KR20060051547A - Polarizing plate and liquid crystal display device - Google Patents

Abstract

(Problem) Providing a polarizing plate having a small difference in film thickness of the polarizer even in a large area, and providing a liquid crystal display device having less unevenness in brightness by using this polarizing plate.

(Solution means) A roll-shaped polarizing plate in which a protective film is bonded to at least one side of a polarizer made of polyvinyl alcohol having a polymerization degree of 1000 to 3800, wherein the difference between the maximum film thickness and the minimum film thickness in the width direction of the polarizer is 0 to 3 µm. It is set as the roll-shaped polarizing plate characterized by the above-mentioned. Moreover, it is set as the liquid crystal display device using the polarizing plate cut out from this roll-shaped polarizing plate.

Polarizer, polarizer, liquid crystal display

Description

POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE}

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows typically the cross-sectional structure of an example of the polarizing plate of this invention.

2 is a diagram schematically showing a cross-sectional structure of an example of a liquid crystal display of the present invention.

※ Brief description of the main parts of the drawings

1, 11, 21 polarizer

2, 12, 22 TAC1, TAC1-1, TAC1-2: one side protective film (arranged on the liquid crystal cell side)

3, 13, 23 TAC2, TAC2-1, TAC2-2: Shield on opposite side

4 functional film

5 polarizer

30 VA mode cell

[Patent Document 1] Japanese Patent No. 2587398

[Patent Document 2] European Patent Application Publication No. 911656

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-71957

[Patent Document 4] Japanese Unexamined Patent Publication No. 2003-270442

[Patent Document 5] Japanese Unexamined Patent Publication No. Hei 10-68821

This invention relates to the roll-shaped polarizing plate with little thickness nonuniformity of the width direction of a polarizer, and the liquid crystal display device using this polarizing plate.

Liquid crystal display devices are widely used for monitors and televisions of personal computers, portable devices, and the like, in terms of low voltage, low power consumption, and miniaturization and thinness. Such a liquid crystal display has been proposed in various modes according to the arrangement state of the liquid crystal molecules in the liquid crystal cell. Conventionally, a TN mode in which the liquid crystal cell is in an arrangement state in which the liquid crystal cell is twisted about 90 ° toward the upper substrate is mainstream.

In general, a liquid crystal display device includes a liquid crystal cell, an optical compensation sheet, and a polarizer. The optical compensation sheet is used in order to eliminate image coloring or to enlarge a viewing angle, and the film which apply | coated the liquid crystal to the stretched birefringent film and the transparent film is used. For example, Patent Literature 1 discloses a technique of applying an optical compensation sheet obtained by applying and orienting a discotic liquid crystal on a triacetyl cellulose film to a liquid crystal cell of TN mode to enlarge a viewing angle. However, the liquid crystal display device for television use, which is assumed to be viewed from various angles in a large screen, has a strict demand for viewing angle dependency, and cannot satisfy the demand even by using the above-described method. For this reason, liquid crystal display devices different from TN modes, such as IPS (In-Plane Switching) mode, OCB (Optically Compensatory Bend) mode, and VA (Vertically Aligned) mode, have been studied. In particular, VA mode has attracted attention as a liquid crystal display for TV because of its high contrast and relatively high production yield.

Generally as a material of the polarizer which is indispensable to a liquid crystal display device, polyvinyl alcohol (Hereinafter, PVA) is mainly used, extending | stretches after uniaxially stretching a PVA film, or dyeing with iodine or a dichroic dye, or extending | stretching And a polarizer is formed by bridge | crosslinking with a boron compound.

Moreover, a cellulose acylate film has the characteristics of high optical isotropy (low retardation value) compared with the other polymer film. Therefore, it is common to use a cellulose acylate film for the use which requires optical isotropy like the protective film of a polarizing plate.

On the other hand, optical anisotropy (high retardation value) is calculated | required by the optical compensation sheet (retardation film) of a liquid crystal display device. In the VA optical compensation sheet, in particular, front retardation (Re) of 30 to 200 nm and film thickness direction retardation (Rth) of 70 to 400 nm are required. Therefore, as an optical compensation sheet, it was common to use a synthetic polymer film with a high retardation value, such as a polycarbonate film and a polysulfone film.

As described above, in the technical field of optical materials, when optical anisotropy (high retardation value) is required for a polymer film, a synthetic polymer film is used, and when optical isotropy (low retardation value) is required, a cellulose acylate film It was a general principle to use.

Patent Document 2 proposes a cellulose acetate film having a high retardation value that can be used for applications in which conventional anisotropy is required, by overcoming conventional general principles. In this proposal, in order to implement | achieve a high retardation value in cellulose triacetate, the extending | stretching process is performed by adding the aromatic compound which has 2 or more aromatic rings, especially the compound which has a 1,3,5-triazine ring. In general, cellulose triacetate is a polymer material which is difficult to be stretched, and it is known that it is difficult to increase the birefringence. However, the birefringence can be increased by aligning the additives simultaneously in the stretching treatment, thereby achieving a high retardation value. Since this film can also serve as the protective film of a polarizing plate, there exists an advantage which can provide the liquid crystal display device which is a thin film at low cost.

A+B

3.0 및 식 A<2.4 를 동시에 만족하는 셀룰로오스에스테르를 함유하는 광학 필름으로서, 또한, 파장 590nm 에서의 지상축 방향의 굴절율 (Nx) 및 진상축 방향의 굴절율 (Ny) 이 식 0.0005

Nx-Ny

0.0050 을 만족하는 것을 특징으로 하는 광학 필름이 개시되어 있다. Patent document 3 has a C2-C4 acyl group as a substituent, the substitution degree of an acetyl group is A, and the substitution degree of a propionyl group or butyryl group is B, Formula 2.0

A + B

An optical film containing a cellulose ester which simultaneously satisfies 3.0 and formula A <2.4, and also has a refractive index Nx in the slow axis direction and a refractive index Ny in the fast axis direction at a wavelength of 590 nm.

Nx-Ny

An optical film is disclosed which satisfies 0.0050.

In patent document 4, in the polarizing plate used for VA mode liquid crystal display device, this polarizing plate has a polarizer and optically biaxially mixed mixed fatty acid cellulose ester film, and this optically biaxially mixed fatty acid cellulose between a liquid crystal cell and a polarizer Disclosed is a polarizing plate comprising an ester film.

On the other hand, Patent Document 5 discloses a method of producing a polarizing plate with less film thickness nonuniformity by adjusting the line pressure at the time of stretching the master film, the line pressure at the time of laminating the protective film on the polarizing film or after.

The method disclosed by the above-mentioned patent documents 1-4 is effective at the point where a cheap and thin liquid crystal display device is obtained. In recent years, however, liquid crystal display devices are rapidly being used for televisions. Since televisions have a brighter backlight and easier to see nonuniformity than a monitor, a surface shape with less nonuniformity is required. In particular, when used for large-sized televisions, a large area and a uniform surface shape are required. Therefore, the polarizing plate to be used also has a large area, little nonuniformity, and the thing of uniform quality is calculated | required.

In the conventional mainstream TN mode, the absorption axis of the polarizing plate is tilted by 45 ° with respect to the sides of the liquid crystal panel, but in VA or IPS mode, the absorption axis of the polarizing plate is 0 ° or 90 ° with respect to the sides of the liquid crystal panel. Since it joins by bonding, the yield of a polarizing plate is high and a sample can be taken without waste. Therefore, it is used to the circumference | surroundings of the polarizing plate which was not used conventionally, and the influence of the film thickness difference of a polarizing plate is observed more clearly, and it becomes a problem.

However, since the current polarizing plate is usually uniaxially stretched in the longitudinal direction, the film thickness difference in the width direction tends to be large. This is because, since it is free uniaxial stretching, a neck-in phenomenon occurs at the time of stretching, and in particular, the film thickness on one side is more likely to be thicker than the center portion. In this case, the film thickness gradually becomes thin from the one end portion to the center portion, and gradually increases over the other end portion. If the film thickness of the polarizers is different, the performance such as transmittance is different. Therefore, when such a polarizing plate is used in a large liquid crystal display device, a different point in brightness occurs in the same screen, which is not preferable.

Therefore, development of a polarizing plate with such a small film thickness difference is desired. In patent document 5, although the manufacturing method of the polarizing plate with few film thickness nonuniformity is disclosed, it was limited when the polymerization degree of PVA was 4000 or more. (The high-polymerization PVA film has the drawback that uniform stretching is difficult and uniformly dyed polarizer without dyeing unevenness is difficult to obtain.) Moreover, the protective film of this polarizing plate was small in Re value and Rth value, and had small optical compensation effect.

The objective of this invention is providing the polarizing plate which is excellent in the optical compensation performance which maintains uniform quality even in a large area, and the liquid crystal display device using this polarizing plate.

(Means to solve the task)

As a result of earnestly examining by the present inventors, it discovered that the said objective can be achieved by using a polarizer with a small film thickness difference in the width direction, and came to complete this invention.

That is, this invention is a polarizing plate and a liquid crystal display device of the following structure, and the said objective of this invention is achieved by this.

(1) A roll-shaped polarizing plate in which a protective film is bonded to at least one side of a polarizer made of polyvinyl alcohol having a polymerization degree of 1000 to 3800, wherein the difference between the maximum film thickness and the minimum film thickness in the width direction of the polarizer is 0 to 3 µm. Roll-shaped polarizing plate to be used.

(2) The film thickness difference between arbitrary 1 cm of the width direction of the said polarizer is 0.25 micrometer / cm or less, The roll-shaped polarizing plate as described in (1) characterized by the above-mentioned.

(3) The roll-shaped polarizing plate according to (1) or (2), wherein the entire width is 400 mm to 3000 mm.

(4) The front side retardation value Re ₍₅₉₀₎ at the wavelength of 590 nm and the retardation value Rth ₍₅₉₀₎ of the film thickness direction at the wavelength of 590 nm of the one side protective film are represented by the following formulas (I) and ( II) is satisfied, The roll-shaped polarizing plate in any one of (1)-(3) characterized by the above-mentioned.

Re₍₅₉₀₎

200nmFormula (I): 20 nm

Re ₍₅₉₀₎

200 nm

Rth₍₅₉₀₎

400nmFormula (II): 70 nm

Rth ₍₅₉₀₎

400 nm

(5) The ratio (Re / Rth ratio) of the value of Re _{(590) and} the value of Rth ₍₅₉₀₎ of the one side protective _film is 0.1 to 0.8, characterized in that any of (1) to (4) The roll-shaped polarizing plate of one.

(6) The said one side protective film is a cellulose acylate film which uses the cellulose acylate which is a mixed fatty acid ester of cellulose whose hydroxy group substituted by the acetyl group and the acyl group of 3 or more carbon atoms as a main polymer component,

The cellulose acylate has a substitution degree (A) of the acetyl group and a substitution degree (B) of an acyl group having 3 or more carbon atoms, which satisfy the following formulas (III) and (IV): The roll-shaped polarizing plate in any one of 5).

A+B

3.0Formula (III): 2.0

A + B

3.0

Formula (IV): 0 <B

(7) The acyl group with 3 or more carbon atoms is a butanoyl group, The roll-shaped polarizing plate as described in (6) characterized by the above-mentioned.

(8) The acyl group of 3 or more carbon atoms is a propionyl group, The roll-shaped polarizing plate as described in (6) characterized by the above-mentioned.

(9) A film comprising cellulose acylate obtained by replacing the hydroxyl group of the glucose unit constituting cellulose with an acyl group having 2 or more carbon atoms, wherein the protective film on one side is an acyl group of the hydroxyl group on the 2nd position of the glucose unit constituting cellulose. When the degree of substitution by DS2, acyl group of hydroxyl group of 3rd position and the degree of substitution by acyl group of hydroxyl group of DS3, 6th position are DS6, cellulose acylate which satisfies following formula (V) and (VI) It is a film, The roll-shaped polarizing plate as described in any one of (1)-(8) characterized by the above-mentioned.

DS2+DS3+DS6

3.0Formula (V): 2.0

DS2 + DS3 + DS6

3.0

0.315Formula (VI): DS6 / (DS2 + DS3 + DS6)

0.315

(10) The roll-shaped polarizing plate according to (9), wherein the acyl group is an acetyl group.

(11) The roll-shaped polarizing plate according to any one of (1) to (10), wherein the protective film on one side contains at least one of a plasticizer, an ultraviolet absorber, a peeling accelerator, a dye, and a mat agent.

(12) The roll-shaped polarizing plate according to any one of (1) to (11), wherein the protective film on one side contains at least one retardation expression agent of a rod-shaped compound or a disc-shaped compound.

(13) The roll-shaped polarizing plate according to any one of (1) to (11), wherein the protective film on one side is an optically anisotropic layer formed on a polymer film.

(14) The roll shape according to any one of (1) to (13), wherein at least one of a hard coat layer, an antiglare layer, and an antireflection layer is formed on a surface of the protective film disposed on the opposite side to the protective film on one side. Polarizer.

(15) The roll-shaped polarizing plate according to any one of (1) to (14), wherein a retardation film is bonded to the protective film side on the one side by using an adhesive.

(16) The polarizing plate cut out by the roll-shaped polarizing plate in any one of (1)-(15).

(17) The liquid crystal display device using the polarizing plate as described in (16) so that the said one side protective film may be arrange | positioned at the liquid crystal cell side.

(The best mode for carrying out the invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In addition, in this specification, when a numerical value shows a physical property value, a characteristic value, etc., description "(value 1)-(value 2)" shows the meaning of "(value 1) or more (value 2) or less." In addition, in this specification, the description of "(meth) acrylate" shows the meaning of "one or more of an acrylate and a methacrylate." "(Meth) acrylic acid" is also the same.

(Polarizing plate)

First, the polarizing plate of this invention is demonstrated.

The polarizing plate of this invention is a roll-shaped polarizing plate which bonded the protective film to at least one side of the polarizer which consists of polyvinyl alcohol of the polymerization degree 1000-3800, The difference of the maximum film thickness and minimum film thickness of the width direction of this polarizer is 0-3. It is a roll-shaped polarizing plate characterized by being micrometer, and the polarizing plate cut out from this roll-shaped polarizing plate (Hereinafter, "roll-shaped polarizing plate" is just described as "polarizing plate" suitably in this specification).

The polarizing plate of this invention, Preferably, the optical cellulose acylate film which concerns on this invention mentioned later uses at least 1 piece as a protective film of a polarizer.

The polarizing plate usually consists of a polarizer and two transparent protective films arrange | positioned at both sides. And in this invention, Preferably the cellulose acylate film which concerns on this invention mentioned later is used as at least one protective film. The other protective film may use the cellulose acylate film which concerns on this invention, and may use a normal cellulose acetate film. In the present invention, even when used as a large liquid crystal display device, uniform display quality is realized by reducing the film thickness difference in the width direction of the polarizer.

The polarizer of a polarizing plate has an iodine type polarizer and a dye type polarizer using a dichroic dye, and a polyene type polarizer. An iodine type polarizer and a dye type polarizer are generally manufactured using a polyvinyl alcohol-type film.

It is preferable to comprise the polarizer which concerns on the polarizing plate of this invention with polyvinyl alcohol (PVA) and a dichroic molecule.

Although PVA is a polymer material which saponified polyvinyl acetate, you may contain the component copolymerizable with vinyl acetate, such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ether, for example. Moreover, modified PVA containing acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group, etc. can also be used.

Although the saponification degree of PVA is not specifically limited, From a viewpoint of solubility, etc., 80-100 mol% is preferable and 90-100 mol% is especially preferable. Moreover, 1000-3800 are preferable and, as for the polymerization degree of PVA, 1500-3800 are especially preferable.

Syndiotacticity of PVA is preferably 55% or more in order to improve durability as described in Japanese Patent No. 2978219, but 45 to 52.5% described in Japanese Patent No. 3317494 is preferably used. Can be.

After PVA film-forming, it is preferable to introduce | transduce a dichroic molecule and comprise a polarizer. As the manufacturing method of a PVA film, the method of cast | flow_spreading and forming a film | membrane which melt | dissolved PVA system resin in water or an organic solvent is generally used preferably. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and a PVA film having a film thickness of 10 to 200 µm can be produced by forming the stock solution by a casting method. The manufacture of a PVA film can be performed with reference to Unexamined-Japanese-Patent No. 3342516, Unexamined-Japanese-Patent No. 9-328593, Unexamined-Japanese-Patent No. 13-302817, and Unexamined-Japanese-Patent No. 14-144401.

Although the crystallinity degree of a PVA film is not specifically limited, In order to reduce the color deviation of 50-75 mass% of average crystallinity degree (Xc) described in Unexamined-Japanese-Patent 332573, and in-plane, Unexamined-Japanese-Patent No. 14-236214 The PVA film of 38% or less of crystallinity described in the above can be used.

It is preferable that birefringence ((DELTA) n) of a PVA film is small, The birefringence described in Unexamined-Japanese-Patent No. 3342516 can use the PVA film of 1.0x10 <^-3> or less preferably. However, as described in Japanese Patent Application Laid-Open No. 14-228835, in order to obtain high polarization while avoiding cutting during stretching of the PVA film, the birefringence of the PVA film may be 0.02 or more and 0.01 or less, As described in Japanese Patent Application Laid-Open No. 14-60505, the value of (nx + ny) / 2-nz may be 0.0003 or more and 0.01 or less. 0 nm or more and 100 nm or less are preferable, and, as for the retardation (in-plane) of a PVA film, 0 nm or more and 50 nm or less are more preferable. Moreover, 0 nm or more and 500 nm or less are preferable, and, as for Rth (film thickness direction) of a PVA film, 0 nm or more and 300 nm or less are more preferable.

In addition, in the polarizing plate of the present invention, a PVA film having a 1,2-glycol bond amount described in Japanese Patent No. 301494 or less and 1.5 mol% or less, and an optical foreign material of 5 μm or more described in JP-A-13-316492 PVA films of 500 or less per 100 cm 2, PVA films having a hydrothermal cleavage temperature nonuniformity in the TD direction of the film described in JP-A-H14-30163, 1.5 ° C. or lower, and 3 to 6-valent polyhydric alcohols such as glycerin The PVA film which mixed 1-100 mass parts or formed into the solution which mixed 15 mass% or more of the plasticizers of Unexamined-Japanese-Patent No. 6-289225 can be used preferably.

Although the film film thickness before extending | stretching of a PVA film is not specifically limited, 1 micrometer-1 mm are preferable and 20-200 micrometers are especially preferable from the viewpoint of the stability of film holding | maintenance, and the homogeneity of extending | stretching. As described in Unexamined-Japanese-Patent No. 14-236212, you may use the thin PVA film in which the stress which arises when extending | stretching 4 to 6 times in water becomes 10 N or less.

As the dichroic molecule, higher order iodine ions or dichroic dyes such as I ₃ -and I ₅ -can be preferably used. In the present invention, higher order iodine ions are particularly preferably used. The higher order iodine ions are liquids obtained by dissolving iodine in an aqueous potassium iodide solution, as described in the Nagata Medical Edition, "Application of Polarizing Plates", CMC Publications and Industrial Materials, Vol. 28, No. 7, p39-p45, and / Or PVA is immersed in boric-acid aqueous solution, and it can produce | generate in the state which adsorbed and aligned to PVA.

When using a dichroic dye as a dichroic molecule, an azo dye is preferable and a bis azo dye and a tris azo dye are especially preferable. The dichroic dye is preferably a water-soluble adult. For this reason, hydrophilic substituents such as sulfonic acid groups, amino groups, and hydroxyl groups are introduced into the dichroic molecules, and are preferably used as free acids or salts of alkali metal salts, ammonium salts and amines.

Specific examples of such dichroic dyes include, for example, CI Direct Red 37, Congo Red (CI Direct Red 28), CI Direct Violet 12, CI Direct Blue 90, CI Direct Blue 22, CI Direct Blue 1, CI Direct Blue. Benzidine series such as 151, CI Direct Green 1, diphenylurea series such as CI Direct Yellow 44, CI Direct Red 23, CI Direct Red 79, stilbene series such as CI Direct Yellow 12, and dinaphthyl such as CI Direct Red 31 J acid systems, such as an amine system, CI Direct Red 81, C, I, Direct Violet 9, C. I, Direct Blue 78, are mentioned.

In addition, CI Direct Yellow 8, CI Direct Yellow 28, CI Direct Yellow 86, CI Direct Yellow 87, CI Direct Yellow 142, CI Direct Orange 26, CI Direct Orange 39, CI Direct Orange 72, CI Direct Orange l06, CI Direct Orange l07, CI Direct Red 2, CI Direct Red 39, CI Direct Red 83, CI Direct Red 89, CI Direct Red 240, CI Direct Red 242, CI Direct Red 247, CI Direct Violet 48, CI Direct Violet 51, CI Direct Violet 98, CI Direct Blue l5, CI Direct Blue 67, CI Direct Blue 71, CI Direct Blue 98, CI Direct Blue 168, CI Direct Blue 202, CI Direct Blue 236, CI Direct Blue 249, CI Direct Blue 270, CI Direct Green 59, CI Direct Green 85, CI Direct Brown 44, CI Direct Brown 106, CI Direct Brown 195, CI Direct Brown 210, CI Direct Brown 223, CI Direct Brown 224, CI Direct Black 1, CI Direct Black 17, CI Direct Black 19, C. I, Direct Black 54, and the like, also disclosed in JP Japanese Patent Application Laid-Open No. 62-70802, Japanese Patent Application Laid-Open No. H11-61202, Japanese Patent Application Laid-Open No. 1-72907, Japanese Patent Application Laid-Open No. 1-72907, Japanese Patent Application Laid-Open No. 1-183602, Japanese Patent Application Laid-Open The dichroic dye described in each of Unexamined-Japanese-Patent No. 1-265205, Unexamined-Japanese-Patent No. 7-261024, etc. can also be used preferably. In order to manufacture the dichroic molecule which has various colors, these dichroic dye may mix 2 or more types. When using a dichroic dye, adsorption thickness may be 4 micrometers or more, as described in Unexamined-Japanese-Patent No. 14-82222.

If the content of this dichroic molecule in the film is too small, the polarization degree is low, and even if the content is too high, the single plate transmittance is lowered, so that the polyvinyl alcohol-based polymer constituting the matrix of the film is usually 0.01% by mass to 5% by mass. Is adjusted to the range of.

The polarizing plate of this invention may have an adhesive layer, a separate film, and a protective film as a component other than the polarizer and protective film which were mentioned above.

Next, the manufacturing process of the polarizing plate of this invention is demonstrated.

It is preferable that the manufacturing process of the polarizing plate in this invention consists of a swelling process, a dyeing process, a film-forming process, an extending process, a drying process, a protective film bonding process, and a post-bonding drying process. The order of a dyeing process, the film-forming process, and an extending process may be changed arbitrarily, and you may carry out combining several processes simultaneously. In addition, as described in Japanese Patent No. 3316615, washing with water after the dura film step can also be preferably performed.

In the present invention, it is particularly preferable to sequentially perform the swelling step, the dyeing step, the dura mating / extending step, the drying step, the protective film laminating step, and the drying step after the lamination in the order described. In addition, you may provide an online surface shape inspection process during or after the process mentioned above.

