. The polarizing plate which has a polarizer and the cellulose acylate film of Claim 1, or the optical compensation film of Claim 10 as a protective film of this polarizer. And a liquid crystal cell and at least one of the following (1) to (3): (1) the cellulose acylate film of claim 1, (2) the optical compensation film of claim 10, and (3) The polarizing plate which has a polarizer and the cellulose acylate film of Claim 1, or the optical compensation film of Claim 10 as a protective film of this polarizer. An IPS liquid crystal display device having a liquid crystal cell of IPS mode and a polarizing plate on both sides of the liquid crystal cell, wherein at least one polarizing plate has a cellulose acylate film according to claim 1 on the liquid crystal cell side. .