WO2008041657A1

WO2008041657A1 - Polycycloolefin resin film, process for producing the same, polarizer, and liquid-crystal display

Info

Publication number: WO2008041657A1
Application number: PCT/JP2007/069091
Authority: WO
Inventors: Hiroyuki Kawanishi; Hiromichi Tachikawa; Saisuke Watanabe; Masato Nagura
Original assignee: Fujifilm Corporation
Priority date: 2006-09-29
Filing date: 2007-09-28
Publication date: 2008-04-10
Also published as: JP2008291204A

Abstract

A polycycloolefin resin film which changes little in optical properties with changing environmental temperature/humidity, is even in film flatness, surface state, transparency, and optical properties, and has excellent mechanical strength; an optical film; a polarizer; and a liquid-crystal display. The polycycloolefin resin film is formed by casting a polycycloolefin resin solution containing, dissolved therein, 10-50 mass% resin composition containing at least a polycycloolefin resin on an endless support and peeling the casting from the support. The film is characterized in that the polycycloolefin resin solution reaches the gelation point during the period from casting on the endless support to peeling off. (The gelation point means a temperature at which the larger of the value of storage modulus (E') and that of loss modulus (E') of the polycycloolefin resin solution becomes the smaller of these.)

Description

Specification

Cyclic polyolefin resin film and manufacturing method thereof, polarizing plate and liquid crystal display device

Technical field

The present invention relates to a cyclic polyolefin resin film, a method for producing the same, a polarizing plate, and a liquid crystal display device.

Background art

[0002] A polarizing plate is usually manufactured by laminating a film mainly composed of cellulose triacetate as a protective film on both sides of a polarizer in which iodine or a dichroic dye is oriented and adsorbed on polybulal alcohol. Yes. Cellulose triacetate has characteristics such as toughness, flame retardancy, and high optical isotropy (low lettering), and is widely used as the protective film for the polarizing plate described above. The liquid crystal display device is composed of a polarizing plate and a liquid crystal cell. Currently, in TN mode TFT liquid crystal display devices, which are the mainstream of liquid crystal display devices, as described in JP-A-8-50206, an optical compensation film is inserted between a polarizing plate and a liquid crystal cell. A liquid crystal display device with high display quality has been realized. However, cellulose triacetate has a problem in that its optical compensation performance changes due to changes in environmental humidity, and the polarizer tends to deteriorate under environmentally forced test conditions.

[0003] Cyclic polyolefin film has attracted attention as a film that can improve the hygroscopicity and moisture permeability of a cell mouth triacetate film, and a polarizing plate protective film has been developed by hot-melt film formation and solution film formation. In addition, the cyclic polyolefin film has high optical characteristics and has been developed as a retardation film (Patent Documents 1 and 2).

[0004] Regarding the method for producing a cyclic polyolefin film, fluctuations in the optical properties in the width direction and the length direction (directions of letter letter and optical axis) have been a problem in hot melt film formation. In recent years, the required level of flatness of films has been increasing especially for optical compensation film applications used in liquid crystal display devices!

[0005] In Patent Document 3, the casting support is adjusted by adjusting the drying performed from the casting of the dope to the casting support until the film in which the dope is slightly solidified is peeled off from the casting support. A method is disclosed that enables the film to be peeled off quickly from the holder.

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-212927

Patent Document 2: Japanese Patent Laid-Open No. 2002-114827

Patent Document 3: Japanese Patent Laid-Open No. 2003-53750

Disclosure of the invention

Problems to be solved by the invention

[0007] By the way, in any of the above-mentioned solution casting methods, the film needs to have sufficient self-supporting properties when peeled off from the casting support. This is an issue that needs to be considered separately from the problem of band and drum casting support and film adhesion. To this end, the viscoelastic properties of the concentrated solution from the casting to the peeling point are considered. (Storage elastic modulus, loss elastic modulus) and its temperature dependence are particularly important. If this viscoelastic property is inappropriate, it cannot be peeled stably and with high productivity. Even if it can be peeled off, if the resistance at the time of peeling is large, there arises a problem that unevenness of the peeling step occurs when peeling off. In particular, unevenness that occurs during drying up to the peeling point is a major problem that degrades the quality of optical films that require excellent flatness, and improvement is required.