Although it is preferable to perform swelling process only with water, as described in Unexamined-Japanese-Patent No. 10-153709, boric acid is used for boric acid for a polarizing plate base material in order to stabilize optical performance and to avoid wrinkle generation of a polarizing plate base material in a manufacturing line. Swelling by aqueous solution can also manage swelling degree of a polarizing plate base material.

Moreover, although the temperature and time of a swelling process can be arbitrarily determined, 10 second or more and 60 degrees C or less, 5 second or more and 2000 second or less are preferable.

The dyeing process can use the method of Unexamined-Japanese-Patent No. 2002-86554. In addition, as a dyeing method, not only immersion but arbitrary means, such as application | coating or spraying of an iodine or dye solution, are possible. Moreover, as described in Unexamined-Japanese-Patent No. 13-290025, you may use the method of dyeing, stirring, the density | concentration of iodine, dye bath temperature, the draw ratio in a bath, and the bath liquid in a bath.

When using higher order iodine ion as a dichroic molecule, in order to obtain a high contrast polarizing plate, it is preferable to use the liquid which melt | dissolved iodine in the aqueous solution of potassium iodide for a dyeing process. In this case, the mass ratio of iodine to 0.05 to 20 g / l, potassium iodide to 3 to 200 g / l, and iodine and potassium iodide in the aqueous solution of iodide-potassium iodide is preferably in a range of 1 to 2000. 10-1200 second of dyeing time is preferable, and 10-60 degreeC of liquid temperature is preferable. More preferably, 0.5-2 g / l of iodine, 30-120 g / l of potassium iodide, the mass ratio of iodine and potassium iodide are 30-120 are preferable, dyeing time is 30-600 second, liquid temperature is 20-50 C is preferred.

As described in Japanese Patent No. 3145747, boron-based compounds such as boric acid and borax may be added to the dyeing solution.

It is preferable that a film formation process is immersed in a crosslinking agent solution, or apply | coats a solution and contains a crosslinking agent. Moreover, as described in Unexamined-Japanese-Patent No. 11-52130, a dura film process can also be performed in several times.

As the crosslinking agent, those described in the specification of U.S. Patent Publication No. 232897 can be used, and as described in Japanese Patent No. 3357109, polyhydric aldehyde may be used as the crosslinking agent in order to improve the dimensional stability. It is preferably used.

When using boric acid as a crosslinking agent used for a film-forming process, you may add a metal ion to boric-acid potassium iodide aqueous solution. Although zinc chloride is preferable as the metal ion, zinc salts such as zinc halides such as zinc iodide, zinc sulfate, and zinc acetate may be used instead of zinc chloride, as described in JP-A-2000-35512.

In this invention, it is preferable to produce the boric-acid potassium iodide aqueous solution which added zinc chloride, and to immerse a PVA film, and to perform a film film. The boric acid is preferably 1 to 100 g / l, the potassium iodide to 1 to 120 g / l, the zinc chloride is preferably 0.01 to 10 g / l, the film formation time is 10 to 1200 seconds, and the liquid temperature is preferably 10 to 60 ° C. More preferably, the boric acid is preferably 10 to 80 g / l, the potassium iodide is 5 to 100 g / l, the zinc chloride is 0.02 to 8 g / l, the film formation time is 30 to 600 seconds, and the liquid temperature is 20 to 50 ° C. desirable.

(보호막 접합 시의 편광자 폭/최종 욕을 나왔을 때의 편광자 폭)

0.95 로 하는 것도 바람직하게 행할 수 있다.As the stretching step, a longitudinal uniaxial stretching method as described in US Patent No. 2,454,515 or the like, or a tenter method as described in JP-A-2002-86554 can be preferably used. Preferable draw ratio is 2 times or more and 12 times or less, More preferably, they are 3 times or more and 10 times or less. In addition, the relationship between a draw ratio, a disk thickness, and a polarizer thickness is set as (polarizing film thickness / film thickness after protective film bonding) * (total draw ratio)> 0.17 described in Unexamined-Japanese-Patent No. 14-040256, or it is final. The relationship between the width of the polarizer at the time of bathing and the width of the polarizer at the time of protective film bonding is 0.80 described in Japanese Patent Application Laid-Open No. 14-040247.

(Polarizer width at the time of leaving polarizer width / last bath at the time of protective film bonding)

It can also be preferably set to 0.95.

A(편광자 막두께)/B(보호막 막두께)

0.16 의 범위로 하는 것도 바람직하다. As a preferable film thickness of a polarizer, 5 micrometers-40 micrometers are preferable, More preferably, they are 10 micrometers-37 micrometers. The ratio of the thickness of a polarizer and the thickness of the protective film mentioned later is 0.01 described in Unexamined-Japanese-Patent No. 14-174727.

A (polarizer film thickness) / B (protective film thickness)

It is also preferable to set it as the range of 0.16.

Moreover, it is preferable that it is 3 micrometers or less, and, as for the film thickness difference of the width direction of a polarizer, it is more preferable that it is 2 micrometers or less. If the film thickness of the polarizer is thick, the transmittance is lowered. Therefore, when the polarizer film thickness is large in the width direction, the polarizing plate is greatly different in transmittance in the width direction, and when used in a liquid crystal display device, bright portions and dark portions are formed on the same screen. As a result of experiments by the present inventors, it was found that the following relations exist between the polarizer film thickness difference and the screen uniformity. If the polarizer film thickness difference is larger than 3 µm, the screen uniformity is deteriorated, which is not preferable.

Polarizer Thickness  Car screen uniformity

0㎛ ◎

1㎛ ◎

2㎛ ◎

3㎛ ○

4 μm ×

5 μm ×

6 μm ××

[Screen Uniformity Evaluation]

(Double-circle): Any part of a screen is the same brightness, and uniformity is very good.

(Circle): On the screen, when it sees well, the part which looks a little dark is confirmed.

×: There is a dark part on the screen.

××: The dark part is clearly seen on the screen.

Moreover, it is also preferable that the maximum value of the film thickness difference between arbitrary 1 cm of the width direction of a polarizer is 0.25 micrometer / cm or less. If there is a difference of 0.25 µm / cm or more, the magnitude of the transmittance is drastically changed, and the contrast on the screen is conspicuous, which is not preferable.

As a method for producing a polarizing plate having a small polarizer film thickness difference in the width direction as in the present invention, the method of preheating by applying a temperature gradient in the width direction of the PVA film and the stretching step before the stretching step, the width-fixed stretching, the biaxial stretching, etc. The method to make it into consideration is considered.

The preheating by applying a temperature gradient in the width direction of the PVA film before the stretching step is effective in heating the edge portion in which the polarizer film thickness becomes thick before stretching, so that the edge portion is soft and easily stretched. Can be reduced.

In addition, width-fixed stretching means extending | stretching, keeping an ear end using a pinch guider, a cross guider, a tenter clip, an expander roll, a spiral roll, etc., and contract | contracts in the width direction of an ear end part. You can extend while preventing.

In addition, biaxial stretching means extending | stretching to two directions of a longitudinal direction and a horizontal direction, simultaneous biaxial stretching may be sufficient, and sequential biaxial stretching may be sufficient as it. In the case of biaxial stretching, the longitudinal direction is preferably 2 times or more and 12 times or less, preferably 3 times or more and 10 times or less, and the width direction is preferably stretched in the range of 1 to 2 times. .

In this invention, the width direction of a polarizing plate means the direction orthogonal to the extending | stretching direction (conveying direction) of a polarizer. The total width of the roll-shaped polarizing plate is preferably 400 mm to 3000 mm, more preferably 600 mm to 2000 mm, and even more preferably 800 mm to 1600 mm. If the total width of the roll-shaped polarizing plate is 400 mm or less, it will be impossible to cut a large size, and if it is 3000 mm or more, it will be difficult to maintain and the production aptitude will be insufficient.

Although the method known in Unexamined-Japanese-Patent No. 2002-86554 can be used for a drying process, the preferable temperature range is 30 degreeC-100 degreeC, and a preferable drying time is 30 second-60 minutes. In addition, as described in Japanese Patent No. 3148513, a heat treatment is performed in which the water color fading temperature is 50 ° C. or higher, or described in Japanese Patent Laid-Open No. 7-325215 or Japanese Patent Laid-Open No. 7-325218. As described above, aging in an atmosphere in which temperature and humidity are managed can also be preferably performed.

A protective film bonding process is a process of bonding both surfaces of the above-mentioned polarizer which passed through the drying process with two protective films. The method of bonding with a pair of rolls is used preferably so that an adhesive liquid may be supplied just before bonding and superimpose a polarizer and a protective film. In addition, as described in Japanese Unexamined Patent Application Publication Nos. 2001-296426 and 2002-86554, in order to suppress groove-shaped irregularities in the record resulting from the stretching of the polarizer, the moisture content of the polarizer at the time of bonding is adjusted. It is preferable to adjust. In the present invention, a water content of 0.1% to 30% is preferably used.

Although the adhesive agent of a polarizer and a protective film is not specifically limited, PVA system resin (including modified PVA, such as an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group), aqueous solution of a boron compound, etc. are mentioned, Especially, PVA system resin is mentioned. Is preferred. 0.01-5 micrometers is preferable and, as for an adhesive bond layer thickness, 0.05-3 micrometers is especially preferable.

Moreover, in order to improve the adhesive force of a polarizer and a protective film, it is preferable to adhere | attach a protective film after surface-treating and making it hydrophilic. Although the surface treatment method does not have a restriction | limiting in particular, A well-known method, such as a saponification method using an alkaline solution and a corona treatment method, can be used. Moreover, you may form easily bonding layers, such as a gelatin undercoat layer, after surface treatment. As described in JP-A-H2-267839, the contact angle with water on the surface of the protective film is preferably 50 ° or less.

Although the drying conditions after bonding are based on the method of Unexamined-Japanese-Patent No. 2002-86554, the preferable temperature range is 30 degreeC-100 degreeC, and a preferable drying time is 30 second-60 minutes. Moreover, as described in Unexamined-Japanese-Patent No. 7-325220, it is also preferable to age in the atmosphere which controlled temperature-humidity.

It is preferable that element content in a polarizer is 0.1-3.0 g / m <2> of iodine, 0.1-5.0 g / m <2> of boron, 0.1-2.0 g / m <2> of potassium, and 0-2.0 g / m <2> of zinc. In addition, potassium content may be 0.2 mass% or less as described in Unexamined-Japanese-Patent No. 13-166143, and zinc content in a polarizer is 0.04 mass%-0.5 described in Unexamined-Japanese-Patent No. 12-35512. It is good also as mass%.

As described in Japanese Patent No. 3323255, in order to increase the dimensional stability of the polarizing plate, the organic titanium compound and / or the organic zirconium compound are added and used in any one of the dyeing step, the stretching step, and the dura film step. It may contain one or more compounds selected from titanium compounds and organic zirconium compounds. Moreover, in order to adjust the color of a polarizing plate, you may add a dichroic dye.

From the roll-shaped polarizing plate obtained as mentioned above, it can cut out to the suitable size matched with a liquid crystal display panel etc., for example. In particular, in the VA mode and the IPS mode polarizing plate, in order to bond the absorption axis of the polarizing plate to 0 ° or 90 ° with respect to the sides of the liquid crystal panel, the sides of the polarizing plate are cut out in parallel so that the yield of the polarizing plate to be cut out is high and without waste. A sample can be taken and can be used even around the circumference which was not used conventionally.

(Cellulose acylate film)

Next, the cellulose acylate used in the present invention will be described in detail. In the present invention, two or more different cellulose acylates may be mixed and used.

The cellulose acylate is a mixed fatty acid ester of cellulose obtained by substituting a hydroxyl group of cellulose with an acetyl group and an acyl group having 3 or more carbon atoms, and the degree of substitution of cellulose with the hydroxyl group satisfies the following formulas (III) and (IV): Cellulose acylate.

A+B

3.0Formula (III): 2.0

A + B

3.0

Formula (IV): 0 <B

Here, in formula, A and B show the substitution degree of the acyl group substituted by the hydroxyl group of cellulose, A is the substitution degree of an acetyl group, and B is the substitution degree of the acyl group of 3 or more carbon atoms.

The β-1 and 4-bonded glucose units constituting cellulose have free hydroxyl groups on the 2nd, 3rd and 6th positions. A cellulose acylate is a polymer (polymer) which esterified some or all of these hydroxyl groups by the acyl group. Acyl substitution degree means the ratio (100% esterification is substitution degree 1) which cellulose is esterifying about 2nd, 3rd, and 6th positions, respectively.

In this invention, the sum total of substitution degree of A and B of hydroxyl group (A + B) is 2.0-3.0, Preferably it is 2.2-2.9, Especially preferably, it is 2.40-, as shown in said Formula (III). 2.85. In addition, as shown in said Formula (IV), substitution degree of B is preferable to be larger than 0, and it is more preferable that it is 0.6 or more.

If A + B is less than 2.0, hydrophilicity becomes strong and it becomes easy to be influenced by environmental humidity.

In addition, it is preferable that 28% or more of B is a substituent of the 6th hydroxyl group, but more preferably 30% or more is a substituent of the 6th hydroxyl group, more preferably 31% or more, particularly 32% or more of the 6th hydroxyl group. It is preferable that it is a substituent.

Moreover, it is preferable that the sum total of substitution degree of A and B of 6th position of a cellulose acylate is 0.75 or more, 0.80 or more are more preferable, and 0.85 or more are especially preferable. By these cellulose acylate films, the solution for film preparation with preferable solubility and filterability can be manufactured, and also the production of a favorable solution is possible also in a non-chlorine organic solvent. Further, a solution having a low viscosity and good filterability can be produced.

In addition, when a cellulose acylate film is a protective film arrange | positioned at the liquid crystal cell side of a polarizing plate, substitution degree by the acyl group of the 2nd hydroxyl group of the glucose unit which comprises a cellulose is DS2, substitution degree by the acyl group of the hydroxyl group of 3rd is DS3 When the degree of substitution by the acyl group of the hydroxyl group on the 6th position is DS6, the following formulas (V) and (VI) are preferably satisfied.

DS2+DS3+DS6

3.0Formula (V): 2.0

DS2 + DS3 + DS6

3.0

0.315Formula (VI): DS6 / (DS2 + DS3 + DS6)

0.315

By satisfy | filling said Formula (V) and (VI), it becomes easy to adjust optical performance to a preferable range, and it is preferable.

The acyl group having 3 or more carbon atoms may be an aliphatic group or an aromatic hydrocarbon group, and is not particularly limited. They are alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc. of cellulose, for example, and may have a substituted group, respectively. Preferred acyl groups having 3 or more carbon atoms include propionyl, butanoyl, butanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso- Butanoyl, t-butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among them, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like are preferable. Especially preferably, they are propionyl and butanoyl group. In addition, in the case of a propionyl group, it is preferable that substitution degree (B) is 1.3 or more.

Specific examples of the mixed fatty acid cellulose acylate include cellulose acetate propionate and cellulose acetate butyrate.

(Synthesis method of cellulose acylate)

The basic principle of the method for synthesizing cellulose acylate is described in Migita et al., Pages 180 to 190 of wood chemistry (Kyoritsu Publication, 1968). A typical synthesis method is a liquid acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst.

Specifically, in order to obtain the cellulose acylate, cellulose raw materials such as cotton linter and wood pulp are pretreated with an appropriate amount of acetic acid, and then added to a pre-cooled carboxylated liquid mixture to be esterified and completely cellulose acylate (second place). , The sum of the acyl substitution degrees at the 3rd and 6th positions synthesizes almost 3.00). The said carboxylated liquid mixture generally contains acetic acid as a solvent, anhydrous carboxylic acid as an esterifying agent, and sulfuric acid as a catalyst. Carboxylic anhydride is usually used in an excess amount stoichiometrically than the sum total of the cellulose which reacts with this, and the moisture which exists in a system. After completion of the esterification reaction, neutralizing agents (e.g., carbonates, acetates or oxides of calcium, magnesium, iron, aluminum or zinc) for the hydrolysis of excess anhydrous carboxylic acid remaining in the system and for the neutralization of part of the esterification catalyst An aqueous solution of) is added. Next, the obtained cellulose acylate is saponified by maintaining at 50 to 90 ° C in the presence of a small amount of an acetylation reaction catalyst (typically, sulfuric acid remaining), and a cellulose having a desired acyl substitution degree and a degree of polymerization. Change to acylate. At the point where the desired cellulose acylate is obtained, the cellulose acylate solution is introduced into water or dilute sulfuric acid (or cellulose acylate) without neutralizing the catalyst remaining in the system completely or using neutralizing agent as described above. The specific cellulose acylate can be obtained by injecting water or dilute sulfuric acid into the late solution, separating the cellulose acylate, performing washing and stabilization treatment, and the like.

It is preferable that the said cellulose acylate film consists of the said specific cellulose acylate substantially the polymer component which comprises a film. "Substantially" means 55 mass% or more (preferably 70 mass% or more, more preferably 80 mass% or more) of a polymer component.

It is preferable to use the said cellulose acylate in particulate form. It is preferable that 90 mass% or more of the particle | grains used have a particle diameter of 0.5-5 mm. Moreover, it is preferable that 50 mass% or more of the particle to use has a particle diameter of 1-4 mm. It is preferable that a cellulose acylate particle has a shape as close to a spherical shape as possible.

The degree of polymerization of the cellulose acylate used preferably in the present invention is a viscosity average degree of polymerization, preferably 200 to 700, more preferably 250 to 550, still more preferably 250 to 400, and particularly preferably 250 to 350 to be. The average degree of polymerization can be measured by an intrinsic viscosity method such as Uchida (Kazuo Uchida, Hideo Saito, Textile Society, 1962, Vol. 18, No. 1, pages 105 to 120). It is also described in detail in Japanese Patent Laid-Open No. 9-95538.

When the low molecular weight component is removed, the average molecular weight (polymerization degree) increases, and since the viscosity is lower than that of the usual cellulose acylate, it is useful to remove the low molecular weight component as the cellulose acylate. The cellulose acylate with few low molecular weight components can be obtained by removing a low molecular weight component from the cellulose acylate synthesize | combined by a conventional method. Removal of the low molecular weight component can be performed by washing a cellulose acylate with a suitable organic solvent. Moreover, when manufacturing the cellulose acylate with few low molecular 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 acylates. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate (uniform in molecular weight distribution) that is preferable also in terms of molecular weight distribution can be synthesized. When used at the time of manufacture of a cellulose acylate, it is preferable that the moisture content is 2 mass% or less, More preferably, it is 1 mass% or less, Especially preferably, it is 0.7 mass% or less. Generally, cellulose acylate contains water and 2.5-5 mass% of water content 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.

The raw material surface and the synthesis method of the said cellulose acylate are the raw material surface and the synthesis method which are described in detail in p.7-12 of the invention association publication publication No. 2001-1745 (published March 15, 2001, invention association). It can be adopted.

The cellulose acylate film which concerns on this invention can be obtained by film-forming using the said specific cellulose acylate and the solution which melt | dissolved the additive in the organic solvent as needed.

(additive)

As an additive which can be used for the said cellulose acylate solution in this invention, a plasticizer, a ultraviolet absorber, a deterioration inhibitor, a retardation (optical anisotropy) expression agent, a retardation (optical anisotropy) reducing agent, a microparticle, peeling A promoter, an infrared absorber, etc. are mentioned. In this invention, it is preferable to use a retardation expression agent. Moreover, it is preferable to use 1 or more types of a plasticizer, a ultraviolet absorber, and a peeling accelerator.

These may be solid or oily matter. That is, it is not specifically limited in the melting point or boiling point. For example, 20 degrees C or less and the ultraviolet absorber 20 degreeC or more can be used in mixture, or a plasticizer can be mixed and used similarly, for example, are described in Unexamined-Japanese-Patent No. 2001-151901.

As a ultraviolet absorber, arbitrary kinds of things can be selected according to the objective, Absorbers, such as a salicylic acid ester type, a benzophenone type, a benzotriazole type, a benzoate type, a cyanoacrylate type, a nickel complex salt type, can be used, Preferably, they are benzophenone series, benzotriazole series, and salicylic acid ester system. Examples of the benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-di- Hydroxy-4-methoxybenzophenone, 2,2'-di-hydroxy-4,4'-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4 -Dodecyloxy benzophenone, 2-hydroxy-4- (2-hydroxy-3- methacryloxy) propoxy benzophenone, etc. are mentioned. As a benzotriazole type ultraviolet absorber, 2 (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2 (2'-hydroxy-5'-tert- Butylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2 (2'-hydroxy-3', 5'-di-tert- Butylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, etc. are mentioned. As salicylic acid ester type, phenyl salicylate, p-octylphenyl salicylate, p-tert- butylphenyl salicylate, etc. are mentioned. Among these exemplified ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, 2,2'-di-hydroxy-4,4'-methoxybenzophenone and 2 (2'-hydroxy-3 ' -tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5 Particular preference is given to '-di-tert-amylphenyl) benzotriazole, 2 (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole.

The ultraviolet absorber is preferably used by combining a plurality of absorbents having different absorption wavelengths, since a high blocking effect can be obtained in a wide wavelength range. It is preferable that the ultraviolet absorber for liquid crystals is excellent in the absorption ability of the ultraviolet-ray with a wavelength of 370 nm or less from the point of the prevention of deterioration of a liquid crystal, and in the liquid crystal display property, the absorption of visible light with a wavelength of 400 nm or more is preferable. Especially preferable ultraviolet absorbers are the above-mentioned benzotriazole type compound, a benzophenone type compound, and a salicylic acid ester type compound. Especially, since the benzotriazole type compound has little unnecessary coloring with respect to a cellulose ester, it is preferable.

In addition, regarding a ultraviolet absorber, Unexamined-Japanese-Patent No. 60-235852, Unexamined-Japanese-Patent No. 3-199201, 5-5-7077073, 5-5-789789, 5-271471, 6-107854 No. 6-118233, No. 6-148430, No. 7-11056, No. 7-11055, No. 7-11056, No. 8-29619, No. 8-239509, Japanese Laid-Open Patent Publication 2000- The compound described in each publication of 204173 can also be used.

0.001-5 mass% is preferable with respect to cellulose acylate, and, as for the addition amount of a ultraviolet absorber, 0.01-1 mass% is more preferable. If the addition amount is less than 0.001% by mass, the effect of addition cannot be sufficiently exhibited. If the addition amount is more than 5% by mass, the ultraviolet absorber may bleed out on the film surface.

In addition, a ultraviolet absorber may be simultaneously added at the time of cellulose acylate melt | dissolution, and may be added to the dope after melt | dissolution. In particular, a form in which the ultraviolet absorber solution is added to the dope immediately before the casting using a static mixer or the like is preferable because the spectral absorption characteristics can be easily adjusted.

The said antideterioration agent can prevent a cellulose triacetate etc. from degrading and decomposing. As a deterioration inhibitor, a butylamine, a hindered amine compound (Unexamined-Japanese-Patent No. 8-325537), a guanidine compound (Japanese Unexamined-Japanese-Patent No. 5-271471), a benzotriazole type UV absorber (Japanese Unexamined Patent Publication No. 6) -235819), and a benzophenone UV absorber (Japanese Patent Laid-Open No. Hei 6-118233).

