JP2006154803A5 - - Google Patents

Description

However, conventional cellulose acylate film is in haze due to increasing trend retardation increases, thereby has a problem that Contrast of a liquid crystal display device is decreased, improvement has been sought .
On the other hand, Patent Document 2 discloses a stretched cellulose acylate film having secondary particles having an average particle size of 0.1 μm to 1.5 μm including primary fine particles having an average particle size of 0.001 or more and less than 0.1 μm. A method is disclosed in which aggregation of fine particles is suppressed and haze is reduced by increasing the content of additives in the vicinity of secondary fine particles from the average content of additives in the film. However, even with this method, haze reduction is insufficient, and improvement has been demanded.
JP2003-170492 JP2003-301049

(1) A cellulose acylate film characterized in that in-plane retardation Re and thickness direction retardation Rth at a wavelength of 590 nm satisfy a range of the following formulas (I) to (III), and a haze is 0.01 or more and 0.8 or less.
Formula (I) 20 ≦ Re ≦ 50
Formula (II) 70 ≦ Rth ≦ 200
Formula (III) 1.0 ≦ Rth / Re ≦ 3.0
Re and Rth are values at 25 ° C. and 60% RH, and the unit is nm.
(2) In-plane retardation Re and thickness direction retardation Rth at a wavelength of 590 nm satisfy the following formulas (IV) and (V), and the relationship between in-plane retardation and thickness direction retardation satisfies the following formula (VI). A cellulose acylate film having a haze of 0.01 or more and 0.8 or less.
Formula (IV) 50 <Re ≦ 200
Formula (V) 150 ≦ Rth ≦ 400
Formula (VI) 2.0 ≦ Rth / Re ≦ 10.0
Re and Rth are values at 25 ° C. and 60% RH, and the unit is nm.
(3) The cellulose acylate film according to (1) or (2), wherein the coefficient of thermal expansion is 20 ppm / ° C. or more and 100 ppm / ° C. or less.
(4) An additive and a matting agent having a primary average particle size of 1 nm or more and 20 nm or less are contained, and the secondary average particle size of the matting agent is 0.05 μm or more and 1.05 μm or less. ) The cellulose acylate film according to any one of the above.
(5) The cellulose reed according to any one of (1) to (4), wherein the number of fine particles of 0.2 μm or more and 3 μm or less per 1 mm ² observed with a confocal laser microscope is 20 or less. Rate film.
(6) After mixing the additive and the matting agent solution in a state where the cellulose acylate concentration is 0.01% by mass or more and less than 5% by mass, a solution in which the cellulose acylate concentration is mixed with a dope having a cellulose acylate concentration of 5% by mass to 35% by mass. (1) to (1) obtained by casting on a support, drying and peeling on the support, and then stretching the film in the transport direction and / or the width direction by 1% or more and 100% or less. The cellulose acylate film according to any one of 5).
(7) The additive premixed with the matting agent is at least one of an ultraviolet absorber, a plasticizer, a retardation developer, a retardation reducing agent, and a deterioration preventing agent (6) The cellulose acylate film according to any one of the above.