[0008] The present invention solves the above-mentioned problems, and by setting the viscoelastic properties of the concentrated solution to be cast within a certain range, the cyclic polyolefin resin film of good quality with stable high productivity. An object is to provide an optical film, a polarizing plate and a liquid crystal display device using the same.

In addition, in order to bring the viscoelastic properties of the concentrated solution to be cast into a certain range, by adjusting the solvent type, amount, and cooling rate at the time of casting, the stripping unevenness that occurs when peeling is excellent. It aims at providing the method of manufacturing the film which has planarity.

Means for solving the problem

[0009] The inventors of the present invention diligently studied to achieve the above-mentioned object, specified viscoelastic properties (storage elastic modulus, loss elastic modulus) of the concentrated solution at the time of casting, and further adjusted its temperature dependency. Thus, it has been found that a cyclic polyolefin resin film having stable and high productivity and good quality (planarity, transparency, optical uniformity, mechanical strength) can be obtained, and the present invention is completed. It came. In addition, the present inventors tried to develop the cooling gelation ability in the cyclic polyolefin resin, and as a result, by applying a specific substituent to the cyclic polyolefin resin and adjusting the ratio appropriately, It has been found that cooling gelation ability can be expressed. Furthermore, it has been found that a polarizing plate using the cyclic polyolefin resin of the present invention as a protective film has excellent adhesion to a polarizer and good adhesion during processing.

The present invention is as follows.

(1)

A film in which a resin composition containing at least a cyclic polyolefin resin is dissolved in an amount of 10 to 50% by mass, and a cyclic polyolefin resin resin solution is cast on an endless support and peeled to form a film. The cyclic polyolefin-based resin film is characterized in that the cyclic polyolefin-based resin solution reaches a gel point before being peeled off after being cast on an endless support.

Here, the gel point is the relationship between the values of E 'and E' when the storage elastic modulus of the cyclic polyolefin resin solution is E 'and the loss elastic modulus is E'. Refers to temperature.

(2)

The cyclic polyolefin resin solution force The temperature dependence of E ′ and E ′ ′ is expressed as E ′ = A * exp (—B * T), E ′, = C * exp (—D * T) [where A -D is a constant and T is temperature (° C)], the cyclic polyolefin resin film according to (1), wherein 0≤D <B is satisfied.

(3) The cyclic polyolefin resin film according to (1) or (2), wherein the solvent in the cyclic polyolefin resin solution contains 4 to 20% by mass of a poor solvent.

(Four)

The cyclic polyolefin resin solution obtained by continuously casting the cyclic polyolefin resin solution on an endless support, peeling the formed film from the endless support, and drying and winding the peeled film. The cyclic polyolefin resin film according to (1) or (2), characterized in that the temperature of the endless support is set to 150 ° C to 10 ° C. When the cooling rate from when the cyclic polyolefin resin solution is cast on the endless support to when it is peeled is expressed as (temperature difference / hour), it is 3 to 5 (° C / sec). (4) The cyclic polyolefin resin film according to (4).

(6)

The cyclic polyolefin resin resin according to (4) or (5), wherein the film is stretched after being peeled off from the endless support and then dried before being wound up.

(7)

A polarizing plate having a transparent protective film on both sides of a polarizer, wherein at least one of the transparent protective films is the cyclic polyolefin resin film according to any one of (1) to (6)! A polarizing plate characterized by.

(8)

The polarizing plate according to (7), wherein at least one of a hard coat layer and an antireflection layer is provided on the surface of one transparent protective film of the polarizer.

(9)

A liquid crystal display comprising the cyclic polyolefin resin film according to any one of (1) to (6) and the polarizing plate according to (7) or (8). apparatus.

(Ten)

An OCB or VA mode liquid crystal display device, characterized in that the polarizing plate according to (7) or (8) is used in at least one of the upper and lower sides of a liquid crystal cell.