As a plasticizer, it is preferable that they are phosphate ester and carboxylic acid ester. Moreover, the said plasticizer is triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate (BDP), trioctyl phosphate, tributyl phosphate, dimethyl phthalate (DMP), diethylphthalate (DEP), dibutylphthalate (DBP), dioctylphthalate (DOP), diphenylphthalate (DPP), diethylhexylphthalate (DEHP), O-acetyl citrate triethyl (OACTE), O-acetyl tributyl citrate (OACTB), acetyl triethyl citrate, acetyl tributyl citrate, butyl oleate, methyl acetyl ricinate, dibutyl sebacate, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl It is more preferable that it is selected from ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. Moreover, it is preferable that the said plasticizer is (di) pentaerythritol ester, glycerol ester, and diglycerol ester.

Examples of the peeling accelerator include ethyl esters of citric acid. Moreover, as an infrared absorber, it is described, for example in Unexamined-Japanese-Patent No. 2001-194522.

Moreover, in this invention, you may add the dye for color adjustment. 10-1000 ppm is preferable at mass ratio with respect to cellulose acylate, and, as for content of dye, 50-500 ppm is more preferable. By containing dye in this way, the light piping of a cellulose acylate film can be reduced and yellow can be improved. These compounds may be added together with a cellulose acylate and a solvent at the time of preparation of a cellulose acylate solution, and may be added in solution preparation or after preparation. Moreover, you may add to the ultraviolet absorber liquid added inline.

The dye used in the present invention is preferably a compound represented by the following general formula (I) or (II).

Formula (I)

In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are a hydrogen atom, a hydroxyl group, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, a cyano group, and a nitro, respectively , COR ⁹ , COOR ⁹ , NR ⁹ R ¹⁰ , NR ¹⁰ COR ¹¹ , NR ¹⁰ SO ₂ R ¹¹ , CONR ⁹ R ¹⁰ , SO ₂ NR ⁹ R ¹⁰ , COR ¹¹ , SO ₂ R ¹¹ , OCOR ¹¹ , NR ⁹ CONR ¹⁰ R ¹¹ , CONHSO ₂ R ¹¹ , and SO ₂ NHCOR ¹¹ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R ¹¹ represents an aliphatic group, an aromatic group, or a heterocyclic group. R ⁹ and R ¹⁰ may be bonded to each other to form a 5 or 6 membered ring, and R ¹ and R ² or R ² and R ³ may be linked to each other to form a ring.

General formula (II)

Wherein, R ^21, R ^23, R ²⁴ is a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, an aliphatic group, an aromatic ^{group, COR 29, COOR 29, NR} 29 R 30, NR 30 COR 31, NR 30 SO 2 R represents ^31, R ²² represents an aliphatic group or an aromatic, R ^29, R ³⁰ are as defined and R ^9, R ¹⁰ in the formula (I), R ³¹ is and R ¹¹ in the formula (I) It is the same meaning. However, at least one of R ²¹ , R ²² , R ²³ and R ²⁴ is a group other than hydrogen.

Each group of general formula (I) is demonstrated in detail below. The aliphatic group represented by R ¹ to R ¹¹ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, isopropyl, 2-ethylhexyl, n-decyl, n-octadecyl), and carbon 1 A cycloalkyl group (eg, cyclopentyl, cyclohexyl) or an allyl group of ˜20, and a substituent [eg, a halogen atom (eg, F, Cl, Br, I), a hydroxyl group, a cyano group, a nitro group , A carboxylic acid group, an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl), an amino group having 0 to 20 carbon atoms (eg, NH ₂ , NHCH ₃ , N (C ₂ H ₅ ) ₂ , N ( C ₄ H ₉ ) ₂ , N (C ₈ H ₁₇ ) ₂ , anilino, 4-methoxyanilino, an amide group having 1 to 20 carbon atoms (eg, acetylamino, hexanoylamino, benzoylamino, octa Decanoylamino), a carbamoyl group having 1 to 20 carbon atoms (e.g., unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, octylcarbamoyl, hexadecylcarbamoyl), 2 carbon atoms 20 ester groups (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, n-butoxycarbonyl, dodecyloxycarbonyl), alkoxy groups having 1 to 20 carbon atoms or aryloxy groups ( Methoxy, ethoxy, butoxy, isopropoxy, benzyloxy, phenoxy, octadecyloxy), sulfonamide groups having 1 to 20 carbon atoms (e.g. methanesulfonamide, ethanesulfonamide, butanesulfonamide, Benzenesulfonamide, octanesulfonamide), sulfamoyl groups having 0 to 20 carbon atoms (e.g., unsubstituted sulfamoyl, methylsulfamoyl, butylsulfamoyl, decylsulfamoyl), 5 or 6 membered heterocycles (eg For example, pyridyl, pyrazolyl, morpholino, piperidino, pyrrolino, benzoxazolyl) may be used.

The aromatic group represented by R ¹ to R ¹¹ represents an aryl group having 6 to 10 carbon atoms (for example, phenyl and naphthyl), and a substituent [for example, each group exemplified as the substituent which the aliphatic group described above may have. In addition, it may have a C1-C20 alkyl group (for example, methyl, ethyl, butyl, t-butyl, octyl).

The heterocyclic group represented by R ¹ to R ¹¹ is a 5 or 6 membered heterocyclic ring (for example, pyridine, piperidine, morpholine, pyrrolidine, pyrazole, pyrazolidine, pyrazoline, pyrazolone, benz Oxazole), and may have a substituent (for example, each group mentioned as a substituent which the said aromatic group may have).

As a 5 or 6 membered ring formed by connecting R <^9> and R <^10> , a morpholine ring, a piperidine ring, and a pyrrolidine ring are mentioned. As a ring formed by connecting R <^1> and R <^2> or R <^2> and R <^3> , a 5 or 6 membered ring (for example, a benzene ring and a phthalimide ring) is preferable.

Next, each group of general formula (II) is demonstrated. The aliphatic group represented by R ²¹ to R ²⁴ has the same meaning as the aliphatic group represented by R ¹ to R ¹¹ in General Formula (I), and the aromatic group represented by R ²¹ to R ²⁴ is R in General Formula (I). ^It is the same meaning as the aromatic group which ^{1-R < 11>} represents.

Although the timing of adding these additives may be added at any time in the 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 expresses. In addition, when a cellulose acylate film is a multilayer, 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. Depending on the type of these additives and the amount of addition, the glass transition point (Tg) measured by the dynamic viscoelasticity measuring instrument (Vibron: DVA-225 (manufactured by Haiti Metrology Control Co., Ltd.)) of the cellulose acylate film is 70 to 150 ° C. More preferably, it is preferable to make glass transition point (Tg) into 80-135 degreeC. In other words, the cellulose acylate film which concerns on this invention is a glass front in terms of process suitability of polarizing plate processing and liquid crystal display device assembly. It is preferable to make advantage (Tg) into the said range.

In addition, about the additive, what was described in detail after p.16 of the invention association publication Unexamined-Japanese-Patent No. 2001-1745 (March 15, 2001, invention association) p. 16 can be used suitably.

(Retardation expression agent)

In this invention, in order to express optically anisotropy largely and to implement a preferable retardation value, it is preferable to use a retardation expression agent.

As a retardation expression agent which can be used in this invention, what consists of a rod-shaped or disk shaped compound is mentioned.

As the rod-shaped or disk-shaped compound, a compound having two or more aromatic rings can be used.

It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components containing a cellulose acylate, and, as for the addition amount of the retardation expression agent which consists of a rod-shaped compound, it is more preferable that it is 0.5-20 mass parts.

It is preferable to use a disc shaped retardation expression agent in 0.05-30 mass parts with respect to 100 mass parts of polymer components containing the said cellulose acylate, It is more preferable to use in the range of 0.1-20 mass parts, It is more preferable to use in the range of 0.2-15 mass parts, and it is most preferable to use in the range of 0.5-10 mass parts.

Since the disk-shaped compound is superior to the rod-shaped compound in Rth retardation expressability, it is preferably used especially when a large Rth retardation is required.

You may use together two or more types of retardation expression agents.

It is preferable that the said retardation expression agent which consists of a rod-shaped or disk shaped compound has maximum absorption in the wavelength range of 250-400 nm, and it is preferable that it does not have absorption in a visible region substantially.

A disk shaped compound is demonstrated. As the disk shaped compound, a compound having two or more aromatic rings can be used.

In the present specification, the "aromatic ring" includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.

It is especially preferable that an aromatic hydrocarbon ring is a 6-membered ring (that is, a benzene ring).

Aromatic heterocycles are generally unsaturated heterocycles. It is preferable that it is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and, as for an aromatic hetero ring, it is more preferable that it is a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the largest number of double bonds. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, and a nitrogen atom is especially preferable. Examples of aromatic hetero rings include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazine ring, triazole ring, pyran ring, pyridine ring, Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

As the aromatic ring, benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring Preferably, the 1,3,5-triazine ring is used preferably. Specifically, for example, the compound disclosed in JP 2001-166144 A is preferably used as a disk-shaped compound.

It is preferable that the number of the aromatic rings which the said disk shaped compound has is 2-20, It is more preferable that it is 2-12, It is further more preferable that it is 2-8, It is most preferable that it is 2-6.

The bonding relationship between two aromatic rings can be classified into (a) forming a condensed ring, (b) directly connecting to a single bond, and (c) bonding through a linking group (because of aromatic rings, spiro bonding). Cannot form). The coupling relationship may be any of (a) to (c).

Examples of the condensed ring (condensed ring of two or more aromatic rings) of (a) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, a naphthacene ring , Pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolidine ring, benzoxazole ring, benzothiazole ring, benzoimidazole ring, benzotriazole ring, purine ring, indazole ring, chromen ring, Quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, sinoline ring, quinoxaline ring, putaladine ring, puteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothia A ring, a phenoxatiin ring, a phenoxadine ring, and a thianthrene ring. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzoimidazole ring, benzotriazole ring and quinoline ring are preferable.

It is preferable that the single bond of (b) is a bond between carbon atoms of two aromatic rings. Two or more single bonds may combine two aromatic rings, and may form an aliphatic ring or a non-aromatic heterocycle between the two aromatic rings.

It is preferable that the linking group of (c) couple | bonds with the carbon atom of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, -CO-, -0-, -NH-, -S-, or a combination thereof. An example of the coupling group which consists of a combination is shown below. In addition, the relationship of the left and right of the example of the following coupler may be reversed.

c1: -CO-O-

c2: -CO-NH-

c3: -alkylene-O-

c4: -NH-CO-NH-

c5: -NH-CO-O-

c6: -O-CO-O-

c7: -O-alkylene-O-

c8: -CO-alkenylene-

c9: -CO-alkenylene-NH-

c10: -CO-alkenylene-O-

c11: -alkylene-CO-O-alkylene-O-CO-alkylene-

c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-

c13: -O-CO-alkylene-CO-O-

c14: -NH-CO-alkenylene-

c15: -O-CO-alkenylene-

The aromatic ring and the linking group may have a substituent.

Examples of the substituent include halogen atom (F, C1, Br, I), hydroxyl group, carboxyl group, cyano group, amino group, nitro group, sulfo group, carbamoyl group, sulfamoyl group, ureido group, alkyl group, alkenyl group , Alkynyl group, aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamide group, aliphatic substituted amino group, aliphatic substituted carbamoyl group , Aliphatic substituted sulfamoyl groups, aliphatic substituted ureido groups, and non-aromatic heterocyclic groups.

It is preferable that carbon number of an alkyl group is 1-8. A chain alkyl group is more preferable than a cyclic alkyl group, and a linear alkyl group is especially preferable. The alkyl group may further have a substituent (for example, a hydroxyl group, a carboxy group, an alkoxy group, an alkyl substituted amino group). Examples of the alkyl group (including a substituted alkyl group) include methyl group, ethyl group, n-butyl group, n-hexyl group, 2-hydroxyethyl group, 4-carboxybutyl group, 2-methoxyethyl group and 2-diethylaminoethyl group Included.

It is preferable that carbon number of an alkenyl group is 2-8. A linear alkenyl group is more preferable than a cyclic alkenyl group, and a linear alkenyl group is especially preferable. The alkenyl group may further have a substituent. Examples of the alkenyl group include a vinyl group, allyl group, and 1-hexenyl group.

It is preferable that carbon number of an alkynyl group is 2-8. A linear alkynyl group is more preferable than a cyclic alkynyl group, and a linear alkynyl group is especially preferable. The alkynyl group may further have a substituent. Examples of the alkynyl group include an ethynyl group, 1-butynyl group and 1-hexynyl group.

It is preferable that carbon number of an aliphatic acyl group is 1-10. Examples of aliphatic acyl groups include acetyl groups, propanoyl groups and butanoyl groups.

It is preferable that carbon number of an aliphatic acyloxy group is 1-10. Examples of aliphatic acyloxy groups include acetoxy groups.

It is preferable that carbon number of an alkoxy group is 1-8. The alkoxy group may further have a substituent (for example, an alkoxy group). Examples of the alkoxy group (including a substituted alkoxy group) include a methoxy group, an ethoxy group, a butoxy group and a methoxyethoxy group.

It is preferable that carbon number of an alkoxycarbonyl group is 2-10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

It is preferable that carbon number of the alkoxycarbonylamino group is 2-10. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group.

It is preferable that carbon number of an alkylthio group is 1-12. Examples of the alkylthio group include methylthio group, ethylthio group and octylthio group.

It is preferable that carbon number of an alkylsulfonyl group is 1-8. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group.

It is preferable that carbon number of an aliphatic amide group is 1-10. Examples of aliphatic amide groups include acetamide groups.

It is preferable that carbon number of an aliphatic sulfonamide group is 1-8. Examples of aliphatic sulfonamide groups include methanesulfonamide groups, butanesulfonamide groups, and n-octanesulfoamide groups.

It is preferable that carbon number of an aliphatic substituted amino group is 1-10. Examples of the aliphatic substituted amino group include a dimethylamino group, diethylamino group and 2-carboxyethylamino group.

It is preferable that carbon number of an aliphatic substituted carbamoyl group is 2-10. Examples of aliphatic substituted carbamoyl groups include methylcarbamoyl groups and diethylcarbamoyl groups.

It is preferable that carbon number of an aliphatic substituted sulfamoyl group is 1-8. Examples of the aliphatic substituted sulfamoyl group include a methyl sulfamoyl group and a diethyl sulfamoyl group.

It is preferable that carbon number of an aliphatic substituted ureido group is 2-10. Examples of aliphatic substituted ureido groups include methylureido groups.

Examples of the nonaromatic heterocyclic group include a piperidino group and a morpholino group.

It is preferable that the molecular weight of the retardation expression agent which consists of a disk shaped compound is 300-800.

In the present invention, in addition to the disk-shaped compound described above, a rod-shaped compound having a linear molecular structure can also be preferably used. The linear molecular structure means that the molecular structure of the rod-shaped compound is linear in the thermodynamic most stable structure. The thermodynamic most stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, the molecular orbital calculation software (for example, WinMOPAC2000, manufactured by Fujitsu Co., Ltd.) can be used to calculate the molecular orbital to obtain the structure of the molecule in which the heat of production of the compound is the smallest. The linear molecular structure means that the angle of the main chain in the molecular structure is 140 degrees or more in the thermodynamic most stable structure calculated and calculated as described above.

As a rod-shaped compound, what has two or more aromatic rings is preferable, and as a rod-shaped compound which has two or more aromatic rings, the compound represented by following General formula (1) is preferable.

Formula (1): Ar ¹ -L ¹ -Ar ²

In General Formula (1), Ar ¹ and Ar ² are each independently an aromatic group.

In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.

An aryl group and substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of the aromatic heterocyclic group is generally unsaturated. It is preferable that it is a 5-membered ring, a 6-membered ring, or a 7-membered ring, and, as for an aromatic hetero ring, it is more preferable that it is a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the largest number of double bonds. As a hetero atom, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable.

As an aromatic ring of an aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring are preferable, and a benzene ring is especially preferable. Do.

Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amino group, an alkylamino group (eg, methylamino group, ethylamino group, butyl) Amino group, dimethylamino group), nitro group, sulfo group, carbamoyl group, alkylcarbamoyl group (e.g., N-methylcarbamoyl group, N-ethylcarbamoyl group, N, N-dimethylcarbamoyl group), sulfamoyl group , Alkyl sulfamoyl group (e.g., N-methyl sulfamoyl group, N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group), ureido group, alkyl ureido group (e.g., N-methyl ureido group, N, N -Dimethylureido group, N, N, N'-trimethylureido group, alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, isopropyl group, s-butyl group, t -Amyl group, cyclohexyl group, cyclopentyl group), alkenyl group (e.g. vinyl group, allyl group, hexenyl group), alkynyl group (e.g. ethynyl group, butynyl ), Acyl group (e.g. formyl group, acetyl group, butyryl group, hexanoyl group, lauryl group), acyloxy group (e.g. acetoxy group, butyryloxy group, hexanoyloxy group, lauryloxy group), alkoxy group (E.g., methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, heptyloxy group, octyloxy group), aryloxy group (e.g. phenoxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxy Carbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, heptyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), alkoxycarbonylamino group (e.g. butoxycarbonylamino group, hexyloxycarbonylamino group) , Alkylthio group (eg methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, heptylthio group, octylthio group), arylthio group (eg phenylthio group), alkylsulfonyl group (E.g., methylsulfonyl group, ethylsulfonyl group, propyl alcohol Nyl group, butylsulfonyl group, pentylsulfonyl group, heptylsulfonyl group, octylsulfonyl group), amide group (e.g. acetamide group, butylamide group, hexylamide group, laurylamide group) and non-aromatic heterocyclic group (e.g. Morpholinyl group, pyrazinyl group).

As a substituent of a substituted aryl group and a substituted aromatic heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a hydroxyl group, an amino group, an alkyl substituted amino group, an acyl group, an acyloxy group, an amide group, an alkoxycarbonyl group, an alkoxy group, an alkyl thi Organic and alkyl groups are preferred.

The alkyl portion and alkyl group of the alkylamino group, the alkoxycarbonyl group, the alkoxy group and the alkylthio group may further have a substituent. Examples of the substituent of the alkyl moiety and the alkyl group include halogen atom, hydroxyl, carboxyl, cyano, amino, alkylamino group, nitro, sulfo, carbamoyl, alkylcarbamoyl group, sulfamoyl, alkylsulfamoyl group, ureido , Alkylureido group, alkenyl group, alkynyl group, acyl group, acyloxy group, acylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfo Neyl group, amide group and non-aromatic heterocyclic group are included. As a substituent of an alkyl part and an alkyl group, a halogen atom, hydroxyl, amino, an alkylamino group, an acyl group, an acyloxy group, an acylamino group, an alkoxycarbonyl group, and an alkoxy group are preferable.

In General formula (1), L <^1> is a bivalent coupling group chosen from the group which consists of an alkylene group, an alkenylene group, an alkynylene group, -O-, -CO-, and its combination.

The alkylene group may have a cyclic structure. As a cyclic alkylene group, cyclohexylene is preferable and 1, 4- cyclohexylene is especially preferable. As a linear alkylene group, a linear alkylene group is more preferable than the alkylene group which has a branch.

The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6 to be.

It is preferable that an alkenylene group and an alkynylene group have a linear structure rather than a cyclic structure, and it is more preferable to have a linear structure rather than the linear structure which has a branch.

The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, still more preferably 2 to 4, and most preferably Preferably 2 (vinylene or ethynylene).

It is preferable that carbon number of an arylene group is 6-20, More preferably, it is 6-16, More preferably, it is 6-12.

In the molecular structure of General formula (1), it is preferable that the angle which Ar <^1> and Ar <^2> form between L < ¹ > is 140 degree or more.

The rod-shaped compound can be synthesized by the method described in the literature. According to the literature, Mol. Cryst, Liq. Cryst., Vol. 53, p. 229 (1979), p. 89, p. 93 (1982), p. 145, p. 111 (1987), p. 170, p. 43 (1989), J. Am. Chem. Soc., Vol. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970), J. Org. Chem., 40, 420 pages (1975), Tetrahedron, 48, 16, page 3437 (1992).

Moreover, it is more preferable to use the rod-shaped compound represented by General formula (1). The compound represented by General formula (1) below is demonstrated.

(In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent each independently, R <^1> , R <^2> , R <^3> , At least one of R ⁴ and R ⁵ represents an electron donating group, R ⁸ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, or a 1 to 12 carbon atoms. Alkoxy group, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, cyano group or halogen atom)

In general formula (1), R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent each independently, and a substituent is a substituent mentioned later (T) can be applied.

At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents an electron donating group. Preferably, one of R ¹ , R ^3, or R ⁵ is an electron donating group, and R ³ is an electron donating group.

The electron donating group indicates that the σp value of Hammet is 0 or less, and Chem. The sigma p value of Hammet described in Rev., 91, 165 (1991) is preferably 0 or less, more preferably -0.85 to 0. For example, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, etc. are mentioned.

The electron donating group is preferably an alkyl group or an alkoxy 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, and particularly preferably C1-C4).

R ¹ is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group or a hydroxyl group, still more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, Especially preferably, it is an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4), Most preferably, a methoxy group to be.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). More preferably, it is a methyl group, and an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Especially preferably, they are a hydrogen atom, a methyl group, and a methoxy group.

R ³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, still more preferably an alkyl group or an alkoxy group, and particularly preferably an alkoxy group ( Preferably it is C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Most preferably, they are n-propoxy group, an ethoxy group, and a methoxy group.

R ⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, still more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Alkoxy group of 12 (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4), Especially preferably, a hydrogen atom and carbon number It is a 1-4 alkyl group and a C1-C4 alkoxy group, Most preferably, they are a hydrogen atom, a methyl group, and a methoxy group.

R ⁵ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). More preferably, they are a methyl group, and an alkoxy group (preferably C1-C12, More preferably, it is C1-C8, More preferably, it is C1-C6, Especially preferably, it is C1-C4). Especially preferably, they are a hydrogen atom, a methyl group, and a methoxy group.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, more preferably a hydrogen atom or a halogen atom, and further Preferably it is a hydrogen atom.

R <^8> is a hydrogen atom, a C1-C4 alkyl group, a C2-C6 alkynyl group, a C6-C12 aryl group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, C2-C12 An alkoxycarbonyl group, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom, and if possible, may have a substituent, and the substituent (T) described below can be applied as the substituent.

R ⁸ is preferably 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, and an aryloxy group having 2 to 12 carbon atoms, more preferably. Is 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, and more preferably an alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms). Preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), and particularly preferably a methoxy group, an ethoxy group, an n-propoxy group and an iso-propoxy group. and n-butoxy group.

More preferably in general formula (I), it is following general formula (I-A).

General formula (I-A)

In the formula, R ¹¹ represents an alkyl group. R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent. R ⁸ represents hydrogen An atom, an alkyl group of 1 to 4 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryloxy group of 6 to 12 carbon atoms, an alkoxycarbonyl group of 2 to 12 carbon atoms, An acylamino group, a cyano group or a halogen atom having 2 to 12 carbon atoms)

In general formula (IA), R <^1> , R <^2> , R <^4> , R <^5> , R <^6> , R <^7> , R <^8> , R <^9> and R <^10> are respectively synonymous with that in general formula (I), and are also preferable The range is the same.