(8) The cellulose acylate film according to any one of (1) to (7), wherein the crystallization index represented by the following formula (A) is from 0.80 to 1.10.
(A) Crystallization index = (X-ray diffraction intensity when 2θ is 27 °) / (X-ray diffraction intensity when 2θ is 25 °)
(9) It was manufactured by casting a dope solution having a solid content concentration of 17% by mass or more and 25% by mass or less on a support and applying and drying with a wind of 1 m / min or more immediately after casting. The cellulose acylate film as described in any one of (1) to (8).
(10) The cellulose acylate film according to any one of (1) to (9), wherein the cellulose acylate film is produced through a process in which a drying temperature and an air volume on a support satisfy the following relationship.
{Average temperature of drying air (℃) x average air velocity of drying air (m / min)} in the first half of the support>> {Average temperature of drying air (℃) × average air velocity of drying air ( m / min)}
(11) Residual solvent represented by the following formula at a temperature of (the glass transition point of the film when the solvent content is less than 0.5% -30 ° C.) or more and the glass transition point of the film when the solvent content is less than 0.5% + 10 ° C. The film is stretched in a state where the content is 1% by mass or more and 30% by mass or less (
The cellulose acylate film according to any one of 1) to (10).
(Residual solvent content) = (mass of solvent contained in the film) / (mass of the entire film)
(12) The cellulose acylate film according to any one of (1) to (11), wherein an in-plane orientation degree determined from X-ray diffraction is 0.20 or more and 0.50 or less.
(13) The cellulose acylate film as described in any one of (1) to (12), wherein the retardation developer is a rod-shaped retardation developer represented by the following general formula (B): .
General formula (B)
Ar ¹ -L ¹ -XL ² -Ar ²
(In the formula, Ar ¹ and Ar ² represent an aryl group or an aromatic heterocycle. L ¹ and L ² represent —C (
= O) O-, -C (= O) NR- (R represents a hydrogen atom or an alkyl group). X represents the following general formula (2) or general formula (3). )
General formula (2)

(In General Formula (4), R ² , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent, R ¹¹ and R ¹³ each represent a hydrogen atom or an alkyl group, and L ¹ and L ² Each represents a single bond or a divalent linking group, Ar ¹ represents an arylene group or a divalent aromatic heterocyclic group, and Ar ² represents an aryl group or a monovalent aromatic heterocyclic group. , n represents an integer of 3 or more, ^L 2 present n kinds, Ar ¹ may each be the same or different. However ^{R 11, R 13} is optionally the same as or different from each other .R ¹³ The alkyl group represented by does not contain a hetero atom.)
(15) The cellulose acylate film according to any one of (1) to (14), wherein the cellulose acylate is a cellulose acetate having an acetylation degree of 2.5 or more and 2.95 or less.
(16) The cellulose acylate has an acetyl group and an acyl group having 3 to 22 carbon atoms as an acyl group, and the substitution degree A of the acetyl group and the substitution degree B of the acyl group having 3 to 22 carbon atoms are The cellulose acylate film according to any one of (1) to (14), wherein the following formulas (VII) and (VIII) are satisfied.
(VII) 2.0 ≦ A + B ≦ 3.0
(VIII) 0.1 ≦ A ≦ 2.5

The cellulose acylate film of the present invention is preferably composed of a cellulose acylate in which the polymer component constituting the film substantially has the above definition. “Substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more) of the polymer component. As the raw material of the film production, as particle shape of the cellulose acylate is good preferable. 90% by mass or more of the particles used preferably have a particle diameter of 0.5 to 5 mm. Moreover, it is preferable that 50 mass% or more of the particle | grains to be used have a particle diameter of 1-4 mm. The cellulose acylate particles preferably have a shape as close to a sphere as possible.

In general formula (1-B), X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms,
An aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a carbonyl group, Represents a cyano group or a halogen atom.
When all of R ¹ , R ² , R ⁴ and R ⁵ are hydrogen atoms, X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group. And an aryloxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, an n -propoxy group, an iso-propoxy group or an n-butoxy group.

[Synthesis Example 21: Synthesis of Exemplified Compound A-42]
After heating 30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene and 1.2 mL of dimethylformamide to 60 ° C., 21.6 g (181) of thionyl chloride was obtained.
Mmol) was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. Thereafter, pre-4 - After heat Dorokishi benzoate 27.6g of (181 mmol) was slowly added a solution prepared by dissolving in dimethylformamide 40 mL, was stirred and heated at 80 ° C. 6 hours, the reaction solution was cooled to room temperature, Methanol (140 mL) was added, and the precipitated crystals were collected by filtration to obtain 24.4 g (yield 47%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum analysis.
¹ H-NMR (CDCl ₃ ) δ 3.92 (m, 9H), 6.56 (m, 2H), 7.27
(M, 2H), 8.09 (m, 3H).