(11)

A VA mode liquid crystal display device using the polarizing plate according to (7) or (8) on the backlight side.

(12)

A method for producing a cyclic polyolefin resin film in which a cyclic polyolefin resin solution is formed by solution casting, wherein the gel point is reached after casting on an endless support until peeling. A cyclic polyolefin resin solution having viscoelastic properties is cast on an endless support of a casting machine adjusted to 50 ° C to 10 ° C, and the cyclic polyolefin When the cooling rate 1 (temperature difference / hour) from when the in-based resin solution is cast on the endless support to when it is peeled is 3 to 5 (° C / _SeC ), A method for producing a cyclic polyolefin resin film.

(13)

Before the cyclic polyolefin resin solution is cast on an endless support of a casting machine, 4 to 20% by mass of a poor solvent is added to the solvent in the cyclic polyolefin resin solution. The manufacturing method of the cyclic polyolefin resin film of description.

Moreover, it is possible to achieve cooling gelation ability in the cyclic polyolefin resin by the following means.

1. Cyclic polyolefin resin containing two repeating units represented by the following general formula (1), at a copolymerization ratio x, y: 0.03≤y / (x + y) ≤0.50 Cyclic polyolefin resin characterized by being.

[0011] [Chemical 1]

General formula (1)

[0012] (In general formula (1),

R ³ independently represents a hydrogen atom or a substituent, and R ² represents an alkyl group having 1 to 10 carbon atoms. ΐ L ² each independently represents a single bond or a divalent linking group. m and p are each independently an integer of 0 or 1, and n and q are each independently an integer of 1 to 4. )

2. The cyclic polyolefin resin as described in 1 above, which comprises two repeating units represented by the general formula (1) and a repeating unit represented by the following general formula (2). [0013] [Chemical 2]

General formula (2)

(In general formula (2), R ⁴ , IT, R °, and R ⁷ are each independently a hydrogen atom, a halogen atom, or a carbon number;! To 10 arenoquinole group, 6 to 20 arenore group, Carbon number:! ~ 10 alkoxy group, carbon number 2-10 acyloxy group, carbon number 2-10 alkoxycarbonyl group, carbon number;! ~ 10 acyl group, carboxyl group r represents 0. Or an integer of 1.

)

3. The cyclic polyolefin according to 1 or 2 above, wherein n = q = l and the total end ratio of the substituents I ^ -OCOR ² and L ² —OH is 50 to 100% Resin.

4. An optical material comprising the cyclic polyolefin resin according to any one of 1 to 3 above.

5. The optical material as described in 4 above, wherein the optical material is in the form of a thin film, film or sheet.

6. The optical material as described in 5 above, wherein Re and Rth are in the following ranges.

(1) 0≤Re≤100nm

(2) 0≤Rth≤400nm

(In the formula, Re and Rth represent in-plane letter-deposition (Re) and thickness-direction letter-decision (Rth) at a wavelength of 590 nm.)

The invention's effect

[0015] According to the present invention, the change in optical characteristics is small and uneven with respect to the change in environmental temperature and humidity. It is possible to provide a cyclic polyolefin resin film having excellent film flatness, planarity, transparency, optical uniformity and excellent mechanical strength. In addition, a polarizing plate and a liquid crystal display device using the cyclic polyolefin film having the effect of the present invention, and a method for producing the cyclic polyolefin film can be provided.

Brief Description of Drawings

FIG. 1 is a diagram for explaining an example of a film production line for a cyclic polyolefin resin film of the present invention.

[Fig. 2] A graph showing the relationship between storage elastic modulus E ', loss elastic modulus E' 'and temperature.

[Figure 3] Relationship between storage elastic modulus E ', loss elastic modulus E' 'and temperature (the intersection of Ε' and E '' is the gel point)

TO. It is a figure for showing.

[Fig. 4] A graph showing the relationship between storage elastic modulus E 'and loss elastic modulus E' '.

FIG. 5 is a schematic view of a film casting line used in the solution casting method according to the present invention.