In General Formula (IA), R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group represented by R ¹¹ may be linear, branched, or may have a substituent, but preferably an alkyl group having 1 to 12 carbon atoms, More preferably, a C1-C8 alkyl group, More preferably, a C1-C6 alkyl group, Especially preferably, a C1-C4 alkyl group (for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group) , n-butyl group, iso-butyl group, tert-butyl group and the like).

More preferably in general formula (I), it is following general formula (I-B).

General formula (I-B)

(In formula, R <^1> , R <^2> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> represent a hydrogen atom or a substituent each independently. R <^11> represents a C1-C12 alkyl group. 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, and an alkoxycarbonyl group having 2 to 12 carbon atoms. , C2-C12 acylamino group, cyano group or halogen atom)

In general formula (IB), R <^1> , R <^2> , R <^4> , R <^5> , R <^6> , R <^7> , R <^9> and R <^10> have the same meaning as that in general formula (I), and its preferable range is also the same. .

In general formula (IB), R <^11> is synonymous with that in general formula (IA), and its preferable range is also the same.

In general formula (IB), X is a C1-C4 alkyl group, a C2-C6 alkynyl group, a C6-C12 aryl group, a C1-C12 alkoxy group, a C6-C12 aryloxy group, carbon number A C2-C12 alkoxycarbonyl group, a C2-C12 acylamino group, a cyano group, or a halogen atom is shown.

R ¹ , R ² , R ⁴ and R ⁵ When all are hydrogen atoms, X is preferably an alkyl group, an alkynyl group, an aryl group, an alkoxy group or an aryloxy group, more preferably an aryl group, an alkoxy group or an aryloxy group, still more preferably an alkoxy group (Preferably 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 ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group.

When at least one of R ¹ , R ² , R ⁴ and R ⁵ is a substituent, X is preferably an alkynyl group, an aryl group, an alkoxycarbonyl group, a cyano group, and more preferably an aryl group (preferably carbon number). 6-12), a cyano group and an alkoxycarbonyl group (preferably having 2 to 12 carbon atoms), more preferably an aryl group (preferably an aryl group having 6 to 12 carbon atoms), and more preferably a phenyl group and p-cyano Phenyl group, p-methoxyphenyl), alkoxycarbonyl group (preferably 2 to 12 carbons, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, particularly preferably methoxycarbonyl, ethoxy Carbonyl, n-propoxycarbonyl), and a cyano group, and particularly preferably, they are a phenyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, and cyano group.

More preferably in general formula (I), it is following general formula (I-C).

General formula (I-C)

Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ¹¹ And X have the same meaning as that in the general formula (IB), and the preferred range is also the same.

More preferable among the compounds represented by the general formula (I) are compounds represented by the following general formula (I-D).

General formula (I-D)

(In formula, R <^2> , R <^4> and R <^5> is synonymous with that in general formula (IC), and its preferable range is also the same. R <^21> , R <^22> is respectively independently a C1-C4 alkyl group. X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group)

R <^21> represents a C1-C4 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is an ethyl group and a methyl group.

R <^22> represents a C1-C4 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is an ethyl group and a methyl group, More preferably, it is a methyl group.

X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a cyano group, more preferably Is a phenyl group, p-cyanophenyl group, p-methoxyphenyl group, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, cyano group, More preferably, it is a phenyl group, methoxycarbonyl group, ethoxycarbonyl group , n-propoxycarbonyl group and cyano group.

Most preferably in the general formula (I) is the following general formula (I-E).

General formula (I-E)

(In formula, R <^2> , R <^4> and R <^5> is synonymous with that in general formula (ID), and although a preferable range is also the same, any one is group represented by -OR <^13> (R <^13> is carbon number R ²¹ , R ²² , and X ¹ are the same as those in the general formula (ID), and the preferred range is also the same).

In general formula (IE), R <^2> , R <^4> and R <^5> are synonymous with that in general formula (ID), and although a preferable range is also the same, any one is group represented by -OR <^13> (R ¹³ is a C1-C4 alkyl group), Preferably R <^4> and R <^5> are group represented by -OR <^13> , More preferably, R <^4> is group represented by -OR <^13> .

R <^13> represents a C1-C4 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is an ethyl group and a methyl group, More preferably, it is a methyl group.

The substituent (T) mentioned above is demonstrated below.

As a substituent (T), it is an alkyl group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably C2-C20, More preferably, C2-C20) 12, particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl, and alkynyl groups (preferably 2 to 20 carbon atoms), more preferably. Is C2-C12, Especially preferably, it is C2-C8, For example, propargyl, 3-pentynyl, etc. are mentioned, The aryl group (preferably C6-C30, More preferably, C6-C20, Especially preferably, it is C6-C12, For example, phenyl, p-methylphenyl, naphthyl, etc. are mentioned. ), A substituted or unsubstituted amino group (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, diethyl Amino, dibenzylamino, etc.), an alkoxy group (preferably C1-C20, More preferably, it is C1-C12, Especially preferably, it is C1-C8, For example, methoxy, Oxyoxy, butoxy, and the like, and an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyloxy, 2). -Naphthyloxy, etc.), an acyl group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, acetyl, benzoyl, a fort Mill, pivaloyl, etc.), alkoxycarbonyl group (wind Preferably it is C2-C20, More preferably, it is C2-C16, Especially preferably, it is C2-C12, For example, methoxycarbonyl, ethoxycarbonyl, etc. are mentioned, An aryloxycarbonyl group ( Preferably it is C7-20, More preferably, it is C7-16, Especially preferably, it is C7-10, For example, Phenyloxycarbonyl etc. are mentioned, Acyloxy group (Preferably carbon number) 2-20, More preferably, it is 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 C2-C16, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (Preferably C2-C20, More preferably Preferably 2 to 16 carbon atoms, It is preferably 2 to 12 carbon atoms, for example, methoxycarbonylamino and the like, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms). Preferably it is C7-12, For example, a phenyloxycarbonylamino etc. are mentioned, A sulfonylamino group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, C1-C12, methanesulfonylamino, benzenesulfonylamino etc. are mentioned, for example, sulfamoyl group (preferably C0-20, More preferably, C0-16, Especially preferably, Is 0 to 12 carbon atoms, for example, sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, and the like, carbamoyl group (preferably C1-20, more preferably C1) -16, Especially preferably It is a minority 1-12, For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. are mentioned, The alkylthio group (preferably C1-C20) is more preferable. Preferably it is C1-C16, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably C6-C20, More preferably, carbon number) 6-16, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned, A sulfonyl group (Preferably C1-C20, More preferably, C1-C16, Especially preferably, Is 1 to 12 carbon atoms, for example, mesyl, tosyl, etc., sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). , For example, methanesulfinyl, benzenesulfinyl, etc.), ureido (Preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid Amide group (preferably C1-C20, More preferably, it is C1-C16, Especially preferably, it is C1-C12, For example, Diethyl phosphate amide, Phenyl phosphate amide, etc. are mentioned), A hydroxyl 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, already No group and heterocyclic group (preferably C1-C30, More preferably, it is 1-12, As a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, Specifically, for example, imidazolyl, pyri Dill, quinolyl, furyl, piperidyl, morphol Lino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and the like, silyl group (preferably, 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 3 carbon atoms). 24, for example, trimethylsilyl, triphenylsilyl, etc.) etc. are mentioned. These substituents may also be substituted.

In addition, when there are two or more substituents, they may be same or different. In addition, when possible, you may connect with each other and form a ring.

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

The compound represented by general formula (I) of this invention can be synthesize | combined by the general ester reaction of substituted benzoic acid and a phenol derivative, and what kind of reaction may be used if it is ester bond formation reaction. For example, after functional group conversion of substituted benzoic acid to an acid halide, the method of condensation with a phenol, the method of dehydrating and condensing a substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, etc. are mentioned.

Considering the production process, a method of condensing with phenol after converting the substituted benzoic acid into an acid halide is preferable.

As the reaction solvent, a hydrocarbon solvent (preferably toluene, xylene), an ether solvent (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), a ketone solvent, an ester solvent , Acetonitrile, dimethylformamide, dimethylacetamide and the like can be used. These solvent may be used individually or in mixture of many types, Preferably it is toluene, acetonitrile, dimethylformamide, and dimethylacetamide as reaction solvent.

As reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 0-100 degreeC, More preferably, it is 0-90 degreeC, Especially preferably, it is 20 degreeC-90 degreeC.

It is preferable that a base is not used for this reaction, and when using a base, any of an organic base and an inorganic base may be sufficient, Preferably it is an organic base, pyridine, tertiary alkylamine (preferably triethylamine, Ethyl diisopropylamine, etc.);

In the ultraviolet absorption spectrum of a solution, you may use together two or more types of rod-shaped compounds whose maximum absorption wavelength ((lambda) max) is shorter than 250 nm.

[Matt Particulates]

It is preferable to add microparticles | fine-particles to a cellulose acylate film which concerns on 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, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate Can be mentioned. It is preferable that microparticles | fine-particles contain silicon from the point which becomes turbidity low, and silicon dioxide is especially preferable. It is preferable that the microparticles of silicon dioxide have a primary average particle diameter of 20 nm or less, and have an apparent specific gravity of 70 g / liter or more. It is more preferable that the average diameter of a primary particle is 5-16 nm as small as it 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 more preferable it is to be possible to make a high concentration dispersion liquid and to increase haze and aggregates.

It is preferable that the usage-amount in the case of using the said silicon dioxide microparticles | fine-particles shall be 0.01-0.3 mass part with respect to 100 mass parts of polymer components containing a cellulose acylate.

These microparticles | fine-particles usually form the secondary particle of 0.1-3.0 micrometers in average particle diameter, and these microparticles | fine-particles exist as an aggregate of primary particle in a film, and form unevenness | corrugation of 0.1-3.0 micrometers in a film surface. 0.2 micrometer or more and 1.5 micrometer or less are preferable, 0.4 micrometer or more and 1.2 micrometer or less are more preferable, and 0.6 micrometer or more and 1.1 micrometer or less are the most preferable. When larger than 1.5 micrometers, a haze becomes strong, and when smaller than 0.2 micrometer, a squeak prevention effect becomes small.

Primary and secondary particle diameters observe the particle | grains in a film with a scanning electron microscope, and let the diameter of the circle circumscribed to particle | grains be a particle diameter. In addition, 200 particles are observed after changing places, and the average value is made the average particle diameter.

As microparticles | fine-particles of silicon dioxide, commercial items, such as aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd. make) are used, for example. Can be. The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerosil R976 and R811 (above, Aerosol Co., Ltd.) and can be used.

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

In this invention, in order to obtain the cellulose acylate film which has a particle | grain with small secondary average particle diameter, some methods are considered when preparing the dispersion liquid of microparticles | 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 further mixing with a 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 hardly further reaggregated. In addition, after adding a small amount of cellulose esters to a solvent, stirring and dissolving, adding a fine particle to this, disperse | distributing with a disperser and making this a fine particle addition liquid, and fully mixing this fine particle addition liquid with a dope liquid with an inline mixer. There is also. 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 silicon dioxide fine particles mixed with 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 with respect to the added amount, and the haze and aggregates are positive, which is preferable. 0.01-1.0 g per 1 m <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 are more preferable, 0.08-0.16g are the most preferable.

Solvents to be used include lower alcohols, preferably methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. 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.

Next, the said organic solvent in which the cellulose acylate which concerns on this invention is melt | dissolved is described.

In the present invention, any of a chlorine-based solvent containing chlorine-based organic solvent as the main solvent and a non-chlorine-based solvent containing no chlorine-based organic solvent can be used.

(Chlorine solvent)

In preparing the solution of the cellulose acylate which concerns on this invention, the chlorine organic solvent is used suitably as a main solvent. In the present invention, as long as the object can be achieved within the range in which the cellulose acylate is dissolved, cast and film forming, the kind of the chlorine organic solvent is not particularly limited. These chlorine organic solvents are preferably dichloromethane and chloroform. Dichloromethane is particularly preferred. In addition, mixing of organic solvents other than chlorine-based organic solvents is not particularly a problem. In that case, 50 mass% or more of dichloromethane needs to be used in the organic solvent whole quantity. Other organic solvents used in combination with the chlorine-based organic solvent in the present invention are shown below. That is, as another preferable organic solvent, the solvent chosen from ester of 3-12 carbon atoms, ketone, ether, alcohol, hydrocarbon, etc. is preferable. The ester, ketone, ether and alcohol may have a cyclic structure. Compounds having two or more functional groups of esters, ketones and ethers (ie, -O-, -CO- and -CO0-) can also be used as the solvent, and other functional groups such as, for example, alcoholic hydroxyl groups You may have it. In the case of the 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. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and the like. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, isobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol. Can be mentioned. 2-ethoxy ethyl acetate, 2-methoxy ethanol, 2-butoxy ethanol, etc. are mentioned as an example of the organic solvent which has two or more types of functional groups.

Moreover, as alcohol used together with a chlorine-type organic solvent, Preferably, it may be linear, may have a branch, or may be cyclic, and it is especially preferable that it is a saturated aliphatic hydrocarbon. The hydroxyl group of alcohol may be any of the 1st class-3rd class. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Moreover, a fluorine-type alcohol can also be used as alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned. In addition, a hydrocarbon may be linear, may have a branch, or may be cyclic. Any of aromatic and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene.

Although the following compositions are mentioned as a combination example of a chlorine organic solvent and another organic solvent, It is not limited to these.

ㆍ dichloromethane / methanol / ethanol / butanol (80/10/5/5, parts by mass),

Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass),

Dichloromethane / methanol / butanol / cyclohexane (80/10/5/5 mass parts),

ㆍ dichloromethane / methylethylketone / methanol / butanol (80/10/5/5, parts by mass),

ㆍ Dichloromethane / acetone / methylethylketone / ethanol / isopropanol (75/8/5/5/7, parts by mass)

ㆍ Dichloromethane / cyclopentanone / methanol / isopropanol (80/7/5/8, parts by mass)

Dichloromethane / methyl acetate / butanol (80/10/10 mass parts),

Dichloromethane / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass),

ㆍ dichloromethane / methylethylketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass),

ㆍ dichloromethane / 1,3 dioxolane / methanol / ethanol (70/20/5/5, parts by mass),

ㆍ dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),

ㆍ dichloromethane / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass),

ㆍ dichloromethane / methylethylketone / acetone / methanol / ethanol (70/10/10/5/5, parts by mass)

ㆍ dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)

ㆍ dichloromethane / acetoacetic acid methyl / methanol / ethanol (65/20/10/5, parts by mass),

ㆍ dichloromethane / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),

Etc. can be mentioned.

(Non-chlorine solvent)

Next, it describes about the non-chlorine organic solvent used preferably in producing the solution of the cellulose acylate which concerns on this invention. In this invention, as long as the objective can be achieved in the range which a cellulose acylate melt | dissolves, it can cast and film forming, a non-chlorine organic solvent is not specifically limited. The non-chlorine organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. The ester, ketone and ether 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 have other functional groups such as, for example, alcoholic hydroxyl groups. You may be. 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. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol. Can be mentioned. 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol are mentioned as an example of the organic solvent which has two or more types of functional groups.

The non-chlorine organic solvent used for the above cellulose acylate is selected from various viewpoints of the above technology, but is preferably as follows. That is, as the non-chlorinated solvent, a mixed solvent having the above-mentioned non-chlorinated organic solvent as the main solvent is preferable, and as a mixed solvent of three or more different solvents, the first solvent is methyl acetate, ethyl acetate, methyl formate, ethyl formate , Acetone, dioxolane, dioxane or one or more thereof or a mixture thereof, wherein the second solvent is selected from ketones or acetoacetic acid esters having 4 to 7 carbon atoms, and the alcohol having 1 to 10 carbon atoms as the third solvent. Or a mixed solvent selected from hydrocarbons, more preferably alcohols having 1 to 8 carbon atoms. Moreover, when a 1st solvent is a liquid mixture of 2 or more types of solvent, there may be no 2nd solvent. More preferably, the first solvent is methyl acetate, acetone, methyl formate, ethyl formate or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or methyl acetyl acetate. A mixed solvent may be sufficient.

The alcohol which is a 3rd solvent may be linear, may have a branch, or may be cyclic, and it is especially preferable that it is a saturated aliphatic hydrocarbon. The hydroxyl group of the alcohol may be any of the first to third classes. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. Moreover, a fluorine-type alcohol is also used as alcohol. For example, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- tetrafluoro-1-propanol, etc. are mentioned. In addition, a hydrocarbon may be linear, may have a branch, or may be cyclic. Any of aromatic and aliphatic hydrocarbons can be used. The aliphatic hydrocarbon may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene and xylene. The alcohol and hydrocarbon which are these 3rd solvents may be individual, or 2 or more types of mixtures may not be specifically limited. As the third solvent, preferred specific compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, hexane, and particularly preferred. Preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol.

The mixing ratio of the above three kinds of mixed solvents is 20 to 95 mass% of the first solvent, 2 to 60 mass% of the second solvent and 2 to 30 mass% of the third solvent in the total amount of the mixed solvent. It is preferable that the first solvent is 30 to 90 mass%, the second solvent is 3 to 50 mass%, and the third alcohol is preferably 3 to 25 mass%. Moreover, it is preferable that especially the 1st solvent is 30-90 mass%, the 2nd solvent is 3-30 mass%, and the 3rd solvent is alcohol, and 3-15 mass% is contained. The non-chlorine-based organic solvent used in the present invention described above is described in detail in p. 12-16 of the Korean Society of Publications Publication No. 2001-1745 (published on March 15, 2001). Although the combination of the preferable non-chlorine organic solvent of this invention is mentioned below, it is not limited to these.

Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5 by mass),

Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5/5/5 by mass),

Methyl acetate / acetone / methanol / butanol / cyclohexane (75/10/5/5/5 by mass),

Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass)

Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass)

Methyl acetate / acetone / ethanol / butanol (80/10/4/6 parts by mass)

Methyl acetate / methyl ethyl ketone / ethanol / butanol (80/10/5/5 mass parts),

Methyl acetate / acetone / methylethyl ketone / ethanol / isopropanol (75/8/5/5/7, parts by mass)

Methyl acetate / cyclopentanone / methanol / isopropanol (80/7/5/8 mass parts),

Methyl acetate / acetone / butanol (85/10/5, parts by mass),

Methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/14/5/6, parts by mass),

Methyl acetate / cyclohexanone / methanol / hexane (70/20/5/5, parts by mass),

Methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass);

Methyl acetate / 1, 3-dioxolane / methanol / ethanol (70/20/5/5, parts by mass)

Methyl acetate / dioxane / acetone / methanol / ethanol (60/20/10/5/5, parts by mass),

Methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass)

Methyl formate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass)

Methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass)

Acetone / acetoacetic acid methyl / methanol / ethanol (65/20/10/5, parts by mass),

Acetone / cyclopentanone / ethanol / butanol (65/20/10/5, parts by mass),

Acetone / 1,3-dioxolane / ethanol / butanol (65/20/10/5, parts by mass),

1,3-dioxolane / cyclohexanone / methylethylketone / methanol / butanol (55/20/10/5/5/5, parts by mass), and the like.

Moreover, the cellulose acylate solution adjusted by the following method can also be used.

ㆍ Method of preparing cellulose acylate solution with methyl acetate / acetone / ethanol / butanol (81/8/7/4 mass parts) and adding 2 parts by mass of butanol after filtration and concentration.

ㆍ Method of preparing cellulose acylate solution with methyl acetate / acetone / ethanol / butanol (84/10/4/2 mass parts) and adding 4 parts by mass of butanol after filtration and concentration.

ㆍ Method of preparing cellulose acylate solution with methyl acetate / acetone / ethanol (84/10/6 parts by mass) and adding 5 parts by mass of butanol after filtration and concentration.

In the dope used for this invention, in addition to the non-chlorine organic solvent of the said invention, you may contain dichloromethane 10 mass% or less of the total amount of the organic solvent of this invention.

(Cellulose Acylate Solution Characteristics)

The solution of cellulose acylate is preferably a solution obtained by dissolving cellulose acylate at a concentration of 10 to 30% by mass in the organic solvent, in terms of film casting flexibility, more preferably 13 to 27% by mass, particularly preferably Is 15-25 mass%. The method of performing cellulose acylate at these concentrations may be carried out so as to be a predetermined concentration in the dissolving step, and further produced in advance as a low concentration solution (for example, 9 to 14 mass%), and then at a predetermined high concentration in the concentration step described later. You may adjust with a solution. Moreover, after making it the cellulose acylate solution of high concentration previously, you may make it the cellulose acylate solution of predetermined | prescribed low density | concentration by adding various additives, and if any method is performed so that it may become the cellulose acylate solution concentration which concerns on this invention, it will not have a problem.

Next, in the present invention, the aggregate molecular weight of the cellulose acylate in the diluted solution in which the cellulose acylate solution is 0.1 to 5% by mass in an organic solvent having the same composition is 150,000 to 15 million. It is preferable at the point which makes it good. More preferably, the association molecular weight is 180,000 to 9 million. This association molecular weight can be calculated | required by the static light scattering method. It is preferable to melt | dissolve so that the inertia square radius calculated | required at the time may be 10-200 nm. More preferred square radius of inertia is 20 to 200 nm. Moreover, it is preferable to melt | dissolve so that a 2nd vial coefficient may be -2x10 <^-4> + 4 * 10 <^-4> , More preferably, a 2nd vireal coefficient is -2x10 <^-4> ++ 2 * 10. ^{- 4.}

Here, the definition of the association molecular weight, the square inertia square, and the second vial coefficient in the present invention will be described. These are measured using the static light scattering method according to the following method. Although the measurements are summed up in the lean region of the device, these measurements reflect the behavior of the dope in the high concentration region of the present invention.

First, a cellulose acylate is dissolved in the solvent used for dope, and the solution of 0.1 mass%, 0.2 mass%, 0.3 mass%, and 0.4 mass% is prepared. In addition, in order to prevent moisture absorption, a cellulose acylate is dried at 120 degreeC for 2 hours, and is performed at 25 degreeC and 10% RH. The dissolution method is performed in accordance with the method (normal temperature dissolution method, cooling dissolution method, high temperature dissolution method) employed at the time of dope dissolution. Subsequently, these solutions and a solvent are filtered through a 0.2 micrometer Teflon filter. And static light scattering of the filtered solution is measured at 10 degreeC from 30 degreeC to 140 degreeC at 25 degreeC using the light-scattering measuring apparatus (Otsuka Electronics Co., Ltd. product DLS-700). The obtained data are analyzed by the BERRY plot method. In addition, the refractive index required for this analysis uses the value of the solvent calculated | required by the Abbe refractometer, and the concentration gradient (dn / dc) of the refractive index is light-scattering measurement using a differential refractometer (DRM-1021 by Otsuka Electronics Co., Ltd.). It measures using the solvent and solution which were used for.