6-2 Synthesis of Exemplified Compound B-7 2,4,5-Trimethoxybenzoic acid-4-ethynylanilide 3.1 g (10 mmol)
2,4,5-trimethoxybenzoic acid 4-iodophenyl 4.1 g (10 mmol),
Triethylamine 5.56 mL (40 mmol) and tetrahydrofuran 15 mL were stirred at room temperature under a nitrogen atmosphere, cuprous chloride 22.8 mg (0.12 mmol), triphenylphosphine 131 mg (0.5 mmol), bis (triphenyl) 70 mg (0.1 mmol) of phosphine) palladium dichloride was added, and the mixture was heated and stirred at 60 ° C. for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and 200 mL of water was added. The obtained crystals were filtered and recrystallized with 100 mL of methanol to obtain 5.6 g (yield 94%) of the target compound as yellowish white crystals.
)Obtained.
Incidentally, the identification of the compound was more ¹ H-NMR (400MHz).
¹ H-NMR (DMSO-d ₆ ) δ 3.92 (s, 3H), 3.93 (s, 3H), 4.
05 (m, 9H) 4.15 (s, 3H) 6.96 (br, 2H), 7.46 (d, 2H)
7.55 (s, 1H), 7.62 (s, 1H), 7.69 (d, 2H), 7.76 (d
, 2H), 7.98 (d, 2H), 10.30 (s, 1H).
The melting point of the obtained compound was 216 to 218 ° C.
General formula (4)

In general formula (4), R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent. Substituent T described later can be applied as the substituent.

R ¹¹ and R ¹³ in the general formula (4) each independently represent a hydrogen atom or an alkyl group, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom. Here, the hetero atom means an atom other than a hydrogen atom or a carbon atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus, silicon, a halogen atom (F, Cl, Br, I), and boron.
The alkyl group represented by R ¹¹ and R ¹³ is linear, branched, or cyclic and represents a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. , substituted or unsubstituted cycloalkyl group having 3 carbon 30, a substituted or unsubstituted bicycloalkyl group having 5 to carbon atoms 30 (That is, by removing one hydrogen atom from bicycloalkane 5 30 carbon monovalent And a tricyclo structure having more ring structures.

In the general formula (4), the aromatic heterocycle represented by Ar ¹ or Ar ² may be an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, preferably
It is an aromatic heterocycle containing at least one of a 5- to 6-membered ring oxygen atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

In general formula (6), R ² , R ⁵ , R ¹¹ and R ¹³ have the same meanings as those in general formula (4), and the preferred ranges are also the same. L ¹ , L ² , Ar ¹ , Ar ² are represented by the general formula (4
), And the preferred range is also the same.
In the general formula (6), R ¹⁴ represents a hydrogen atom or an alkyl group, and the alkyl group shown as a preferred example of R ¹¹ and R ¹³ is preferably used as the alkyl group. R ^1
4 is also preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. R ¹¹ and R ^{1 4} may be different or may be the same, and it is most preferred that both are methyl groups.

Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing the hydrogen atom. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include specific examples, methylsulfonyl aminocarbonyl group, p- methylphenylsulfonylaminocarbonyl group, acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

Is represented by preferred as the compound of general formula (6-A) and general formula ^(6-B), both ^{R 11} is a methyl ^group, neither R 2, ^{R 5} is hydrogen atom , R ¹³ is an alkyl group having 3 or more carbon atoms, and L ¹ is a single bond, —O—, —CO—, —NR—, —SO ₂ NR—, —NRSO ₂ —, —CONR—, -NRCO-, -COO-, and -OCO-, an alkynylene group (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group, preferably a hydrogen atom), and L ^2. Is —O— or —NR— (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group, preferably a hydrogen atom), Ar ¹ represents an arylene group, and n Can be exemplified by 3 to 6.

The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.
Further, the present reaction is rather is preferably not with a base, organic in the case of using a salt group base may be either an inorganic base, preferably an organic base, pyridine, tertiary alkylamines (preferably triethylamine And ethyl diisopropylpropylamine).

(In the formula, A ′ represents a reactive group such as a carboxyl group, and R ¹¹ , R ² , R ¹³ , R ⁴ , R ⁵ , Ar ¹ , and L ¹ are as described above.)
Compound C

(In the formula, B and B ′ represent a reactive group such as a hydroxyl group and an amino group, and Ar ² and L ² have the same meanings as Ar ¹ and L ¹ described above.)