6 is an enlarged schematic view of the main part of the film production line shown in FIG.

7 is an enlarged schematic view of the main part of the film production line shown in FIG.

Explanation of symbols

[0017] 110 Dope Preparation Department

111 Stir tank

112 Liquid feed pump

113 Huinoleta

120 Casting part

121 Casting die

122 Rotating drum (casting support)

123 Stripping roller

124 Conveyor roller

10 Film production line

11 Mixing tank

12 Dope

13 Stirring blade 14 Pump

15 Filtration equipment

19 Dry air

20 Casting room

21 Casting die

22 Rotating drum

22a Landing line

22b Stripped line

22c Gel-free membrane surface

23 Casting beads

23b Casting bead back

24 Gel membrane

25 Stripping roller

26 films

27 Gas supply device

27a Gas pipeline

28, 30, 48, 49 Gas

29 Blower

31 Recovery device

31 a stiff face

Otsu? Plate / £ s B +

40, 41 Support rotating shaft 42, 43 Bearing 44 Refrigerant

45 Refrigerant supply device 60 Tenter chamber

61 Drying room

62 Dryer 63 Laura

64 Cooling room

65 Winder

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, the present invention will be described in detail.

(Solution casting method)

In the present invention, a cyclic polyolefin resin film is obtained by using a cyclic polyolefin resin solution obtained by dissolving 10 to 50% by mass of a resin composition containing a cyclic polyolefin resin in a solvent and using a solution casting method. Manufacturing. The solution casting method is excellent in terms of flatness and film thickness uniformity. In particular, the solution casting method is preferable in that a film can be formed even by using a cyclic polyolefin-based polymer having a glass transition temperature (Tg) force of ¾00 ° C. or higher and 400 ° C. or lower, which is difficult to form a melt. The solution casting method in the present invention is disclosed in JP 2000-301555, JP 2000-301558, JP 7-0332391, JP 3-193 316, JP 5-086212, JP 62. The cellulose acylate film forming techniques described in JP-A-037113, JP-A-2-276607, JP-A-55-014201, JP-A-2-111511, and JP-A-2-208650 can be applied.

[0019] As a solution casting method, the prepared cyclic polyolefin resin solution (also referred to as a dope) is uniformly extruded onto a metal support from a pressure die, and once cast on the metal support. A method using a force pressure die, such as a method using a doctor blade for adjusting the film thickness with a blade or a method using a reverse roll coater for adjusting with a reverse rotating roll is preferable. There are Coutno, Nger type, T die type, etc. as the pressure die, and any of them can be preferably used. In addition to the methods listed here, it can be carried out by various known methods for casting a cellulose triacetate solution, and by setting each condition in consideration of differences in the boiling point of the solvent used, etc. The same effect as described in each publication can be obtained. The support used for producing the cyclic polyolefin resin film in the present invention is preferably a metal support that travels endlessly. For example, a drum whose surface is mirror-finished by chrome plating or mirror-finished by surface polishing. A bent stainless steel belt (also called a band) or the like is used. The pressure die used for the production of the cyclic polyolefin resin film of the present invention may be one or two or more installed above the metal support. One or two groups are preferred. When two or more units are installed, the dope to be cast can be divided into various proportions for each die, or the dope can be fed to the die at each proportion from multiple precision quantitative gear pumps! The temperature of the cyclic polyolefin resin solution used for casting is preferably 10 ° C to 55 ° C, more preferably 25 ° C to 50 ° C. In that case, all of the processes may be the same or different at different points in the process. If they are different, the temperature may be a desired temperature just before casting.

[0020] The drying of the dope on the metal support involved in the production of the cyclic polyolefin resin film is generally performed from the surface side of the metal support (for example, drum or band), that is, from the surface of the web on the metal support. A method of applying hot air, a method of applying hot air from the back side of the drum or band, a temperature-controlled liquid is contacted from the back side opposite to the dope casting surface of the band or drum, and the drum or band is heated by heat transfer. There are liquid heat transfer methods that control the surface temperature. As long as the surface temperature of the metal support before casting is less than the boiling point of the solvent used for the dope, it can be repeated! However, to promote drying and to lose fluidity on the metal support, 1 ° C to the boiling point of the lowest boiling solvent used; 10 ° C It is preferable to set the temperature lower. This is not the case when the casting dope is cooled and peeled off without drying.