(Dope preparation)

Next, the preparation of a cellulose acylate solution (dope) is said. The dissolving method of cellulose acylate is not specifically limited, It may be room temperature, Furthermore, it is performed by the cooling dissolution method or the high temperature dissolution method, and also the combination of these. About these, for example, Unexamined-Japanese-Patent No. 5-163301, Unexamined-Japanese-Patent No. 61-106628, Unexamined-Japanese-Patent No. 58-127737, Unexamined-Japanese-Patent No. 9-95544, Japan Japanese Patent Application Laid-open No. Hei 10-95854, Japanese Patent Application Laid-open No. Hei 10-45950, Japanese Patent Application Laid-Open No. 2000-53784, Japanese Patent Application Laid-Open No. 11-322946, and Japanese Patent Application Laid-open No. Hei 11-322947, Japan Japanese Patent Laid-Open No. 2-276830, Japanese Patent Laid-Open No. 2000-273239, Japanese Patent Laid-Open No. 11-71463, Japanese Patent Laid-Open No. 04-259511, Japanese Patent Laid-Open No. 2000-273184, Japanese Patent Laid-Open The preparation method of a cellulose acylate solution is described in each of Unexamined-Japanese-Patent No. 11-323017, Unexamined-Japanese-Patent No. 11-302388, etc. are described. As for the dissolution method of these cellulose acylates to the organic solvent described above, these techniques can be applied as long as it is a range of this invention suitably also in this invention. These details are particularly carried out by the method described in detail in the Invention Association Publication No. 2001-1745 (published on March 15, 2001, Invention Association) p.22-25 regarding non-chlorine solvent systems. . In addition, solution concentration and filtration of the dope solution of the cellulose acylate which concerns on this invention are normally performed, and similarly it is explained in full detail in p. 25 by the invention association publication publication No. 2001-1745 (published on March 15, 2001, invention association). It is described. Moreover, when melt | dissolving at high temperature, the case more than the boiling point of the organic solvent to be used is most, and in that case, it is used in a pressurized state.

It is preferable that a cellulose acylate solution is easy to be flexible and it is the range which the viscosity and the dynamic storage elastic modulus of this solution describe below. 1 mL of the sample solution is measured on a rheometer (CLS 500) using a Steel Cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. The measurement conditions were measured by varying the range of 40 ° C.-10 ° C. to 2 ° C./min with an Oscillation Step / Temperature Ramp, and storing a static non-Newtonian viscosity (n * (Pa · s)) of 40 ° C. and a storage of −5 ° C. Elastic modulus (G '(Pa)) is calculated | required. In addition, the sample solution is measured before the liquid temperature is maintained at a measurement start temperature in advance until the liquid temperature is constant. In this invention, it is preferable that the viscosity in 40 degreeC is 1-400 Pa.s, and the dynamic storage elastic modulus in 15 degreeC is 500 Pa or more, More preferably, the viscosity in 40 degreeC is 10-200 Pa.s, 15 The dynamic storage elastic modulus in ° C is 1 to 1 million. Moreover, the larger the dynamic storage elastic modulus at low temperature is preferable. For example, when the flexible support is -5 ° C, the dynamic storage elastic modulus is preferably 10,000 to 1 million Pa at -5 ° C, and the support is -50 ° C. In the case, the dynamic storage modulus at −50 ° C. is preferably 10,000 to 5 million Pa.

In this invention, since the specific cellulose acylate of the said technique is used, the high concentration dope is obtained, and the cellulose acylate solution excellent in stability at high concentration and excellent also is obtained, without resorting to a means of concentration. Moreover, in order to make it easy to melt | dissolve, you may melt | dissolve at low density | concentration, and you may concentrate using a concentration means. The concentration method is not particularly limited, but for example, the low concentration solution is guided between the cylinder and the rotational trajectory of the rotor blades rotating in the circumferential direction thereof, and a temperature difference is provided between the solution and the solvent. Method of obtaining a high concentration solution while evaporating (for example, Japanese Patent Application Laid-open No. Hei 4-259511, etc.), blowing a heated low concentration solution into the container from the nozzle, and flashing the solvent while the solution reaches the inner wall of the container from the nozzle. With evaporation, the solvent vapor is withdrawn from the vessel and the high concentration solution is withdrawn from the vessel bottom (e.g., US Pat. No. 2,541,012, US Pat. No. 2,858,229, US Pat. No. 4,414,341, US Pat. No. 4,504,355) The method described in the back) and the like can be carried out.

It is preferable to filter out foreign matters, such as undissolved matter, garbage, and impurities, using a suitable filter medium, such as a wire mesh and a flannel, before casting | flow_spreading. It is preferable to use the filter of 0.1-100 micrometers of absolute filtration precision, and to use the filter of 0.5-25 micrometers of absolute filtration precision for the filtration of a cellulose acylate solution. 0.1-10 mm is preferable and, as for the thickness of a filter, 0.2-2 mm is preferable. In that case, the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, more preferably 1.0 MPa or less, particularly preferably 0.2 MPa or less. As a filter medium, conventionally well-known materials, such as fluororesins, such as glass fiber, a cellulose fiber, a filter paper, and ethylene tetrafluoride resin, can be used preferably, Especially ceramics, a metal, etc. are used preferably. The viscosity just before film forming of a cellulose acylate solution should just be a range which can be flexible at the time of film forming, It is preferable to be prepared in the range of 10Pa * s-2000Pa * s normally, 30Pa * s-1000Pa * s are more preferable, 40Pa S to 500 Pa · s are more preferable. Moreover, if the temperature at this time is the temperature at the time of the casting | flow_spread, it will not specifically limit, Preferably it is -5-+70 degreeC, More preferably, it is -5-+55 degreeC.

(Production)

The cellulose acylate film which concerns on this invention can be obtained by forming into a film using the said cellulose acylate solution. As a film forming method and a facility, the conventional solution casting film forming method and solution casting film forming apparatus which supply to a cellulose triacetate film manufacture are used. The dope (cellulose acylate solution) prepared in the dissolving machine (kiln) is once stored in a storage kiln, the foam contained in the dope is defoamed and finally prepared. The dope is sent from the dope outlet to the press die through a pressurized metering gear pump capable of metering fluid with high precision, for example, by rotational speed, and the dope is driven endlessly from the detention (slit) of the press die. At a peel point where the metal support is uniformly flexible on the negative metal support and the metal support is almost round, the less dry dope film (also called a web) is peeled off the metal support. Both ends of the web obtained are picked up with a clip, conveyed by a tenter, and dried, maintaining width, then conveyed by the roll group of a drying apparatus, and complete | finish drying, and wind up to a predetermined length with a winder. The combination of a tenter and the drying apparatus of a roll group changes with the objective. In the solution casting film formation method used for the functional protective film for electronic displays, in addition to a solution casting film forming apparatus, it is a coating apparatus for surface processing to films, such as a lower layer, an antistatic layer, an anti-halation layer, a protective layer. Is often added. Although each manufacturing process is briefly described below, it is not limited to these.

First, when the prepared cellulose acylate solution (dope) produces a cellulose acylate film by the solvent cast method, dope is cast on a drum or a band, a solvent is evaporated and a film is formed. As for the dope before casting | flow_spread, it is preferable to adjust density | concentration so that solid content may be 5-40 mass%. It is preferable to finish the surface of a drum or a band in a mirror surface state. It is preferable that dope is flexible on the drum or band whose surface temperature is 30 degrees C or less, and it is especially preferable that it is a metal support temperature of -10-20 degreeC. Japanese Unexamined Patent Application Publication No. 2000-301555, Japanese Unexamined Patent Application Publication No. 2000-301558, Japanese Unexamined Patent Application Publication No. 07-032391, Japanese Unexamined Patent Application Publication No. 03-193316, Japanese Unexamined Patent Application Publication No. 05-086212, Japan Each of Unexamined-Japanese-Patent No. 62-037113, Unexamined-Japanese-Patent No. 02-276607, Unexamined-Japanese-Patent No. 55-014201, Unexamined-Japanese-Patent No. 02-111511, and Unexamined-Japanese-Patent No. 02-208650 The method described in the publication can be used in the present invention.

(Middle layer flexible)

The cellulose acylate solution may be cast as a monolayer liquid on a smooth band or drum as a metal support, or a plurality of cellulose acylate liquids of two or more layers may be cast. In the case where a plurality of cellulose acylate solutions are cast, a film may be produced while flexing and laminating a solution containing cellulose acylate in a plurality of oil studies formed at intervals in the advancing direction of the metal support, for example, in Japan. The method described in Unexamined-Japanese-Patent No. 61-158414, Unexamined-Japanese-Patent No. 1-22419, Unexamined-Japanese-Patent No. 11-198285, etc. can be applied. Moreover, you may make it film by casting a cellulose acylate solution in two oil studies, For example, Unexamined-Japanese-Patent No. 60-27562, Unexamined-Japanese-Patent No. 61-94724, and Japan Unexamined-Japanese-Patent No. 61-947245. , Unexamined-Japanese-Patent No. 61-104813, Unexamined-Japanese-Patent No. 61-158413, and Unexamined-Japanese-Patent No. 6-134933 can be implemented by the method as described in each publication. Further, the flow of the high viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped in a low viscosity cellulose acylate solution, and the cellulose acylate film cast which simultaneously extrudes the high viscosity and low viscosity cellulose acylate solution is cast. It may be a method. Moreover, it is also a preferable aspect that the solution of the outer side described in each of Unexamined-Japanese-Patent No. 61-94724 and Unexamined-Japanese-Patent No. 61-94725 contains more alcohol component which is a poorer solvent than an inside solution. Or using two oil studies, the film shape | molded to the metal support body by 1st oil research is peeled off, and 2nd casting | flow_spreading may be performed to the side which contacted the metal support surface, and a film may be produced, for example It is the method described in Unexamined-Japanese-Patent No. 44-20235. The flexible cellulose acylate solution may be the same solution, or may be a different cellulose acylate solution, and is not particularly limited. In order to have a function to a some cellulose acylate layer, what is necessary is just to extrude the cellulose acylate solution according to the function in each oil research. Moreover, a cellulose acylate solution can also carry out simultaneously softening other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorption layer, a polarizing layer, etc.).

In the conventional monolayer liquid, in order to achieve the required film thickness, it is necessary to extrude the cellulose acylate solution of high viscosity at a high concentration, and in that case, the stability of the cellulose acylate solution is poor, and solids are generated, resulting in protrusion failure or poor planarity. It was often a problem. As a solution, by plural cellulose acylate solutions in oil studies, a solution of high viscosity can be extruded simultaneously on a metal support, so that the planarity is good, and an excellent planar film can be produced. Reduction of a dry load can be achieved by using a cellulose acylate solution, and the production speed of a film can be raised. In the case of the covalent lead, the thickness of the inside and the outside is not particularly limited, but preferably the outside is 1 to 50% of the total film thickness, and more preferably 2 to 30%. Here, in the case of 3 or more layers of covalent lead, the total film thickness of the layer which contacted the metal support body, and the layer which contact | connected the air side is defined as outer thickness. In the case of the covalent lead, the cellulose acylate solution having different additive concentrations such as the above-described plasticizer, ultraviolet absorbent, matting agent and the like can be covalently produced to produce a cellulose acylate film having a laminated structure. For example, the cellulose acylate film of the structure called a skin layer / core layer / skin layer can be made. For example, a matting agent is many in a skin layer, or can be put only in a skin layer. A plasticizer and a ultraviolet absorber can be put in a core layer more than a skin layer, and you may put only a core layer. In addition, the kind of the plasticizer and the ultraviolet absorber may be changed in the core layer and the skin layer. For example, the plastic layer having excellent plasticity or the ultraviolet absorbent may be included in the core layer by including at least one of a low-volatile plasticizer and an ultraviolet absorber. This excellent ultraviolet absorber can also be added. Moreover, it is also a preferable aspect to contain a peeling accelerator only in the skin layer on the metal support side. Moreover, in order to cool a metal support body by a cooling drum method and gelatinize a solution, it is also preferable to add more alcohol which is a poor solvent to a skin layer more than a core layer. Tg of a skin layer and a core layer may differ, and it is preferable that Tg of a core layer is lower than Tg of a skin layer. Moreover, although the viscosity of the solution containing the cellulose acylate at the time of casting | flow_spread may differ from a skin layer and a core layer, it is preferable that the viscosity of a skin layer is smaller than the viscosity of a core layer, but even if the viscosity of a core layer is smaller than the viscosity of a skin layer do.

(softness)

As a method of casting the solution, a method of uniformly extruding the prepared dope from the press die onto the metal support, a method of adjusting the film thickness of the dope once cast on the metal support with the blade, or a reverse rotation Although there exist a method by the counter roll coater adjusted with a roll, the method by a press die is preferable. The press die includes a coat hanger type and a T die type, but any one can be preferably used. In addition to the methods exemplified herein, the present invention can be carried out by various methods for flexibly forming a cellulose lylacetate solution known in the art, and the contents described in each publication by setting the respective conditions in consideration of the difference in boiling point of the solvent to be used. The same effect as is obtained. As a metal support which runs with the endless used to manufacture the cellulose acylate film which concerns on this invention, the surface mirror-finished by the chrome plating, or the stainless steel belt (it is also called a band) mirror-finished by surface grinding | polishing is Used. 1 group or 2 or more groups may be provided in the pressurization die used for manufacture of the cellulose acylate film which concerns on this invention above a metal support body. Preferably it is 1 group or 2 groups. In the case where two or more units are installed, the flexible dope amount may be divided into various dies at various ratios, and the dope may be fed to the dies at respective ratios in a plurality of precision metering gear pumps. As for the temperature of the cellulose acylate solution used for casting, -10-55 degreeC is preferable, More preferably, it is 25-50 degreeC. In that case, all of the processes may be the same or may be different in each part of the process. When different, what is necessary is just a desired temperature just before casting | flow_spread.

(dry)

Drying of the dope on the metal support which concerns on manufacture of a cellulose acylate film is generally a method of exposing hot air in the surface side of a metal support (drum or belt), ie, the surface of the web on a metal support, a drum or a belt. There is a method of heating hot air from the back side of the surface, and a liquid heat transfer method of controlling the surface temperature by heating the drum or the belt by heat transfer by contacting the temperature-controlled liquid with the back side opposite to the dope flexible surface of the belt or drum. Liquid electrothermal is preferred. Any temperature may be sufficient as the surface temperature of the metal support body before casting | flow_spread if it is below the boiling point of the solvent used for dope. However, in order to promote drying and to lose the fluidity on the metal support, it is preferable to set the temperature at a temperature of 1 to 10 ° C. lower than the boiling point of the solvent having the lowest boiling point. Moreover, the case where peeling without cooling and drying cast dope is not limited to this.

(Stretching processing)

The cellulose acylate film which concerns on this invention can adjust retardation by an extending | stretching process. Moreover, there also exists a method of actively extending | stretching in the width direction, For example, Unexamined-Japanese-Patent No. 62-115035, Unexamined-Japanese-Patent No. 4-152125, Unexamined-Japanese-Patent No. 4-284211, Unexamined-Japanese-Patent No. It describes in Unexamined-Japanese-Patent No. 4-298310, Unexamined-Japanese-Patent No. 11-48271, etc., and the like. This stretches the produced film in order to make in-plane retardation value of a cellulose acylate film into a high value.

Stretching of a film is performed under normal temperature or heating conditions. It is preferable that heating temperature is below the glass transition temperature of a film. Stretching of a film may be longitudinal or uniaxial uniaxial stretching, and simultaneous or sequential biaxial stretching may be sufficient as it. Stretching is performed by 1 to 200% of stretching. Preferably 1 to 100% of stretching is particularly preferably 1 to 50% of stretching. As for the birefringence of an optical film, it is preferable that the refractive index of the width direction becomes larger than the refractive index of the longitudinal direction. Therefore, it is preferable to extend more in the width direction. In addition, an extending | stretching process may be performed in the middle of a film forming process, and you may extend | stretch the raw film which formed and wound up. In the former case, you may extend | stretch in the state containing the residual solvent amount, and it can extend | stretch preferably at 2-30%.

The film thickness of the cellulose acylate film which concerns on this invention obtained after drying differs according to a use purpose, It is preferable that it is the range of 5-500 micrometers normally, The range of 20-300 micrometers is still more preferable, Range is particularly preferred. Moreover, it is preferable that it is 40-110 micrometers for optics especially for VA liquid crystal display devices. What is necessary is just to adjust the solid content concentration contained in dope, the slit gap of the die | dye of a die, the extrusion pressure from a die, the metal support speed, etc. so that film thickness may be made into desired thickness. The width of the cellulose acylate film obtained as described above is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, still more preferably 0.8 to 2.2 m. It is preferable to wind up in length 100-10000m per roll, More preferably, it is 500-7000m, More preferably, it is 1000-6000m. When winding up, it is preferable to give knurling to at least one end, 3 mm-50 mm are preferable, as for width, More preferably, 5 mm-30 mm, and 0.5-500 micrometers are preferable, and more preferable Preferably it is 1-200 micrometers. This may be one press or both presses.

It is preferable that the deviation of the Re ₍₅₉₀₎ value of the full width is ± 5 nm, and more preferably ± 3 nm. In addition, the deviation of the Rth ₍₅₉₀₎ value is preferably ± 10 nm, more preferably ± 5 nm. Moreover, it is preferable that the deviation of Re value and Rth value of a longitudinal direction also exists in the deviation range of a width direction.

(Optical Properties of Cellulose Acylate Film)

It is preferable that the optical characteristics of the cellulose acylate film according to the present invention satisfy the following formulas (I) and (II) in order to widen the viewing angle of the liquid crystal display device, in particular, the VA mode liquid crystal display device. It is especially preferable when a cellulose acylate film is used for the protective film on the liquid crystal cell side of a polarizing plate.

Re₍₅₉₀₎

200nmFormula (I): 20 nm

Re ₍₅₉₀₎

200 nm

Rth₍₅₉₀₎

400nmFormula (II): 70 nm

Rth ₍₅₉₀₎

400 nm

In the present invention, the Re / Rth ratio is preferably adjusted to 0.1 to 0.8. More preferably, it is adjusted to 0.25 to 0.6. These adjustment can be performed according to the kind of additive, addition amount, and draw ratio.

In this specification, Re ((lambda)) and Rth ((lambda)) represent the in-plane retardation in wavelength (lambda), and the retardation of the thickness direction, respectively. Re ((lambda)) is measured by making light of wavelength ((lambda) nm) into a film normal line direction in KOBRA 21ADH (made by Oji measurement equipment Co., Ltd.). Rth (λ) is a light having a wavelength (λnm) in a direction inclined at + 40 ° with respect to the film normal direction using Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the inclination axis (rotation axis). A total of three retardation values measured by incidence and a retardation value measured by injecting light having a wavelength (λ nm) in a direction inclined at -40 ° with respect to the film normal direction using the in-plane slow axis as the inclination axis (rotation axis). KOBRA 21ADH is calculated based on the retardation value measured in the direction. The assumption value of the average refractive index can use the value of the catalog of a polymer handbook (JOHN WILEY & SONS, INC) and various optical films here. The average refractive index of cellulose acylate is 1.48. KOBRA 21 ADH calculates nx, ny, and nz by inputting the assumption value and film thickness of these average refractive indices.

When using the cellulose acylate film which concerns on this invention in VA mode, 2 methods of the form (two sheets) used in total of two sheets, one sheet on both sides of a cell, and the form (one sheet type) used only in the upper and lower sides of a cell are used. There is this.

In the case of the bimodal form, Re is preferably 20 to 100 nm, more preferably 30 to 70 nm. Regarding Rth, 70-300 nm is preferable and 100-200 nm is more preferable.

In the case of a single sheet, Re is preferably 30 to 150 nm, more preferably 40 to 100 nm. Regarding Rth, 100-300 nm is preferable and 150-250 nm is more preferable.

The deviation of the slow axis angle in the film plane of the cellulose acylate film according to the present invention is preferably in the range of -2 degrees to +2 degrees with respect to the reference direction of the roll film, and is in the range of -1 degrees to +1 degrees. More preferably, it is most preferably in the range of -0.5 degrees to +0.5 degrees. Here, a reference direction is a longitudinal direction of a roll film in the case of longitudinally stretching a cellulose acylate film, and a width direction of a roll film in the case of horizontal stretching.

Moreover, in the cellulose acylate film which concerns on this invention, the difference (Re (= Re10% RH-Re80% RH) of Re value in 25 degreeC 10% RH and Re value in 25 degreeC 80% RH is 0- The time lapse of the liquid crystal display device is 10 nm, and the difference ΔRth (= Rth 10% RH-Rth 80% RH) between the Rth value at 25 ° C and 10% RH and the Rth value at 25 ° C and 80% RH is 0 to 30nm. It is preferable in reducing the color change by.

Moreover, it is preferable in the cellulose acylate film which concerns on this invention that equilibrium moisture content in 25 degreeC 80% RH is 3.2% or less in reducing the color change with time of a liquid crystal display device.

The measurement method of moisture content measures the 7 mm x 35 mm of cellulose acylate film samples which concern on this invention with the moisture meter and the sample drying apparatus (CA-03, VA-05, Mitsubishi Chemical Corporation). It calculates by subtracting the moisture content (g) by the sample mass (g).

Moreover, the cellulose acylate film which concerns on this invention is 60 degreeC, 95% RH, and the water vapor transmission rate (equivalent to 80 micrometers) of 24 hr is 400 g / m <2> * 24hr or more and 1800g / m <2> * 24hr or less of a liquid crystal display device. It is desirable for reducing the color change over time.

If the film thickness of a cellulose acylate film is thick, a water vapor transmission rate will become small, and if a film thickness is thin, water vapor transmission rate will become large. Therefore, it is necessary to convert the sample of any film thickness into 80 micrometers of reference | standards. The film thickness conversion is calculated | required as (permeability | moisture permeability of 80 micrometers conversion = film thickness (micrometer) / 80 micrometer of actual measurement) x actual measurement.

As a method for measuring the moisture permeability, the method described in pages 285 to 294: Measurement of Vapor Permeation (Mass Method, Thermometer Method, Vapor Pressure Method, and Adsorption Method) of Polymer Properties II (Polymer Experiment Lecture 4 Kyoritsu Publication) can be applied. Can be.

The measurement of a glass transition temperature is a dynamic viscoelasticity measuring instrument (Vibron) after 5 mm x 30 mm of cellulose acylate film samples (unstretched) concerning this invention are humidified for 2 hours or more at 25 degreeC 60% RH for 2 hours or more. : Measured at DVA-225 (manufactured by Haiti Measurement Control Co., Ltd.) at a distance of 20 mm between clamps, a heating rate of 2 ° C / min, a measuring temperature range of 30 ° C to 200 ° C, and a frequency of 1Hz, and stored on a vertical axis with large shrinkage. When the temperature (° C.) is taken as the linear modulus on the elastic modulus and the horizontal axis, a drastic decrease in the storage modulus seen when the storage modulus transitions from the solid region to the glass transition region is obtained by drawing a straight line 1 in the solid region and a straight line 2 in the glass transition region. The intersection of the straight line 1 and the straight line 2 at the time of drawing is the temperature at which the storage elastic modulus decreases rapidly at the time of heating and the film starts to soften, and the temperature starts to move to the glass transition region. It was set as (Tg; dynamic viscoelasticity).