The cellulose acylate film of the present invention has a wind speed of 1 m / min immediately after casting the dope onto a support.
It is preferable to dry by applying a wind of min or more. Velocity of the drying air 3m / min or higher good Mashiku Furthermore, more preferably 5 m / min or more, more 10 m / min is most preferred.
Moreover, it is preferable that the cellulose acylate film of this invention is manufactured through the process in which the average drying temperature and average airflow on a support satisfy | fill the following relationship.
In the first half of the support:
{Average temperature of drying air (℃) x Average air velocity of drying air (m / min)}> Support In the latter half of drying:
{Average temperature of drying air (℃) x Average air velocity of drying air (m / min)}
More preferably, in the first half of the support:
{Average temperature of drying air (℃) x Average air velocity of drying air (m / min)}> Support In the latter half of drying:
{Average temperature of drying air (℃) x Average air velocity of drying air (m / min)} + 4000
It is.
Here, the average temperature of the drying air is an average value of the drying temperature recorded every 10 seconds of the drying air in a predetermined period, and the average wind speed is the air speed recorded every 10 seconds of the drying air in the predetermined period. Represents the average value.

<Photoelasticity>
The photoelastic coefficient of the cellulose acylate of the present invention is preferably 60 × 10 ⁻⁸ cm ² / N or less, and more preferably 20 × 10 ⁻⁸ cm ² / N. The photoelastic coefficient can be obtained by an ellipsometer.
<Glass transition temperature>
The glass transition temperature of the cellulose acylate of the present invention is preferably 120 ° C. or higher, and further 14
0 degreeC or more is preferable. The glass transition temperature is a temperature at which the base line derived from the glass transition of the film starts to change and a temperature at which it returns to the base line again when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). Is obtained as an average value of.

The medium refractive index layer and the high refractive index layer preferably have a constitution in which ultrafine particles of high refractive index having an average particle size of 100 nm or less are dispersed in a matrix material. As the inorganic compound fine particles having a high refractive index, inorganic compounds having a refractive index of 1.65 or more, for example, Ti, Zn, Sb, Sn,
Oxides such as Zr, Ce, Ta, La, and In, composite oxides containing these metal atoms, and the like can be preferably used. Such ultrafine particles may be obtained by treating the particle surface with a surface treatment agent (silane coupling agent, etc .: JP-A Nos. 11-295503, 11-153703, 2000-9908, anionic compounds or Organometallic coupling agent: JP-A-2001-3
No. 10432), or a core-shell structure with high refractive index particles as a core (Japanese Patent Laid-Open No.
1-166104, etc.), can be used in a particular dispersant for a 併 (e.g., JP-A-11-153703 and JP-Patent No. US6210858B1, JP-Open No. 2002-2776069, etc.) and the like aspect.

As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. polyacrylates of polyols such as hexaacrylate; diacrylate of bisphenol a diglycidyl ether, epoxy acrylates such as diacrylate hexanediol diglycidyl ether; obtained by reacting polyiso cyanate and hydroxyl group-containing acrylates such as hydroxyethyl acrylate Urethane acrylate etc. can be mentioned as a preferable compound. Moreover, as a commercially available compound, EB-600, EB-40
, EB-140, EB-1150, EB-1290K, IRR214, EB-2220,
TMPTA, TMPTMA (above, manufactured by Daicel UCB), UV-6300
, UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

1.3 parts by weight of the matting agent solution and 2.9 parts by weight of the retardation developer solution were mixed using an in-line mixer after filtration, and 96.1 parts by weight of cellulose acylate solution A was added. The in-line mixer was mixed and cast using a band casting machine.
Residual solvent content of 33% the film was detached from the band, after transverse stretching up to 120% using a tenter a full Irumu at ambient temperature of 140 ° C., held for 30 seconds at 140 ° C.. The residual solvent content at the start of stretching was 10%. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film. The resulting cellulose acylate film had a residual solvent amount of 0.1% and a film thickness of 82 μm.