An example of an apparatus that can be used for the casting method in the present invention is shown in FIG.

In this figure, 110 is a dope preparation section, and 120 is a casting section for casting the dope onto a casting support.

[0023] The dope preparation unit 110 is provided with a stirring tank 111 for stirring and mixing a cyclic polyolefin resin, a solvent, a plasticizer, and the like, and a filter 113 is connected to the stirring tank 111 via a liquid feed pump 112. Has been. The casting part 120 is provided with a casting die 121 and a rotating drum 122 as a casting support, and the dope is sent from the filter 113 to the casting die 121. Further, a peeling roller 123 for peeling the film from the rotating drum 122 is provided, and a conveying roller 124 for conveying the film to a tenter drying unit (not shown) is provided. [0024] The casting support is preferably cooled to promote the solidification of the dope. Specifically, the surface temperature of the casting support is preferably 10 ° C or less. 8 ° It is more preferable to set it to C or lower. Most preferable to set it to 5 ° C or lower. The means for cooling the casting support is not particularly limited, and various conventionally used means can be used.

In particular, in the present invention, it is preferable to use an endless support as the casting support, and the temperature is from 50 ° C to 10 ° C, preferably from 45 ° C to 8 ° C, more preferably from 40 ° C. By setting the temperature to C to 5 ° C., the viscoelastic characteristics defined in the present invention can be fully utilized, and stripping unevenness and the like that occur during peeling can be prevented.

[0025] The cooling rate from when the dope is cast on the endless support to when it is peeled is preferably 3 to 5 (° C / sec) in terms of temperature difference / time.

[0026] Further, from the viewpoint of improving the uniformity of drying and releasability, it is preferable that the temperature difference between any two points of the portion of the casting support where the dope is cast is 5 ° C or less. It is more preferable that the temperature is 3 ° C or less.

[0027] Further, by setting the surface temperature of the casting support to 10 ° C or less and the temperature difference between the two points to 5 ° C or less, the stripping speed can be increased and the drying becomes uniform. It is extremely preferable because a film having uniform physical properties and flatness can be obtained.

[0028] The oxygen concentration of the drying air for drying the dope cast on the casting support is preferably 10% by volume or less, more preferably 5% by volume or less. The dew point of the solvent contained in the wind is preferably 5 ° C or more lower than the surface temperature of the casting support, and more preferably 10 ° C or more. By adopting such a configuration, ignition and explosion can be prevented even when a flammable solvent is used. Further, by reducing the dew point, it is possible to prevent condensation on the casting support or casting bead.

[0029] The dope cast from the casting die to the casting support is dried on the casting support to be in a solid state that is dry. Then, the solidified film is sent to a drying section composed of a tenter device and dried.

[0030] In the casting method of the present invention, a single-layer liquid may be cast on a smooth band or a drum as a casting support, or a plurality of dopes of two or more layers may be cast or co-casted sequentially. It may be cast by casting. When casting multiple dopes, leave a gap in the direction of travel of the support. A film may be produced while casting and laminating a plurality of dope casting forces provided, for example, JP 61-158414, JP 1-122419, JP 11 198285, etc. Can be applied. It is also possible to form a film by casting two cast loca dopes, for example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-947245 It can be carried out by the methods described in JP-A-61-104813, JP-A-61-158413, and JP-A-6-134933. Alternatively, a cellulose acylate film casting method described in JP-A-56-162617 may be used in which a high-viscosity dope stream is wrapped with a low-viscosity dope and the high- and low-viscosity dopes are simultaneously extruded.

[0031] Alternatively, the two casting rolls are used to peel off the film formed on the support by the first casting port, and to perform the second casting on the side that is in contact with the support surface. A film can also be produced, and for example, the method described in Japanese Examined Patent Publication No. 44-20235 may be used.