Moreover, it is preferable that haze of the cellulose acylate film which concerns on this invention is 0.01 to 2%. Here, haze can be measured as follows.

The measurement of haze measures the 40 mm x 80 mm of cellulose acylate film samples which concern on this invention with a haze meter (HGM-2DP, Suga test machine) at 25 degreeC and 60% RH according to JISK-6714.

Moreover, as for the cellulose acylate film which concerns on this invention, it is preferable that the mass change at the time of leaving for 48 hours on 80 degreeC and the conditions of 90% RH is 0 to 5%.

In addition, the cellulose acylate film which concerns on this invention has both the dimensional change at the time of standing for 24 hours on 60 degreeC and 95% RH conditions, and the dimensional change at the time of 24 hours standing on 90 degreeC 5% RH conditions, all 0. It is preferable that it is-5%.

It is preferable that a photoelastic coefficient is 50x10 <^13> cm <2> / dyne or less in order to reduce the color change with time of a liquid crystal display device.

As a specific measuring method, a tensile stress is applied to the major axis direction of 10 mm x 100 mm of a cellulose acylate film sample, and the retardation at that time is measured with an ellipsometer (M150, Nippon Bunco Co., Ltd.), The photoelastic coefficient is calculated from the change amount of the retardation with respect to.

(Optical anisotropic layer)

Moreover, what provided the optically anisotropic layer on the polymer film may be sufficient as a protective film. It is preferable that an optically anisotropic layer has an orientation layer and an optically anisotropic layer in this order on a transparent polymer film.

The alignment layer can be formed by means such as rubbing treatment of an organic compound (preferably a polymer), evaporation of an inorganic compound, formation of a layer having micro groups. Moreover, although the orientation layer which an orientation function produces by provision of an electric field, provision of a magnetic field, or light irradiation is also known, the orientation layer formed by the rubbing process of a polymer is especially preferable. The rubbing treatment is preferably carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. It is preferable that the absorption axis direction of a polarizer and a rubbing direction are substantially parallel. As a kind of polymer used for an orientation layer, the polymer etc. which have a polymerizable group of polyimide, polyvinyl alcohol, Unexamined-Japanese-Patent No. 9-152509, etc. can be used preferably. It is preferable that it is 0.01-5 micrometers, and, as for the thickness of an orientation layer, it is more preferable that it is 0.05-2 micrometers.

It is preferable that an optically anisotropic layer contains a liquid crystalline compound. It is especially preferable that the liquid crystalline compound used for this invention has a discotic compound (discotic liquid crystal). The discotic liquid crystal molecule has a disk-like core portion like the triphenylene derivative of D-1, and has a structure in which side chains are extended radially therefrom. Moreover, in order to provide time-lapse stability, it is also preferable to introduce | transduce group which reacts with heat, light, etc. further. Preferable examples of the discotic liquid crystal are described in Japanese Patent Laid-Open No. 8-50206.

Discotic Liquid Crystal Molecules (I)

The discotic liquid crystal molecules are oriented substantially parallel to the film plane with a pretilt angle in the rubbing direction in the vicinity of the alignment layer, and the discotic liquid crystal molecules are oriented so as to be perpendicular to the plane on the opposite air surface side. As the whole discotic liquid crystal layer, hybrid orientation is taken, and by this layer structure, the viewing angle enlargement of the TFT-LCD of TN mode can be implement | achieved.

The optically anisotropic layer is generally applied by applying a solution obtained by dissolving a discotic compound and other compounds (for example, a polymerizable monomer and a photopolymerization initiator) to a solvent on an alignment layer, followed by drying, followed by a discotic nematic phase formation temperature. It heats to and after, it superposes | polymerizes by irradiation of UV light, etc., and is obtained by cooling again. As a discotic nematic liquid crystal phase-solid-state transition temperature of the discotic liquid crystalline compound used for this invention, 70-300 degreeC is preferable, and 70-170 degreeC is especially preferable.

In addition, as a compound other than the discotic compound added to the said optically anisotropic layer, it is compatible with a discotic compound, and unless a liquid crystal discotic compound changes a preferable inclination-angle or does not inhibit orientation, Compounds can also be used. Among them, additives for orientation control on the air interface side, such as polymerizable monomers (eg, compounds having vinyl group, vinyloxy group, acryloyl group, and methacryloyl group) and fluorine-containing triazine compounds, include cellulose acetate and cellulose acetate. And polymers such as propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. These compounds are generally used in an amount of 0.1 to 50 mass%, preferably 0.1 to 30 mass%, based on the discotic compound.

It is preferable that it is 0.1-10 micrometers, and, as for the thickness of an optically anisotropic layer, it is more preferable that it is 0.5-5 micrometers.

The optically anisotropic layer may be a non-liquid crystalline polymer layer prepared by dissolving a non-liquid crystalline compound in a solvent, applying it on a support, and heating and drying. In this case, the non-liquid crystalline compound is, for example, excellent in heat resistance, chemical resistance, transparency, and rich in rigidity, and thus polyamide, polyimide, polyester, polyether ketone, polyarylether ketone, polyamideimide, poly Polymers, such as esterimide, can be used. These polymers may be used individually by any one type, and may be used as 2 or more types of mixtures which have a different functional group like the mixture of polyaryl ether ketone and a polyamide, for example. Among these polymers, polyimide is preferred in terms of high transparency, high orientation, and high stretchability. Moreover, as a support body, a TAC film is preferable.

Moreover, it is also preferable that the laminated body of a non-liquid crystal layer and a support body is extended | stretched tenter horizontally by 1.05 times, and the support body side is joined to a polarizer.

In addition, the optically anisotropic layer may be an orientation solidification layer of cholesteric liquid crystal whose wavelength range of selective reflection is 350 nm or less. As cholesteric liquid crystal, Unexamined-Japanese-Patent No. 3-67219, Unexamined-Japanese-Patent No. 3-140921, Unexamined-Japanese-Patent No. 5-61039, Unexamined-Japanese-Patent No. 6-186534, Japan Suitable ones exhibiting the selective reflection characteristics described in Japanese Patent Application Laid-open No. Hei 9-133810 and the like can be used. What can be used suitably from the surface of the stability of an orientation solidification layer etc. is forming the liquid crystal polymer by superposition | polymerization process by the nematic liquid crystal polymer of cholesteric liquid crystal polymer or chiral agent mix | blending, light, heat, etc., for example. The cholesteric liquid crystal layer which consists of a compound etc. can be formed.

The optically anisotropic layer in this case can be formed, for example by the method of coating a cholesteric liquid crystal on a support base material. In that case, the method etc. which apply | coat the same type or different types of cholesteric liquid crystals repeatedly etc. can also be employ | adopted as needed for the purpose of control of a phase difference, etc. as needed. For the coating treatment, for example, a suitable method such as a gravure method, a die method, or a dipping method can be adopted. A suitable thing, such as a TAC film or another polymer film, can be used for the said support base material.

In the formation of the optically anisotropic layer, a means for orienting the liquid crystal is employed. The alignment means is not particularly limited, and any suitable means capable of orientating the liquid crystal compound can be employed. In addition, as an example, the method of coating and orienting a liquid crystal on an oriented film is mentioned. Moreover, as the orientation film, a rubbing treatment film made of an organic compound such as a polymer, an evaporated film of an inorganic compound, a film having a micro groove, or an organic compound such as ω-trichoic acid, dioctadecylmethylammonium chloride or methyl stearyl acid The film | membrane which accumulated the LB film | membrane by the Langviewer project method of this etc. is mentioned. Moreover, the alignment film etc. which generate | occur | produce an orientation function by irradiation of light are mentioned. On the other hand, the method of coating and aligning a liquid crystal on a stretched film (JP-A-39325), the method of orienting a liquid crystal under application of an electric field, a magnetic field, etc. are mentioned. Moreover, it is preferable that the alignment state of a liquid crystal is as uniform as possible, and it is preferable that it is a solidified layer fixed by the alignment state as much as possible.

When using the cellulose acylate film which concerns on this invention as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. For example, there exists a method of alkali-processing the obtained cellulose acylate film and bonding the polyvinyl alcohol film to the both surfaces of the polarizer produced by immersion extending | stretching and extending in iodine solution using the fully saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, an easy adhesion process 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 butylacrylate, etc. are mentioned, for example. A polarizing plate is comprised by the polarizer and the protective film which protects both surfaces, Moreover, you may comprise by attaching a protective film to one surface of this polarizing plate and a separate film to the opposite surface. A protective film and a separate film are used for the purpose of protecting a polarizing plate at the time of a polarizing plate shipment, a product inspection, etc. 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 with a liquid crystal cell. In addition, a separator film is used for the purpose of covering the contact bonding layer bonded by a liquid crystal cell, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

It is preferable to bond together the bonding method with respect to the polarizer of the cellulose acylate film which concerns on this invention so that the transmission axis of a polarizer may match the slow axis of the cellulose acylate film which concerns on this invention.

Moreover, if the orthogonal precision of the slow axis of the cellulose acylate film which concerns on this invention, and the absorption axis (axis orthogonal to a transmission axis) of the polarizer produced under polarizing plate cross nicol is larger than 1 degree, polarization under polarizing plate cross nicol In addition, since the performance deteriorates and light leaks and sufficient black level and contrast are not obtained when combined with a liquid crystal cell, the direction of the main refractive index nx of the cellulose acylate film according to the present invention and the direction of the transmission axis of the polarizing plate It is preferable that the deviation is 1 degree or less, Preferably it is 0.5 degrees or less.

(Surface treatment)

The cellulose acylate film which concerns on this invention can achieve the improvement of the adhesion of a cellulose acylate film and each functional layer (for example, an undercoat layer and a white layer) by surface-treating in some cases. As the surface treatment, 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 occurring 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, and freons such as tetrafluoromethane, and mixtures thereof. These are described in detail in JP-A No. 2001-1745 (published March 15, 2001, Invention Association) p. 30-32. Moreover, the irradiation process of 20-500 Kgy is used, for example under 10-1000 Kev, and the irradiation energy of 20-300 Kgy is used more preferably under 30-500 Kev for the plasma process which is attracting attention recently. Among these, especially preferably, it is an alkali saponification process and it is very effective as a surface treatment of a cellulose acylate film.

It is preferable to perform an alkali saponification process by the method of directly immersing a cellulose acylate film in the tank of a saponification liquid, or the method of apply | coating a saponification liquid to a cellulose acylate film. Examples of the coating method include a dip coating method, curtain coating method, extrusion coating method, bar coating method and E type coating method. In order to apply | coat a saponification liquid with respect to a cellulose acylate film, the solvent of an alkali saponification process coating liquid has good wettability, and does not form unevenness | corrugation on the surface of a cellulose acylate film with a saponification liquid solvent, and keeps a surface shape favorable. It is preferable to select the solvent to hold. Specifically, an alcohol solvent is preferable and isopropyl alcohol is especially preferable. Moreover, the aqueous solution of surfactant can also be used as a solvent. The alkali which the alkali saponification coating liquid dissolves in the said solvent is preferable, and KOH and NaOH are more preferable. 10 or more are preferable and, as for pH of saponification coating liquid, 12 or more are more preferable. 1 second or more and 5 minutes or less are preferable at room temperature, as for reaction conditions at the time of alkali saponification, 5 seconds or more and 5 minutes or less are more preferable, 20 seconds or more and 3 minutes or less are especially preferable. After the alkali saponification reaction, it is preferable to wash the saponified solution coated surface with water or acid and then wash with water.

Moreover, it is preferable that the polarizing plate of this invention provided one or more layers of a hard-coat layer, an anti-glare layer, and an antireflection layer on the surface of the protective film on the other side of a polarizing plate. That is, when using the liquid crystal display device of a polarizing plate, it is preferable to form a functional film, such as an anti-reflective layer, in the protective film TAC2 arrange | positioned on the opposite side to a liquid crystal cell, and as such a functional film, it is 1 of a hard-coat layer, an anti-glare layer, and an anti-reflective layer. It is preferable to form more than a layer. In addition, it is not necessary to form each layer as a separate layer, for example, You may form by making an anti-glare layer function as an anti-reflection layer and an anti-glare layer by making an anti-glare layer have the function in an anti-reflection layer or a hard-coat layer. (FIG. 1).

(Reflective layer)

In the present invention, an antireflection layer in which at least a light scattering layer and a low refractive index layer are laminated in this order on a protective film, or an antireflection layer in which a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a protective film is preferably used. do. These preferable examples are described below.

The preferable example of the anti-reflective layer which provided the light scattering layer and the low refractive index layer on a protective film is mentioned.

It is preferable that mat particle is disperse | distributed to a light-scattering layer, It is preferable that the refractive index of raw materials of parts other than mat particle of a light-scattering layer exists in the range of 1.50-2.00, and the refractive index of a low refractive index layer is in the range of 1.20-1.49. It is desirable to have. In the present invention, the light scattering layer has anti-glare properties and hard coat properties, and may be one layer, or may be composed of a plurality of layers, for example, two to four layers.

The antireflection layer has a surface irregularity shape with a center line average roughness Ra of 0.08 to 0.40 µm, a ten point average roughness Rz of 10 times or less of Ra, and an average valley distance Sm of 1 to 100 µm. By designing the standard deviation of the convex height at the deepest part of the unevenness to be 0.5 µm or less, the standard deviation of the mean valley distance Sm from the center line to 20 µm or less, and the inclination angle of 0 to 5 degrees, the surface being 10% or more. Sufficient anti-glare property and a uniform matte feeling to the naked eye are achieved and it is preferable. The color of the reflected light under the C light source is a ratio of the minimum value and the maximum value of the reflectance within the range of a * value -2 to 2, b * value -3 to 3, 380 nm to 780 nm, and 0.5 to 0.99. It is preferable to become this neutral. Moreover, it is preferable that the b * value of the transmitted light under C light source shall be 0-3, and yellow of white display at the time of applying to a display apparatus is reduced. In addition, if the standard deviation of the luminance distribution at the time of measuring the luminance distribution on a film by inserting a 120 micrometers x 40 micrometers grating between a surface light source image and the antireflection film of this invention is a high definition panel, The deviation when the film of this invention is applied to is reduced and is preferable.

The antireflection layer which can be used in the present invention is preferable because its optical properties can be suppressed by reflection of external light by improving the reflectivity of 2.5% or less, 90% or more of transmittance, and 70% or less of glossiness of 60 degrees. Do. In particular, the mirror reflectance is more preferably 1% or less, and most preferably 0.5% or less. 20% to 50% of haze, 0.3 to 1 ratio of internal haze / total haze value, haze value after formation of low refractive index layer within 15% of haze value to light scattering layer, transmission image clarity at comb width 0.5 mm 20 By setting the transmittance ratio in the inclination direction of 2 degrees in% to 50% and vertically transmitted light / vertical to 1.5 to 5.0, it is preferable to achieve the prevention of the deviation on the high-definition LCD panel and the reduction of the desired characters.

(Low refractive index layer)

The refractive index of the low refractive index layer that can be used in the present invention is preferably 1.20 to 1.49, more preferably in the range of 1.30 to 1.44. In addition, it is preferable that the low refractive index layer satisfy the following formula from the viewpoint of low reflectivity.

(m / 4) λ × 0.7 <n1d1 <(m / 4) λ × 1.3

In formula, m is positive odd number, n1 is the refractive index of a low refractive index layer, and d1 is the film thickness (nm) of a low refractive index layer. In addition, (lambda) is a wavelength and is a value of the range of 500-550 nm.

The raw material which forms a low refractive index layer is demonstrated below.

It is preferable that a low refractive index layer contains a fluorine-containing polymer as a low refractive index binder. As the fluorine polymer, a fluorine-containing polymer that crosslinks by heat or ionizing radiation having a coefficient of dynamic friction of 0.03 to 0.20, a contact angle to water of 90 to 120 degrees, and a sliding angle of pure water of 70 degrees or less is preferable. When the polarizing plate of the present invention is mounted on an image display device, the lower the peeling force with a commercially available adhesive tape, the easier it is to peel after adhering a seal or a memo, and preferably 500 gf or less when measured by a tensile tester. , 300 gf or less is more preferable, and 100 gf or less is most preferred. In addition, the higher the surface hardness measured by the microhardness meter, the less likely to be scratched, 0.3 GPa or more is preferable, and 0.5 GPa or more is more preferable.

Fluorine-containing polymers used in the low refractive index layer include the hydrolysis of perfluoroalkyl group-containing silane compounds (e.g. (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) In addition to a dehydration condensate, the fluorine-containing copolymer which makes a constituent unit a fluorine-containing monomer unit and the structural unit for providing crosslinking reactivity is mentioned.

Specific examples of the fluorine-containing monomers include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro- 2,2-dimethyl-1,3-dioxol, etc., partial or fully fluorinated alkylester derivatives of (meth) acrylic acid (e.g., biscot 6 FM (manufactured by Osaka Organic Chemicals) or M-2020 (Daikin) Production), etc.), fully or partially fluorinated vinyl ethers, and the like, but are preferably perfluoroolefins, and particularly preferably hexafluoropropylene from the viewpoint of refractive index, solubility, transparency, availability, and the like.

As a structural unit for providing crosslinking reactivity, the structural unit obtained by superposition | polymerization of the monomer which already has a self-crosslinkable functional group in a molecule like glycidyl (meth) acrylate and glycidyl vinyl ether, a carboxyl group, a hydroxyl group, an amino group, Monomers having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, Structural unit obtained by superposition | polymerization of crotonic acid, etc., Structural unit which introduce | transduced bridge | crosslinking reactive groups, such as a (meth) acryloyl group, by polymer reaction to these structural units (for example, makes acrylate react with respect to a hydroxyl group, etc.) Can be introduced by a method).

-메틸스티렌 등), 비닐에테르류 (메틸비닐에테르, 에틸비닐에테르, 시클로헥실비닐에테르 등), 비닐에스테르류 (아세트산비닐, 프로피온산비닐, 신남산비닐 등), 아크릴아미드류 (N-tert-부틸아크릴아미드, N-시클로헥실아크릴아미드 등), 메타크릴아미드류, 아크릴로니트릴 유도체 등을 들 수 있다.In addition to the fluorine-containing monomer unit and the structural unit for imparting crosslinking reactivity, a monomer that does not contain a fluorine atom may be copolymerized appropriately from the viewpoint of solubility in a solvent, transparency of the film, and the like. It does not specifically limit to the monomer unit which can be used together, For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate) Methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene,

-Methyl styrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tert-butyl Acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamide, an acrylonitrile derivative, etc. are mentioned.

About the said polymer, you may use together a hardening | curing agent suitably as described in Unexamined-Japanese-Patent No. 10-25388 and Unexamined-Japanese-Patent No. 10-147739, respectively.

(Light scattering layer)

The light scattering layer is formed for the purpose of imparting the light diffusibility by at least one of surface scattering and internal scattering, and hard coat property for improving scratch resistance of the film. Therefore, it is formed including a binder for imparting hard coat properties, mat particles for imparting light diffusivity, and inorganic fillers for high refractive index, prevention of crosslinking shrinkage, and high strength, as necessary. Moreover, by forming such a light scattering layer, this light scattering layer also functions as an anti-glare layer, and a polarizing plate has an anti-glare layer.

1-10 micrometers is preferable and, as for the film thickness of a light-scattering layer, 1.2-6 micrometers is more preferable. If it is too thin, hardness will be insufficient, and if too thick, curl or brittleness will deteriorate and processing aptitude will be insufficient.

As a binder of a light-scattering layer, it is preferable that it is a polymer which has a saturated hydrocarbon chain or a polyether chain as a principal chain, and it is more preferable that it is a polymer which has a saturated hydrocarbon chain as a principal chain. Moreover, it is preferable that a binder polymer has a crosslinked structure. As a binder polymer which has a saturated hydrocarbon chain as a main chain, the polymer of ethylenically unsaturated monomer is preferable. As a binder polymer which has a saturated hydrocarbon chain as a main chain and has a crosslinked structure, the (co) polymer of the monomer which has two or more ethylenically unsaturated groups is preferable. In order to make a binder polymer high refractive index, the thing containing 1 or more types of atoms in an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom can also be selected in the structure of this monomer.

Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohols with (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate). 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylic Latent, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3 Cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), the ethylene oxide modified product, vinylbenzene and its derivatives (e.g. 1,4-divinyl) Benzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (e.g. divinylsulfone), acrylamide (e.g. methylenebisacrylamide) and methacryl And amides. You may use together 2 or more types of said monomers.

Specific examples of the high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether, and the like. have. You may use together 2 or more types of these monomers.

Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation of ionizing radiation or heating in the presence of an optical radical initiator or a thermal radical initiator.

Therefore, the coating liquid containing the monomer which has an ethylenically unsaturated group, an optical radical initiator or a thermal radical initiator, mat particle | grains, and an inorganic filler is prepared, and this coating liquid is apply | coated on a protective film, and it hardens | cures by the polymerization reaction by ionizing radiation or heat. The antireflection film can be formed. These photo radical initiators and the like can be used.

As for the polymer which has a polyether as a principal chain, the ring-opening polymer of a polyfunctional epoxy compound is preferable. The ring-opening polymerization of the polyfunctional epoxy compound can be carried out by irradiation of ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

Therefore, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, mat particles, and an inorganic filler is prepared, and the coating liquid is coated on a protective film and then cured by polymerization reaction by ionizing radiation or heat, followed by reflection. A prevention film can be formed.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinkable functional group is introduced into the polymer using a monomer having a crosslinkable functional group, and the crosslinked structure is incorporated into the binder polymer by reaction of the crosslinkable functional group. You may introduce.

Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group and an active methylene group. Metal alkoxides such as vinylsulfonic acid, acid anhydride, cyanoacrylate derivatives, melamine, etherified methylol, esters and urethanes, and tetramethoxysilanes can also be used as monomers for introducing a crosslinked structure. Like a block isocyanate group, you may use the functional group which shows crosslinkability as a result of a decomposition reaction. That is, in this invention, a crosslinkable functional group may not show an immediate reaction, but may show reactivity as a result of decomposition | disassembly.

The binder polymer which has these crosslinkable functional groups can form a crosslinked structure by heating after apply | coating.

The light scattering layer contains mat particles larger than the filler particles and having an average particle diameter of 1 to 10 µm, preferably 1.5 to 7.0 µm, for example, particles of an inorganic compound or resin particles, for the purpose of imparting antiglare properties.

The inorganic compound particles, such as concrete examples of the matt particles, for example silica particles, TiO ₂ particles; Resin particles, such as an acryl particle, a crosslinked acrylic particle, a polystyrene particle, a crosslinked styrene particle, a melamine resin particle, and benzoguanamine resin particle, are mentioned preferably. Among them, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable. The shape of a mat particle can use any of spherical form or indefinite form.

Moreover, you may use together 2 or more types of mat particle from which a particle diameter differs. It is possible to impart anti-glare property to mat particles of larger particle diameter and to impart additional optical properties to mat particles of smaller particle diameter.