After 1.3 parts by mass of the matting agent solution and 6.0 parts by mass of the retardation developer solution are filtered and mixed with an in-line mixer, the cellulose acylate solution B is further added to 92.7.
A part by mass was added, mixed with an in-line mixer, and cast using a band casting machine. The film with a residual solvent content of 36% was peeled away from the band, after transverse stretching to 130% using a tenter a full Irumu at ambient temperature of 130 ° C., held for 30 seconds at 140 ° C.. The residual solvent content at the start of stretching was 15%. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film . The resulting cellulose acylate film had a residual solvent amount of 0.1% and a film thickness of 90 μm.

[Example 3]
(Preparation of cellulose acylate film 8)
<Preparation of cellulose acetate solution C>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution C.

94.5 parts by mass of the cellulose acylate solution C, 1.3 parts by mass of the matting agent solution, and 3.4 parts by mass of the retardation developer solution were mixed after filtration, and cast using a band casting machine. . The film with a residual solvent content of 31% was peeled away from the band, the film in an atmosphere temperature of the 160 ° C. stretching time 5 seconds using a tenter, at a stretching rate of drawing speed 6.0% / sec, and transversely stretched up to 130% After that, it was relaxed to 125% and held at 140 ° C. for 30 seconds. The residual solvent content at the start of stretching was 15%. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film. The resulting cellulose acylate film had a residual solvent amount of 0.2% and a film thickness of 83 μm.

<Production of liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Was formed. Retardation of the liquid crystal layer (i.e., the product [Delta] n · d of the thickness d ([mu] m) and refractive index anisotropy [Delta] n of the liquid crystal layer) was an 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

[Example 9]
(Preparation of cellulose acylate film 11)
<Preparation of cellulose acetate solution>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution D.

Claims (4)

The cellulose acylate film according to claim 1, wherein the retardation developer is a rod-shaped retardation developer represented by the following general formula (B).
General formula (B)
Ar ¹ -L ¹ -XL ² -Ar ²
(In the formula, Ar ¹ and Ar ² represent an aryl group or an aromatic heterocycle. L ¹ and L ² represent —C (
= O) O-, -C (= O) NR- (R represents a hydrogen atom or an alkyl group). X represents the following general formula (2) or general formula (3). )
General formula (2)

(R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a substituent.)
General formula (3)

(R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ represent a hydrogen atom or a substituent.) The cellulose acylate film according to claim 1, wherein the retardation developer is a rod-like retardation developer represented by the following general formula (4).
General formula (4)

(In General Formula (4), R ² , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent,
R ¹¹ and R ¹³ each represent a hydrogen atom or an alkyl group, and L ¹ and L ² each represent a single bond or a divalent linking group. Ar ¹ represents an arylene group or a divalent aromatic heterocyclic group, Ar ² represents an aryl group or a monovalent aromatic heterocyclic group, and n is 3
The above integers are represented, and n types of L ² and Ar ¹ may be the same or different. However, R ¹¹ and R ¹³ may be the same or different from each other . The alkyl group represented by R ¹³ does not contain a hetero atom. ) The cellulose acylate has an acetyl group as an acyl group and an acyl group having 3 to 22 carbon atoms, and the substitution degree A of the acetyl group and the substitution degree B of the acyl group having 3 to 22 carbon atoms are represented by the following formula ( The cellulose acylate film according to claim 1, wherein VII) and (VIII) are satisfied.
(VII) 2.0 ≦ A + B ≦ 3.0
(VIII) 0.1 ≦ A ≦ 2. 5 A retardation developer is contained , and after mixing the retardation developer solution and the matting agent solution in a state where the cellulose acylate concentration is 0.01% by mass or more and less than 5% by mass, the cellulose acylate concentration is 5% by mass or more and 35% by mass. A liquid mixed with the following dope is cast, and the film is stretched in the transport direction and / or the width direction by 1% or more and 100% or less to obtain the cellulose acylate film according to claim 1. A method for producing a cellulose acylate film.