[0032] The dope to be cast may be the same solution or different solutions, and is not particularly limited. In order to give a function to a plurality of cyclic polyolefin resin layers, a dope corresponding to the function may be extruded from each casting port. Furthermore, the dope of the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer).

[0033] Depending on the material and solvent system to be selected, it is necessary to extrude a high-concentration and high-viscosity dope in order to obtain the required film thickness in a single-layer solution. In this case, the dope stability is poor. In some cases, solid matter is generated, which may cause troubles and poor flatness. As one of the solutions here, by casting a plurality of dopes from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time, improving the flatness and improving the surface shape. If a film can be produced, the drying load can be reduced by using a thick dope that can be reduced by using a thick film. In some cases, the production speed of the film can be increased.

[0034] When a dry film is peeled from a casting support, the peel resistance (peeling load) is large, and the film is irregularly stretched in the film forming direction, resulting in optical anisotropic unevenness (stripping step). Cause unevenness). In particular, when the peeling load is large, the stretched portions in the film forming direction and the unstretched portions are alternately generated, resulting in a distribution in the letter dean. When mounted in a liquid crystal display device, irregularities appear in the form of lines or strips. Do not cause such problems For this purpose, it is preferable to set the film peeling load to 0.25 mm or less per lcm of the film peeling width. The peeling load is more preferably 0.2 N / cm or less, further preferably 0.15 N or less, and particularly preferably 0.10 N or less. When the peeling load is 0.2 N / cm or less, even in a liquid crystal display device in which unevenness is likely to appear, no unevenness due to peeling is observed at all, which is particularly preferable. There are two methods for reducing the peeling load: adding a release agent and selecting the solvent composition to be used. In the case of the present cyclic polyolefin resin film, the effect becomes remarkable by increasing the addition amount of the alcohol solvent.

[0035] The peel load is measured as follows. A dope is dropped on a metal plate having the same material and surface roughness as the casting support of the film forming apparatus, and is cast to a uniform thickness using a doctor blade and dried. Make a cut of equal width into the film with a cutter knife, peel off the film tip by hand, pinch it with a clip connected to the strain gauge, and measure the load change while pulling the strain gauge diagonally at 45 degrees. The volatile content in the peeled film is also measured. The same measurement is performed several times while changing the drying time, and the peeling load at the same time as the residual volatile content at the peeling in the actual film forming process is determined. As the peeling speed increases, the peeling load tends to increase, and it is preferable to measure at a peeling speed close to actual.

[0036] When the cyclic polyolefin resin film of the present invention is stretched, it is preferably performed in a state where the solvent still remains in the film immediately after peeling. The purpose of stretching is (1) to obtain a film with excellent flatness without any deformation, and (2) to increase the in-plane letter pattern of the film. When stretching is performed for the purpose of (1), it is preferable to perform stretching at a relatively high temperature and to perform stretching at a low ratio of 1% to 15%. A stretch of 2 to 10% is particularly preferred. When stretching for the purposes of both (1) and (2), or only for the purpose of (2), it is preferable to stretch at a relatively low temperature and a stretching ratio of 2 to 150%.

[0037] If the film is stretched when the residual solvent remains in the film, it can be stretched at a lower temperature than the dry film. Many cyclic polyolefin resins have a high glass transition temperature (Tg), but can be stretched at a temperature lower than the inherent Tg of the polymer.

The film may be stretched uniaxially or longitudinally or laterally, or simultaneously or sequentially biaxially. The birefringence of retardation films for VA liquid crystal cells and OCB liquid crystal cells It is more preferable that the refractive index is larger than the refractive index in the length direction, and that polybutyl alcohol and rolls can be bonded together. Therefore, it is preferable to stretch more in the width direction.

[0038] In the cyclic polyolefin resin film of the present invention, the resin composition containing the cyclic polyolefin resin is 10 to 50% by mass, preferably 15 to 45% by mass, more preferably 18 to 40% by mass, Preferably, a cyclic polyolefin resin solution in which 20 to 35% by mass is dissolved is cast by casting a solution. Here, the resin composition refers to the solid content in the cyclic polyolefin resin solution.