Moreover, as particle size distribution of the said mat particle, it is most preferable that it is monodispersion, and the particle diameter of each particle should just be the same, respectively. For example, when the particle | grains larger than 20% or more of an average particle diameter are prescribed | regulated as a coarse particle, it is preferable that the ratio of this coarse particle is 1% or less of the total particle number, More preferably, it is 0.1% or less. More preferably, it is 0.01% or less. The mat particle which has such a particle diameter distribution is obtained according to classification after a normal synthetic reaction, and the mat agent of a more preferable distribution can be obtained by raising the collection | recovery of classification, or strengthening the grade.

The mat particles are contained in the light scattering layer so that the amount of the matte particles of the formed light scattering layer is preferably 10 to 1000 mg / m 2, more preferably 100 to 700 mg / m 2.

The particle size distribution of the mat particle is measured by the Coulter counter method, and the measured distribution is converted into the particle number distribution.

The light scattering layer is made of one or more metal oxides selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the mat particles in order to increase the refractive index of the layer, and has an average particle diameter of 0.2 µm or less. It is preferable to contain the inorganic filler which is preferably 0.1 micrometer or less, More preferably, it is 0.06 micrometer or less. On the contrary, in order to increase the refractive index difference with the mat particles, it is also preferable to use an oxide of silicon in the light scattering layer using the high refractive index mat particles in order to keep the refractive index of the layer low. Preferred particle diameters are the same as those of the inorganic fillers described above.

Specific examples of the inorganic filler used in the light scattering layer, there may be mentioned _{TiO 2, ZrO 2, Al 2} O 3, In 2 O 3, ZnO, Sn0 2, Sb 2 O 3, ITO , and SiO ₂ and the like. TiO ₂ and ZrO ₂ are particularly preferred in terms of high refractive index. It is preferable that the surface of this inorganic filler is silane coupling process or titanium coupling process, and the surface treating agent which has a functional group which can react with a binder species on the filler surface is used preferably.

It is preferable that the addition amount of these inorganic fillers is 10 to 90% of the total mass of a light-scattering layer, More preferably, it is 20 to 80%, Especially preferably, it is 30 to 75%.

In addition, since the particle size is sufficiently smaller than the wavelength of light, scattering does not occur, and the dispersion in which the filler is dispersed in the binder polymer acts as an optically uniform substance.

The bulk refractive index of the mixture of the binder of the light scattering layer and the inorganic filler is preferably 1.50 to 2.00, more preferably 1.51 to 1.80. What is necessary is just to select suitably the kind and quantity ratio of a binder and an inorganic filler in order to make refractive index into the said range. How to choose can be easily known in advance experimentally.

The light scattering layer contains, in particular, a surfactant of either fluorine or silicon type or both thereof in the coating composition for light scattering layer formation in order to ensure surface uniformity such as coating unevenness, dry unevenness, and point defects. In particular, the fluorine-based surfactant is suitably used because the effect of improving surface defects such as coating unevenness, dry unevenness, and point defects of the antireflection film of the present invention appears in a smaller amount of addition. It is an object to improve productivity by providing high-speed coating aptitude while increasing planar uniformity.

Next, the antireflection layer in which the medium refractive index layer, the high refractive index layer, and the low refractive index layer are laminated in this order on the protective film will be described.

On the protective film, an antireflection layer having a layer structure of at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) is designed to have a refractive index that satisfies the following relationship.

Refractive Index of High Refractive Index Layer> Refractive Index of Middle Refractive Index Layer> Refractive Index of Protective Film> Refractive Index of Low Refractive Index Layer

Moreover, you may form a hard-coat layer between a protective film and a medium refractive index layer. Moreover, you may consist of a medium refractive index hard-coat layer, a high refractive index layer, and a low refractive index layer.

For example, the antireflection layer described in Unexamined-Japanese-Patent No. 8-122504, 8-110401, 10-300902, Unexamined-Japanese-Patent No. 2002-243906, Unexamined-Japanese-Patent No. 2000-111706, etc. are mentioned. have.

In addition, different functions may be imparted to each layer, for example, an antifouling low refractive index layer and an antistatic high refractive index layer (e.g., Japanese Unexamined Patent Application Publication No. 10-206603). Patent Publication No. 2002-243906, etc.) etc. are mentioned.

It is preferable that it is 5% or less, and, as for the haze of an antireflection layer, 3% or less is more preferable. In addition, the strength of the film is preferably at least H, more preferably at least 2H, and most preferably at least 3H in a pencil hardness test according to JIS K5400.

(High refractive index layer and medium refractive index layer)

The layer in which the antireflection film has a high refractive index consists of a cured film containing at least an inorganic compound fine particle having a high refractive index and an average particle diameter of 100 nm or less and a matrix binder.

Examples of the inorganic compound fine particles having a high refractive index include inorganic compounds having a refractive index of 1.65 or more, and those having a refractive index of 1.9 or more are preferable. For example, oxides, such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In, a complex oxide containing these metal atoms, etc. are mentioned.

In order to make such microparticles | fine-particles, the particle surface is treated with a surface treating agent (for example, a silane coupling agent etc .: Unexamined-Japanese-Patent No. 11-295503, 11-153703, Unexamined-Japanese-Patent No. 2000-9908, Anionic compounds or organometallic coupling agents: JP-A-2001-310432, etc., having a core-shell structure composed of high refractive index particles as a core (JP-A-2001-166104, etc.), using a specific dispersant (eg, , Japanese Unexamined Patent Application Publication No. Hei 11-153703, US Patent No. 6210858, Japanese Unexamined Patent Publication No. 2002-277609, and the like.

As a material which forms a matrix, a conventionally well-known thermoplastic resin, curable resin film, etc. are mentioned.

Further preferred materials include polyfunctional compound-containing compositions having at least two polymerizable groups of radical polymerizable and cationic polymerizable, compositions containing organometallic compounds containing hydrolyzable groups, and partial condensates thereof. 1 or more types of compositions chosen from a composition are mentioned.

For example, the compound described in Unexamined-Japanese-Patent No. 2000-47004, 2001-315242, 2001-31871, 2001-296401, etc. are mentioned.

Moreover, the curable film obtained from the colloidal metal oxide obtained from the hydrolysis-condensation product of a metal alkoxide and a metal alkoxide composition is also preferable. For example, it is described in Unexamined-Japanese-Patent No. 2001-293818.

It is preferable that the refractive index of a high refractive index layer is 1.70-2.20. It is preferable that it is 5 nm-10 micrometers, and, as for the thickness of a high refractive index layer, it is more preferable that it is 10 nm-1 micrometer.

The refractive index of the medium refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. It is preferable that the refractive index of a medium refractive index layer is 1.50-1.70. Moreover, it is preferable that it is 5 nm-10 micrometers, and, as for thickness, it is more preferable that it is 10 nm-1 micrometer.

(Low refractive index layer)

The low refractive index layer is formed by sequentially laminating the high refractive index layer. The refractive index of the low refractive index layer is preferably 1.20 to 1.55. More preferably, it is 1.30-1.50.

It is preferable to construct a low refractive index layer as an outermost layer which has scratch resistance and antifouling property. As a means of greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and a means of a thin film layer made of the introduction of conventionally known silicon, the introduction of fluorine, or the like can be applied.

Moreover, the compound containing a crosslinkable or polymerizable functional group which contains a fluorine atom in the range of 35-80 mass% is preferable.

For example, Japanese Unexamined Patent Application Publication No. Hei 9-222503, Paragraph Nos. [0018] to [0026], Japanese Patent Application Laid-Open No. 11-38202, Paragraph No. [0019] to [0030], and Japanese Unexamined Patent Application Publication No. 2001-40284 The compound as described in No.-[0028], Unexamined-Japanese-Patent No. 2000-284102, etc. are mentioned.

It is preferable that the refractive index of a fluorine-containing compound is 1.35-1.50. More preferably, it is 1.36-1.47.

It is preferable that it is a compound which has a polysiloxane structure, contains a curable functional group or a polymerizable functional group in a polymer chain, and has a bridge structure in a film | membrane as a silicone compound. For example, reactive silicone (for example, cyraprene (made by Jisso) etc.), polysiloxane containing a silanol group in a sock end (Japanese Unexamined-Japanese-Patent No. 11-258403, etc.) etc. are mentioned.

The crosslinking or polymerization reaction of at least one of a fluorine-containing polymer and a siloxane polymer having a crosslinking or polymerizable group is carried out by irradiating or heating a coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer, or the like at the same time. It is preferable to form a low refractive index layer.

Moreover, the sol-gel cured film which hardens organometallic compounds, such as a silane coupling agent, and the specific fluorine-containing hydrocarbon group containing silane coupling agent by condensation reaction under catalyst coexistence is also preferable.

For example, a polyfluoroalkyl group containing silane compound or its partial hydrolysis-condensation product (Japanese Unexamined-Japanese-Patent No. 58-142958, 58-147483, 58-147484, Unexamined-Japanese-Patent No. 9-157582). , A compound described in Japanese Patent Application Laid-Open No. 11-106704, and a silyl compound containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (JP-A-2000-117902, 2001-48590, and 2002-53804). Compounds of a base material, etc.) etc. are mentioned.

The low refractive index layer is a low refractive index inorganic compound having a primary particle average diameter of primary particles such as fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride), etc. as additives other than the above. , Organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), a silane coupling agent, a lubricant, a surfactant, and the like.

When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a gas phase method (vacuum vapor deposition method, sputtering method, ion plating method, plasma CVD method, or the like). An application method is preferable at the point which can be manufactured inexpensively.

The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

(Hard coat layer)

The hard coat layer is formed on the surface of the protective film in order to impart physical strength to the protective film on which the antireflection layer is formed. In particular, it is preferable to form between a transparent support body and the said high refractive index layer. It is preferable that a hard-coat layer is formed by the crosslinking reaction of a curable compound of light and / or heat, or a polymerization reaction. As a curable functional group in a curable compound, a photopolymerizable functional group is preferable. Moreover, the organometallic compound and organic alkoxysilyl compound containing a hydrolysable functional group are also preferable.

As a specific example of these compounds, the thing similar to what was illustrated by the high refractive index layer is mentioned. As a specific structural composition of a hard-coat layer, what was described in Unexamined-Japanese-Patent No. 2002-144913, 2000-9908, international publication 00/46617 pamphlet, etc. are mentioned, for example.

The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to finely disperse the fine particles by using the method described in the high refractive index layer and to contain the fine coat in the hard coat layer.

The hard coat layer may also serve as an antiglare layer containing particles having an average particle diameter of 0.2 to 10 μm and imparting an antiglare function (antiglare function).

The film thickness of a hard coat layer can be designed suitably according to a use. It is preferable that the film thickness of a hard-coat layer is 0.2-10 micrometers, More preferably, it is 0.5-7 micrometers.

In the pencil hardness test according to JIS K5400, the strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. In the taper test according to JIS K5400, the smaller the amount of abrasion of the test pieces before and after the test, the more preferable.

(Other layers of antireflective layer)

Moreover, you may form a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, etc.

(Antistatic layer)

When forming an antistatic layer, it is preferable to provide electroconductivity whose volume resistivity is ^10-8 (ohm ^- cm- ³ ) or less. Although it is possible to impart a volume resistivity of 10 ^-8 (Ωcm ^-3 ) by using a hygroscopic substance, a water-soluble inorganic salt, a surfactant of any kind, a cationic polymer, an anionic polymer, colloidal silica, etc., the temperature and humidity dependence is large and low humidity There is a problem in that sufficient conductivity cannot be secured. Therefore, a metal oxide is preferable as a conductive layer material. Although some metal oxides are colored, when these metal oxides are used as a conductive layer material, the whole film is colored, which is not preferable. Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W, or V is mentioned as a metal which forms a metal oxide without coloring, and it is preferable to use the metal oxide which has these as a main component. Specific examples thereof include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , WO ₃ , V ₂ O _5, and the like, or composite oxides thereof. ZnO, TiO ₂ , and SnO ₂ are preferred. Examples including the heteroatom is, for example, additives, such as Al, In with respect to ZnO, the addition of such as Sb, Nb, a halogen element with respect to SnO _2, also added, such as Nb, Ta with respect to TiO ₂ is effective. As described in Japanese Patent Publication No. 59-6235, a material in which the metal oxide is attached to other crystalline metal particles or fibrous material (for example, titanium oxide) may be used. In addition, although the volume resistance value and surface resistance value are separate physical property values and cannot be compared simply, in order to ensure the conductivity of 10 ^-8 (Ωcm ^-3 ) or less in the volume resistance value, this conductive layer is roughly 10 ^-10 (Ω / □) What is necessary is just to have the following surface resistance values, More preferably, it is ^10-8 ((ohm / square)). The surface resistance value of a conductive layer needs to be measured as a value when the antistatic layer is made into the outermost layer, and can be measured in the middle of forming the laminated | multilayer film of this patent.

(Liquid crystal display device)

The liquid crystal display device of this invention uses the liquid crystal display device (1st form) which used the polarizing plate of this invention, and the VA mode, OCB mode, and TN mode liquid crystal display device which used two sheets of the polarizing plate of this invention above and below a cell. 2 type) and VA mode liquid crystal display device (3rd aspect) which used either one of the polarizing plate of this invention for the backlight side.

That is, the polarizing plate of this invention is used advantageously for a liquid crystal display device. The polarizing plate 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), and Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. Among these, it can use suitably for VA mode or OCB mode.

In the liquid crystal cell of VA mode, rod-shaped liquid crystalline molecules are oriented substantially vertically when no voltage is applied.

The liquid crystal cell of VA mode WHEREIN: (1) Liquid crystal cell of narrow VA mode which orientates a rod-shaped liquid crystalline molecule substantially vertically when a voltage is not applied, and substantially horizontally when a voltage is applied. In addition to 2-176625, (2) a liquid crystal cell (of MVA mode) (SID97, Digest of tech. Papers (Preliminary Publication) 28 (1997) 845, which multi-domains VA mode for viewing angle enlargement. ), (3) a liquid crystal cell (n-ASM mode, CPA mode) of a liquid crystal cell (n-ASM mode, CPA mode) in which the rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and are distorted when voltage is not applied. 58 to 59 (1998)) and (4) liquid crystal cells of SURVAIVAL mode (presented by LCD International 98).

As a liquid crystal display device of VA mode, what consists of a liquid crystal cell (VA mode cell) and two polarizing plates (TAC1, polarizer, and TAC2) arrange | positioned at the both sides is mentioned (FIG. 2). The liquid crystal cell carries liquid crystal between two electrode substrates.

The liquid crystal cell of the OCB mode is a liquid crystal display device using a liquid crystal cell of a bend alignment mode in which rod-shaped liquid crystalline molecules are oriented (symmetrically) in substantially opposite directions at the top and bottom of the liquid crystal cell. The liquid crystal cell of the OCB mode is disclosed in the specifications of US Pat. No. 4,458,525 and 5410422. Since the rod-shaped liquid crystal molecules are symmetrically aligned at the top and the bottom of the liquid crystal cell, the liquid crystal cell in the bend alignment mode has a magneto-optical compensation function. Therefore, this liquid crystal mode is also called OCB (Otically Compensatory Bend) liquid crystal mode. The liquid crystal display device of the bend alignment mode has an advantage that the response speed is high.

In another aspect of the transmissive liquid crystal display device of the present invention, the cellulose acylate film according to the present invention is used as a protective film for the polarizing plate disposed between the liquid crystal cell and the polarizer. The cellulose acylate film may be used only for the protective film (between the liquid crystal cell and the polarizer) of one polarizing plate, or the cellulose acylate film may be used for two protective films (between the liquid crystal cell and the polarizer) of both polarizing plates. do. It is preferable to make the cellulose acylate film (TAC1) which concerns on this invention to the VA cell side for the bonding to a liquid crystal cell. When the said cellulose acylate film is used only for the protective film (between a liquid crystal cell and a polarizer) of one polarizing plate, this may be good in either of an upper polarizing plate (observation side) and a lower polarizing plate (backlight side), and there is no problem functionally. . However, when it is used as an upper polarizing plate, it is necessary to form a functional film on an observation side (upper side), and since a production yield may fall, it is considered that it is high when it is used as a lower polarizing plate, and is considered to be more preferable embodiment.

And the liquid crystal display device of the 2nd form which formed both the light source side and the observer side in the polarizing plate of this invention is the liquid crystal display device of the 3rd form which formed only the light source side in the polarizing plate of this invention.

A normal cellulose acylate film may be sufficient as the protective film (TAC2), for example, commercially available KC4UX2M (40 micrometers manufactured by Konica Opt Co., Ltd.), KC5UX (60 micrometers manufactured by Konica Opt Co., Ltd.), KC80UVSFD (Konica Opt) Although 80 micrometers of Corporation | KK make, TD80U (80 micrometers of FUJIphotograph Film Co., Ltd.), TF80U (80 micrometers of FUJIphotograph Film Co., Ltd.) etc. are mentioned, It is not limited to these.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to an Example.

[Film Formation of Cellulose Acylate Film (Films 1 to 19)]

(Cellulose acylate)

The kind of acyl group of Table 1, and the cellulose acylate from which substitution degree differs were prepared. This added sulfuric acid (7.8 mass parts with respect to 100 mass parts of cellulose) as a catalyst, added the carboxylic acid used as a raw material of an acyl substituent, and performed the acylation reaction at 40 degreeC. At this time, the kind and substitution degree of an acyl group were adjusted by adjusting the kind and quantity of carboxylic acid. Furthermore, aging was performed at 40 degreeC after acylation. In addition, the low molecular weight component of this cellulose acylate was removed by washing with acetone. In the table, CAB is an abbreviation of cellulose acetate butyrate (cellulose ester derivative consisting of acetyl group and butyryl group), and CAP is an abbreviation of cellulose acetate propionate (cellulose ester derivative containing acyl group of acetyl group and propionyl group). And CTA means cellulose triacetate (cellulose ester derivative whose acyl group consists only of an acetyl group).

(Dissolution)

The cellulose acylate, the plasticizer (TPP: triphenyl phosphate, BDP: biphenyl diphenyl phosphate) shown in Table 1, the following ultraviolet absorbers 1, 2, the following retardation expression agents 1, 2, the following mixed solvent, dichloromethane / methanol It was added to (87/13 parts by mass) while stirring so that the mass concentration of cotton was 15% by mass, and the mixture was heated and stirred to dissolve. At the same time, 0.05 part by mass of a mat agent (AEROSIL R972, manufactured by Nippon Airzyl Co., Ltd.) as fine particles was added to 100 parts by mass of cellulose acylate and stirred while heating. The additive amount in Table 1 is the mass of the additive with respect to the cotton mass 100.

Ultraviolet absorbers 1

UV absorbers 2

Retardation Expression Agents 1

Retardation Expression Agents 2

(softness)

The dope described above was cast using a band softener. Drawing ratio of peeling film from band at 25-35 mass% of residual solvent amount to draw ratio of 10%-30.5% using a tenter on the condition that extending | stretching temperature is about Tg-10-Tg + 10 degreeC (refer Table 1) ) In the width direction to form a cellulose acylate film (1 to 19). In Table 1, the draw ratio in a tenter is shown.

In addition, the measuring method of Tg is as follows. That is, after the film sample (non-stretched) 5 mm x 30 mm was humidified at 25 degreeC 60% RH for 2 hours or more, it was clamped with a dynamic viscoelasticity measuring apparatus (Vibron: DVA-225 (made by Haiti Measurement Control Co., Ltd.)). When measured at a distance of 20 mm, a heating rate of 2 ° C./min, a measurement temperature range of 30 ° C. to 200 ° C., and a frequency of 1 Hz, the storage elastic modulus is obtained when the storage elastic modulus is taken as the major axis on the vertical axis, and the temperature (° C.) as the linear axis on the horizontal axis The rapid decrease in storage modulus seen in the transition from the solid region to the glass transition region results in the intersection of the straight line 1 and the straight line 2 when the straight line 1 is drawn in the solid region and the straight line 2 is drawn in the glass transition region. Since it is a temperature which decreases rapidly and starts to soften a film, and starts to transition to a glass transition area | region, it was set as glass transition temperature (Tg; dynamic viscoelasticity). When Tg of the film of Example was irradiated by the said method, it was all in the range of 110-160 degreeC.

The produced cellulose acylate film (optical compensation sheet; 1 to 19) was humidified at 25 ° C. 60% RH for 2 hours or more, and a birefringence measuring device (KOBRA 21ADH, manufactured by Oji Meter Co., Ltd.) was used at 25 ° C. 60 The Re retardation value and Rth retardation value in wavelength 590nm were measured at% RH. The results are shown in Table 3.

As for the haze of the film obtained by the present Example, the mass mean change at the time of leaving 0.1-0.9 and the 2nd average particle diameter of a mat agent is 1.0 micrometer or less for 48 hours on 80 degreeC 90% RH conditions is 0 to 3%. It was. In addition, the photoelastic coefficient of any sample was 50 × 10 ^-13 cm 2 / dyne or less.

[Preparation of protective film with optically anisotropic layer (films 20 to 23)]

[Protective films 20 and 21 with optically anisotropic layer]

5.2 ml / m <2> of the following composition was apply | coated on the cellulose acetate films 20 and 21 (refer Table 1) produced as mentioned above, and it dried at 60 degreeC for 10 second. The surface of the film was washed with running water for 10 seconds, and the film surface was dried by separating air at 25 ° C.

(Soap liquid composition)

Isopropyl alcohol 818 parts by mass

167 parts by mass of water

187 parts by mass of propylene glycol

68 parts by mass of potassium hydroxide

12 parts by mass of surfactant (nC ₁₆ H ₃₃ O (C ₂ H ₄ O) ₁₀ H)

(Formation of alignment film)

On the saponified cellulose acetate films 20 and 21, the coating liquid of the following composition was apply | coated 24 ml / m <2> with the wire bar coater of # 14. It dried for 60 second by the warm air of 60 degreeC, and 150 second by the warm air of 90 degreeC.

Next, the rubbing process was performed to the film | membrane formed in the extending direction (nearly coinciding with the ground axis) of the cellulose acetate films 20 and 21, and the direction of 45 degrees.

(Orientation film coating liquid composition)

20 parts by mass of modified polyvinyl alcohol (1)

360 parts by mass of water

120 parts by mass of methanol

Glutalaldehyde (crosslinking agent) 1.0 parts by mass

Modified Polyvinyl Alcohol (1)

(Formation of Optically Anisotropic Layer)

91 parts by mass of the following discotic liquid crystalline molecules (I), 9 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate (CAB531) -1, produced by Eastman Chemical Co., Ltd. 1.5 parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Chiba Co., Ltd.) 3 parts by mass, sensitizer (Gayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass, The coating liquid which melt | dissolved 1.0 mass part of citrate ester mixtures in 214.2 mass parts methyl ethyl ketone was apply | coated 6.2 ml / m <2> by the wire bar coater of # 3.6 in 25 degreeC atmosphere. This was attached to a metal mold and heated in a thermostat at 140 ° C. for 2 minutes to orient the discotic liquid crystalline molecules. Next, using a 120 W / cm high pressure mercury lamp at 90 ° C., UV irradiation was performed for 1 minute to polymerize the discotic liquid crystalline molecules. Then, it cooled to room temperature and produced the protective films 20 and 21 with an optically anisotropic layer.