The reason for specifying the concentration of the resin composition in the cyclic polyolefin resin solution as described above is that the storage elastic modulus E ′ and E ′ ′ of the present invention can be obtained by adjusting the solid content concentration to an appropriate range. The solid content concentration is 10% by mass or more, the environmental load is small, and the productivity is low. It is preferable because it is excellent in gelation performance when cooled, does not induce a surface-like failure, particularly a skin-like failure, or a skin-like failure, and does not cause vertical stripes in the casting direction. The constituent components of the resin composition will be described below.

[0039] (Cyclic polyolefin resin)

The cyclic polyolefin resin in the present invention (also referred to as cyclic polyolefin or cyclic polyolefin polymer) represents a polymer resin having a cyclic olefin structure. Examples of the polymer resin having a cyclic olefin structure used in the present invention include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugation polymer, (4 ) Bull alicyclic hydrocarbon polymers and hydrides of (1) to (4). Preferred polymers for the present invention are addition (co) polymer cyclic polyolefins containing at least one repeating unit represented by the following general formula (II) and, if necessary, a repeating unit represented by the general formula (I): An addition (co) polymer cyclic polyolefin further comprising at least one unit. Moreover, a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III) can also be suitably used.

[0040] [Chemical 3]

Go [Ran]

(I)

贿 800Z OAV

[9 ^ 1] [00]

(Π) One

91-

T60690 / .00Zdf / X3d 贿 800Z OAV General formula (m)

[0043] In the formula, m represents an integer of 0 to 4. ! ^ ~ Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; ~, Y ¹ ^ is a hydrogen atom, carbon number;! To a carbon atom having ¹ to 10 carbon atoms substituted by a hydrocarbon group, halogen atom or halogen atom ~; 10 hydrocarbon groups, (CH) COOR ^U (CH) O

2 n 2 n

COR ¹² , — (CH) NCO, — (CH) NO, — (CH) CN, — (CH) CONR ¹³ R ¹⁴ ,-(C

2 n 2 n 2 2 n 2 n

H) NR ¹³ R ¹⁴ , — (CH) OZ, — (CH) W, or X ¹ and Y ¹ or X ² and Y ² or X ³

2 η 2 η 2 η

— Indicates (—CO) 0 and (-CO) NR ¹⁵ composed of ³ . R ^u , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with halogen, W is SiR ¹⁶ D (R ¹⁶ is carbon number;! ~ 10 hydrocarbon group, D is halogen atom

P 3-p

Child, —OCOR ¹⁶ or —OR ¹⁶ , p represents an integer of 0 to 3), and n represents an integer of 0 to 10.

^{[0044] ^ ~X 3, Y} 1 by introducing a polarizable large functional group in a substituent to Y ^3, by increasing the thickness direction retardation Chillon optical full Ilm (Rth), the in-plane Retade The expression of Chillon (Re) can be increased. A film with a high Re developability can increase the R straightness by stretching it during the film formation process. [0045] Norbornene polymer hydrides are disclosed in JP-A-1 240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-1159767. As disclosed in Kaikai 2004-309979 and the like, it is prepared by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation. In the norbornene-based polymer used in the present invention, R ^{5 to} R ⁶ are preferably a hydrogen atom or X ³ , and Y ³ is a hydrogen atom, and other groups such as Cl and —COOCH are suitably selected. The This norbornene resin is sold under the trade name of Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF1 4, ZF16, Zeonex from Nippon Zeon Co., Ltd. (Zeonex) 250 or ZEONEX 280 are sold under the trade name and can be used with these products.