Discotic liquid crystalline molecule (I)

Citrate Ester Mixtures

[Protective film 22 with optically anisotropic layer]

A biaxially stretched PET film of a cholesteric liquid crystal liquid formed by mixing a nematic liquid crystalline compound represented by the above formula and a chiral agent represented by the following formula so as to have a selective reflection wavelength of 290 to 310 nm and adding a photopolymerization initiator thereto. Coated on, heat-treated at 80 ° C. for 3 minutes, and irradiated with ultraviolet rays to crosslink to obtain a retardation layer (B) having a thickness of 1.9 μm, Re of 2 nm and Rth of 132 nm, and acrylic adhesive having a thickness of 15 μm. Laminated retardation film 22 having Re and 2nm and Rth of 182nm by laminating with a cellulose acylate film (Fujitack TD80U (manufactured by Fuji Photographic Film Co., Ltd.)) commercially available through layers and peeling a biaxially stretched PET film. Got.

[Protective film 23 with optically anisotropic layer]

Polycycloimide synthesized from 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl It melt | dissolved in the paddy field and prepared the 15 mass% solution. This polyimide solution was applied onto a 80 μm thick TAC film (Fuji Photo Film Co., Ltd. TD80U) (substrate), dried at 120 ° C. for 10 minutes, and a non-liquid crystalline polymer layer having a thickness of 5 μm and a TAC film. A laminate was obtained. The laminated body was tentatively axially stretched by 1.05 times, and the protective film 23 with an optically anisotropic layer which is a laminated body of 73 micrometers in thickness was obtained. This laminated body is a laminated body of the stretched TAC film which is an optical compensation layer, and the stretched non-liquid crystalline polymer layer which is an optical compensation layer.

[Production of protective films (films 24 and 25) with antireflection function]

[Protective film with antireflection function 24]

(Preparation of coating liquid for light scattering layer)

50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. Furthermore, 2g of polymerization initiators (Irgacure 184, Chiba Specialty Chemicals Co., Ltd. product) were added, and it stirred and mixed. The refractive index of the coating film obtained by apply | coating this solution and UV-curing was 1.51.

1.7 g of a 30% toluene dispersion of a crosslinked polystyrene particle having an average particle diameter of 3.5 μm (refractive index of 1.60, SX-350, manufactured by Soken Chemical Co., Ltd.), which was dispersed in a solution at 10000 rpm for 20 minutes using a polytron disperser, was 1.7 g and an average particle diameter of 3.5 μm. 13.3 g of a 30% toluene dispersion of cross-linked acrylic-styrene particles (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) was added, and finally, 0.75 g of a fluorine-based surface modifier (FP-1) and a silane coupling agent (KBM-5103, 10g of Shin-Etsu Chemical Co., Ltd. product) was added and it was set as the completion liquid.

The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 µm to prepare a coating liquid for a light scattering layer.

(Preparation of coating liquid for low refractive index layer)

First, the sol liquid (a) was prepared as follows. A reactor with a stirrer, a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyl trimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxy aluminum ethyl acetoacetate were added, After mixing, 30 parts of ion-exchanged water was added, the mixture was reacted at 60 ° C for 4 hours, and then cooled to room temperature to obtain a sol solution (a). The mass average molecular weight was 1600, and the component whose molecular weight is 1000-20000 was 100% among the components more than an oligomer component. In addition, in gas chromatography analysis, acryloyloxypropyltrimethoxysilane as a raw material did not remain at all.

Thermal crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN-7228, 6% solid content, manufactured by JSR Co., Ltd.) 13 g, silica sol (silica, MEK-ST particle size is different, average particle diameter 45nm, solid content concentration 30%, Nissan Chem. Co., Ltd.) 1.3 g, the sol solution (a) 0.6 g, methyl ketone 5 g, cyclohexanone 0.6 g was added and stirred, and then filtered through a polypropylene filter having a pore diameter of 1 μm to obtain a low refractive index. The coating liquid for layers was prepared.

(Production of a transparent protective film with an antireflection layer)

A triacetyl cellulose film (Fuji-Tak TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 µm was started to be rolled, and the coating liquid for the functional layer (light scattering layer) was 180 pieces / inch, and a depth of 40 µm. Using a gravure roll having a gravure pattern of 50 mm in diameter and a doctor blade, the coating was applied under conditions of a gravure roll rotation speed of 30 rpm and a conveying speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further 160 W under nitrogen purge. Using an air-cooled metal halide lamp (manufactured by IGraphics Co., Ltd.) / cm, irradiated with ultraviolet light of 400 mW / cm 2 irradiance of 250 mJ / cm 2 irradiated, the coating layer was cured, and a functional layer having a thickness of 6 μm was formed and wound up. .

The triacetyl cellulose film coated with this functional layer (light scattering layer) is started to be wound again, and on the light scattering layer side, the prepared low refractive index coating liquid has a diameter of 50 mm having a gravure pattern of 180 pieces / inch and a depth of 40 µm. Using a microgravure roll and a doctor blade, and applied under conditions of a gravure roll rotation speed of 30 rpm and a conveying speed of 15 m / min, drying at 120 ° C. for 150 seconds, further drying at 140 ° C. for 8 minutes, and then 240 W under nitrogen purge. UV light having an illuminance of 400 mW / cm 2 and an irradiation dose of 900 mJ / cm 2 using a / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to form a low refractive index layer having a thickness of 100 nm and wound up, with antireflection function A protective film (film 24) was produced.

[Protective film with antireflection function (25)]

(Preparation of coating liquid for hard coat layer)

Trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.) 750.0 parts by mass, 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 3000, methyl ethyl ketone 730.0 g, cyclohexanone 500.0 g and a photopolymerization initiator (Irgacure 184, manufactured by Nippon Chiba Co., Ltd.) 50.0 g were added and stirred. It filtered with the polypropylene filter of pore diameter 0.4 micrometer, and prepared the coating liquid for hard-coat layers.

(Preparation of titanium dioxide fine particle dispersion)

As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129, manufactured by Ishihara Industries Co., Ltd.) containing cobalt and surface-treated using aluminum hydroxide and zirconium hydroxide were used.

38.6 g of the following dispersants and 704.3 g of cyclohexanone were added to this particle 257.1 g, and it disperse | distributed with dynomil, and prepared the titanium dioxide dispersion liquid of the mass mean diameter of 70 nm.

(Preparation of coating liquid for medium refractive index layer)

To 88.9 g of the titanium dioxide dispersion, 58.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerization initiator (irgacure 907), a photosensitizer (gayacure DETX, Nippon Kayaku Co., Ltd. product) 1.1g, methyl ethyl ketone 482.4g, and cyclohexanone 1869.8g were added and stirred. After stirring sufficiently, it filtered with the polypropylene filter of 0.4 micrometer of pore diameters, and prepared the coating liquid for medium refractive index layers.

(Preparation of coating liquid for high refractive index layer)

To 586.8 g of the titanium dioxide dispersion, 47.9 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (irgacure 907, Nippon Chibaga 4.0 g of Iki Co., Ltd., a photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd. product) 1.3g, methyl ethyl ketone 455.8g, and cyclohexanone 1427.8g were added and stirred. It filtered with the polypropylene filter of pore diameter 0.4 micrometer, and prepared the coating liquid for high refractive index layers.

(Preparation of coating liquid for low refractive index layer)

The following copolymer (P-1) was melt | dissolved in methyl isobutyl ketone so that it may be set to the density | concentration of 7 mass%, and terminal methacrylate group containing silicone resin X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) was prepared with respect to solid content 3 % And an optical radical generating agent Irgacure 907 (brand name) were added 5 mass% with respect to solid content, and the coating liquid for low refractive index layers was prepared.

Copolymer (P-1)

(Production of a transparent protective film with an antireflection layer)

The coating liquid for hard-coat layers was apply | coated using the gravure coater on the triacetyl cellulose film (Fuji-Tak TD80U, Fujifilm Film Co., Ltd. product) of 80 micrometers in film thickness. After drying at 100 ° C., a roughness of 400 mW / cm 2 and irradiation amount of 300 mJ / cm 2 were obtained using an air-cooled metal halide lamp of 160 W / cm (manufactured by Igraphics) while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less. Was irradiated with ultraviolet light to cure the coating layer to form a hard coat layer having a thickness of 8 µm.

On the hard coat layer, the coating liquid for the medium refractive index layer, the coating liquid for the high refractive index layer, and the coating liquid for the low refractive index layer were successively applied using a gravure coater having three coating stations.

Drying conditions of the medium refractive index layer were 100 ° C. for 2 minutes, and UV curing conditions were performed using an air-cooled metal halide lamp of 180 W / cm 2 (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less. It used as the irradiation dose of roughness 400mW / cm <2> and irradiation amount 400mJ / cm <2>. The medium refractive index layer after hardening became refractive index 1.630 and film thickness 67 nm.

The drying conditions of the high refractive index layer and the low refractive index layer were both 90 ° C. and 1 minute, and then 100 ° C. and 1 minute. The UV curing conditions were air-cooled at 240 W / cm 2 while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less. Using a metal halide lamp (manufactured by Isographix Co., Ltd.), the irradiation amount was set at an illuminance of 600 mW / cm 2 and an irradiation amount of 600 mJ / cm 2.

The high refractive index layer after curing was 1.905, a film thickness of 107 nm, and the low refractive index layer had a refractive index of 1.440 and a film thickness of 85 nm. In this way, the transparent protective film (film 25) with an antireflection layer was produced.

Example 1

(Production of Polarizing Plate 1)

In the width direction of the polyvinyl alcohol (PVA) film of thickness 75 micrometers and polymerization degree 2400, it connected so that an infrared heater (manufactured by Nippon Kasei Co., Ltd.) could be controlled at 70 mm intervals. After giving a temperature gradient in the width direction so that a center part may be 30 degreeC, and an edge part may be 40 degreeC, and heat-processing for about 5 second, after swelling for 40 second with 30 degreeC warm water, 0.06 mass% of iodine concentrations and potassium iodide While immersing in 6 mass% aqueous solution for 60 second at 30 degreeC, and then immersing at 40 degreeC for 60 second in the aqueous solution of 4 mass% of boric acid concentration, and 3 mass% of potassium iodide, the longitudinal direction was 5.2 of the original length. Stretched to double. At this time, stretching is carried out sequential biaxial stretching using a tenter clip, as described above, after stretching 5.2 times in the longitudinal direction, stretching in the transverse direction 1.1 times, and finally stretching so that the longitudinal direction becomes 5 times the original length. It was.

Then, it dried for 4 minutes at 50 degreeC, and obtained the polarizer (1). The maximum film thickness in the width direction of the polarizer 1 was 32.0 μm, the minimum film thickness was 30.0 μm, and the difference between the maximum film thickness and the minimum film thickness was 2.0 μm.

The already produced cellulose acylate film (1) and Fuji Photographic Film Co., Ltd. TD80U were immersed in an aqueous solution of sodium hydroxide at 55 ° C. at 1.5 mol / liter, and then sodium hydroxide was sufficiently washed out with water. Then, after immersing in 35 degreeC diluted sulfuric acid aqueous solution at 0.005 mol / liter for 1 minute, it was immersed in water and the dilute sulfuric acid aqueous solution was wash | cleaned sufficiently. Finally, the sample was sufficiently dried at 120 ° C.

The cellulose acylate film (1) subjected to saponification as described above and TD80U manufactured by Fuji Photographic Film Co., Ltd. were bonded together using a polyvinyl alcohol adhesive so as to sandwich the polarizer, and further heated at 70 ° C. for 30 minutes. Then, the ear | edge part was cut out with 3 cm and the cutter in the width direction, and the effective width 1200mm and the polarizing plate 1 of the roll form of length 50m were produced.

Table 3 shows the polarization performance (single plate transmittance, polarization degree) of the polarizer maximum film thickness part of the width direction of the obtained polarizing plate 1, and the polarization performance (single plate transmittance, polarization degree) of the minimum film thickness part.

(Production of Polarizing Plates 2 to 23 and 27 to 30)

In addition, using the already prepared protective film 2-25 and a commercially available cellulose acylate film, in the combination of Table 3, it carried out similarly to the case of the polarizing plate 1, and made the polarizing plates 2-23 and 27-30. Produced. It is as showing in Table 2 except the film thickness of the PVA film which produced each polarizing plate, polymerization degree, and the manufacturing conditions of a polarizer.

The maximum film thickness as the width direction of the obtained polarizer, the minimum film thickness, the polarization performance of the maximum film thickness part of the obtained polarizing plate, and the polarization performance of the minimum film thickness part were shown in Table 2, Table 3.

As a commercially available cellulose acylate film, Fujitaek TF80U, Fujitaek TD80U (manufactured by Fuji Photo Film Co., Ltd.), and KC80UVSFD (manufactured by Konica Opt Co., Ltd.) were used.

At this time, since the polarizer and the protective films on both sides of the polarizer are produced in a roll form, the longitudinal direction of each roll film is parallel and is continuously bonded. Moreover, in the protective film arrange | positioned at the cell side, the transmission axis of a polarizer and the slow axis of each cellulose acylate films 1-19 are parallel.

In the case of the protective films 20-23 with an optically anisotropic layer, the transparent support body side was adhere | attached on the one side of the polarizer using a polyvinyl alcohol-type adhesive agent. It was arrange | positioned so that the slow axis of a transparent support body and the transmission axis of a polarizer might become parallel.

(Production of Polarizing Plate 31)

Similarly, the polarizing plate of 1200 mm in total width | variety which is a cellulose acylate film (TD80U manufactured by Fujiphotograph Film Co., Ltd.) by which both sides of a polarizer (refer Table 3 polarizing plate No.31) is marketed was produced. The stretched film with a thickness of 90 micrometers was stuck to the one side through the acrylic adhesive layer of thickness 25 micrometers, and the polarizing plate 31 was obtained. Moreover, the said stretched film is obtained by carrying out a lateral stretch process of the norbornene-type resin film (JSR Corporation make, ARTON) of thickness 100micrometer through a tenter, and is Re95nm, Rth 50nm. In addition, Re and Rth were computed with the refractive index measured by the Oji Scientific Instruments Co., Ltd. product, and KOBRA 21ADH.

The separator film was affixed on the acryl-type adhesive material and the adhesive material to the cell side surface of the polarizing plate 31 produced above. The protective film was attached to the surface opposite the cell.

Comparative Example 1 (Production of Polarizing Plates 24 to 26)

Polarizing plates 24 to 26 were produced in the same manner as in Example 1 except that the infrared heater was not connected and the stretching was not the biaxial stretching but the free monoaxial stretching. The combination of a protective film is as showing in Table 3.

Reflectance Measurement

Using a spectrophotometer (manufactured by Nippon Bunco Co., Ltd.), the spectral reflectance at the incident angle of 5 ° was measured on the functional film side in the wavelength region of 380 to 780 nm, and the integral sphere average reflectance of 450 to 650 nm was obtained. It was 0.4% in the polarizing plates 4 and 12 using the film 26 which is a transparent protective film with a protective layer, and 0.4% in the polarizing plates 7 and 13 using the film 27 which is a transparent protective film with an antireflection layer. The protective film on the transparent protective film with a reflection prevention layer peeled here and the reflectance measurement was performed.

[Mounting on Panel]

Example 2

(Mount for VA Panel)

The polarizing plate and the retardation plate of the front and back of the liquid crystal TV (LC-30AD1, Sharp Co., Ltd.) of VA mode are peeled off, and it is shown in Table 4 in the polarizing plates (1-23, 27-31) produced in Example 1 on the front and back side. What was shown and the commercially available polarizing plate (HLC2-5618, Sanlitz Co., Ltd.) without a viewing angle compensation plate were made into the panel size (30 inches, 65 cm x 39 cm), and it bonded by the combination of Table 4.

At this time, the absorption axis of the polarizing plate on the viewer side was set to the panel horizontal direction, the absorption axis of the polarizing plate on the backlight side was set to the panel vertical direction, and the adhesive material surface was arrange | positioned so that it might become the liquid crystal cell side.

After peeling off the protective film, using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle (contrast ratio is 10 or more and black tones are reversed in eight steps from black display L1 to white display L8) No range) was measured. Even when either polarizing plate was used, favorable viewing angle characteristics were obtained.

(Evaluation of Screen Uniformity)

Screen uniformity was evaluated about the liquid crystal panel using the polarizing plate produced in Example 1 produced above.

The liquid crystal TV was assembled and the backlight was turned on using the liquid crystal panel which bonded the polarizing plate. 30 inches of liquid crystal panels were used for evaluation.

The screen uniformity was evaluated as follows. The results are shown in Table 4.

(Double-circle): Any part of a screen is the same brightness, and uniformity is very good.

(Circle): On the screen, when it sees well, the part which looks a little dark is recognized.

×: There is a dark part on the screen.

××: A dark part is clearly recognized on the screen.

Comparative Example 2

About the polarizing plates 24-26 produced by the comparative example 1, it carried out similarly to Example 2, and mounted to VA panel.

After peeling off the protective film, using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle (contrast ratio is 10 or more and black tones are reversed in eight steps from black display L1 to white display L8) Range), the viewing angle characteristic was poor even when either polarizing plate was used, and was inferior to the case where the polarizing plate of the present invention was used.

In addition, evaluation of the uniformity of the screen was similarly performed, but there was a dark portion on the screen, which was inferior to that of the polarizing plate of the present invention (Table 4).

Example 3

(Production of bend alignment liquid crystal cell)

The polyimide film was formed as an orientation film in the glass substrate with an ITO electrode, and the rubbing process was performed to the orientation film. The obtained glass substrates were faced with the arrangement | positioning which a rubbing direction becomes parallel, and the cell gap was set to 5.7 micrometers. A liquid crystal compound (ZLI1132, manufactured by Merck Co., Ltd.) having a Δn of 0.1396 was injected into the cell gap to prepare a bend alignment liquid crystal cell (30 inches, 65 cm × 39 cm).

(Production of liquid crystal display device)

The produced polarizing plates 27 and 28 were bonded so as to sandwich the produced bend alignment cell. (Combination is described in Table 5) The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were arranged so as to be antiparallel.

As a result of lighting and observing the thus produced liquid crystal display device, it was found that the liquid crystal display device using the polarizing plate of the present invention is preferable because the change in contrast viewing angle and color viewing angle is small.

(Evaluation of Screen Uniformity)

Moreover, screen uniformity was evaluated about the said liquid crystal panel. Evaluation was performed as follows. The results are shown in Table 5.

(Double-circle): Any part of a screen is the same brightness, and uniformity is very good.

(Circle): On the screen, when it sees well, the part which looks a little dark is recognized.

×: There is a dark part on the screen.

××: A dark part is clearly recognized on the screen.

Comparative Example 3

About the polarizing plates 24-26 produced by the comparative example 1, it carried out similarly to Example 3, and mounted to the panel.

After peeling off the protective film, using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle (contrast ratio is 10 or more and black tones are reversed in eight steps from black display L1 to white display L8) Range), the viewing angle characteristic was poor even when either polarizing plate was used, and was inferior to the case where the polarizing plate of the present invention was used.

Moreover, although evaluation of the uniformity of the screen was performed similarly, there was a dark part on the screen and it was inferior to the polarizing plate of this invention (Table 5).

The roll-shaped polarizing plate of this invention is small in the film thickness difference of a polarizer, and can use the polarizing plate of this invention, and can manufacture the liquid crystal display device of uniform display quality also in a big screen.

Claims (17)

As a roll-shaped polarizing plate which bonded the protective film to at least one side among the polarizer which consists of polyvinyl alcohol of the polymerization degree 1000-3800, The difference between the largest film thickness and the minimum film thickness in the width direction of the said polarizer is 0-3 micrometers, The roll-shaped polarizing plate characterized by the above-mentioned. The method of claim 1, The film thickness difference between arbitrary 1 cm of the width directions of the said polarizer is 0.25 micrometer / cm or less, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, Roll-shaped polarizing plate, characterized in that the overall width is 400mm to 3000mm. The method according to claim 1 or 2, The front side retardation value Re ₍₅₉₀₎ at the wavelength 590 nm and the retardation value Rth ₍₅₉₀₎ of the film thickness direction at the wavelength 590 nm of the said one side protective film are following formula (I) and (II), Formula (I): 20 nm

Re ₍₅₉₀₎

200 nm Formula (II): 70 nm

Rth ₍₅₉₀₎

400 nm Roll-shaped polarizing plate which satisfies. The method according to claim 1 or 2, The ratio of the value of Re _{(590) to} the value of Rth ₍₅₉₀₎ (Re / Rth ratio) of the said one side protective _{film is 0.1-0.8,} The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The said one side protective film is a cellulose acylate film which makes the main polymer component the cellulose acylate which is the mixed fatty acid ester of cellulose substituted with the acetyl group and the acyl group of 3 or more carbon atoms, As for the said cellulose acylate, substitution degree (A) of an acetyl group and substitution degree (B) of an acyl group having 3 or more carbon atoms are represented by the following formulas (III) and (IV), Formula (III): 2.0

A + B

3.0 Formula (IV): 0 <B Roll-shaped polarizing plate which satisfies. The method of claim 6, The acyl group of 3 or more carbon atoms is a butanoyl group, The roll-shaped polarizing plate characterized by the above-mentioned. The method of claim 6, The acyl group of 3 or more carbon atoms is a propionyl group, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The said one side protective film is a film which consists of cellulose acylate obtained by substituting the hydroxyl group of the glucose unit which comprises a cellulose with the acyl group of 2 or more carbon atoms, When substitution degree by the acyl group of the 2nd hydroxyl group of the glucose unit which comprises a cellulose is DS2, substitution degree by the acyl group of the hydroxyl group of 3rd position DS3, when substitution degree by the acyl group of the hydroxyl group of 6th position is DS6, Formulas (V) and (VI), Formula (V): 2.0

DS2 + DS3 + DS6

3.0 Formula (VI): DS6 / (DS2 + DS3 + DS6)

0.315 It is a cellulose acylate film which satisfy | fills the roll-shaped polarizing plate characterized by the above-mentioned. The method of claim 9, The acyl group is a roll-shaped polarizing plate, characterized in that the acetyl group. The method according to claim 1 or 2, The said one side protective film contains 1 or more types of a plasticizer, an ultraviolet absorber, a peeling accelerator, a dye, and a mat agent, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The said one side protective film contains 1 or more types of retardation expression agents of a rod-shaped compound or a disk shaped compound, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The said one side protective film is an optically anisotropic layer formed on the polymer film, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The at least one layer of a hard-coat layer, an anti-glare layer, and an antireflection layer was formed in the surface of the protective film arrange | positioned on the opposite side to the said protective film on one side, The roll-shaped polarizing plate characterized by the above-mentioned. The method according to claim 1 or 2, The retardation film was bonded to the said protective film side of the said one side using an adhesive, The roll-shaped polarizing plate characterized by the above-mentioned. It cut out by the roll-shaped polarizing plate of Claim 1 or 2, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 16 was used so that the said one side protective film may be arrange | positioned at the liquid crystal cell side, The liquid crystal display device characterized by the above-mentioned.

Images