[0046] Norbornene-based addition (co) polymers are disclosed in Japanese Patent Application Laid-Open No. 10-7732, Special Table 2002-504184, US Published Patent No. 2004229157A1, and other publications (such as WO2004 / 070463A1)! It can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds and, if necessary, norbornene-based polycyclic unsaturated compounds and conjugates such as ethylene, propylene, butene, butadiene and isoprene. Gen; non-conjugated gen such as ethylidene norbornene; and linear gen compounds such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic acid ester, methacrylic acid ester, maleimide, butyl acetate and butyl chloride This norbornene-based addition (co) polymer is available from Mitsui Chemicals, Inc. under the name of Apel, Different glass transition temperatures (Tg), such as APL8008T (Tg70 ° C), APL6013T (Tgl25 ° C) or APL6015 T (Tgl45 ° C), etc. TOPAS8007, 601 3, and 6015 from Polyplastics Co., Ltd. In addition, Ferearia has released Appear3000.

[0047] In the present invention, there is no limitation on the glass transition temperature (Tg) of cyclic polyolefin! /, For example, 200-400 ° C! /, Such a high! /, Tg The following cyclic polyolefin can also be used.

[0048] The cyclic polyolefin resin in the present invention is particularly preferably a polymer containing a repeating unit represented by the general formula (II). This is because the structure of the main chain is stiffer than the general formula (I) and the general formula (III), and therefore it is very easy to arrange. This makes this The resin is characterized by being easily gelled.

[0049] The cyclic polyolefin resin of the present invention contains two repeating units represented by the following general formula (1) in order to develop cooling gelation ability, and has copolymerization ratios x, y Even if it is 0 · 03≤y / (x + y) ≤0.50, J:

[0050] [Chemical 6]

General formula (1)

[0051] (In the general formula (1),

[0052] Of the repeating units represented by the general formula (1), the repeating units represented by the following general formula (1A) will be described.

General formula (1A)

[0053] [Chemical 7]

[0054] In the general formula (1A), R ³ ,

p, q, and y have the same meanings as shown in the general formula (1).

The repeating unit represented by the general formula (1A) can be formed by addition polymerization of a cyclic olefin represented by the following general formula (4).

General formula (4)

[0056] [Chemical 8]

P

R ³ teeth ² - 0H In general formula (4), R ³ , L ² , p, and q have the same meanings as those shown in general formula (1).

[0058] R ³ represents a hydrogen atom or a force representing a substituent. The substituent is preferably a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (preferably having a carbon number of 1 force, etc. Of an alkenylquinole group, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 carbon atoms, 30 substituted or unsubstituted cyclohexane) An alkyl group such as cyclohexyl, cyclopentyl, 4 n dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, having 5 to 30 carbon atoms). This is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane such as bicyclo [1,2,2] heptane-2-yl, bicyclo [2,2,2] octa. -3 I-le),

[0059] An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as bur or aryl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms) Groups, that is, monovalent groups in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed, for example, 2-cyclopentene 1-yl, 2-cyclohexene 1-yl), bicycloalkenyl group (substituted) Or an unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hepto-2-yl-1, bicyclo [2,2,2] otato-2ene-4yl), alkynyl groups (preferably carbon A substituted or unsubstituted alkynyl group having a number of 2 to 30, for example, ethur, propargyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, ptolyl, naphthyl), hetero A cyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number of 3 To 30-membered 5- or 6-membered aromatic heterocyclic groups such as 2-furinole, 2-chechinorole, 2-pyrimidininole, 2-benzthiazolinole), cyano group, hydroxy group, nitro group, A carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, Toxyl, n-octyloxy, 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-tbutylphenoxy, 3-nitrophenoxy, 2-tetra Decanoinoreminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclicoxy group, 1-phenyltetrazole-5 oxy, 2 tetrahydroviranyloxy, acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms) Xoxy group, substitution of 6 to 30 carbon atoms Or an unsubstituted arylylcarbonyloxy group, such as honoleminoreoxy, acetyloxy, bivalyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy, and rubamoyloxy groups (preferably having 1 carbon atom). To 30 substituted or unsubstituted canolevamoyloxy groups, for example, N, N dimethylcarbamoyloxy, N, N deethylcarbamoyloxy, morpholino force noreblonoxy, N, N genyloctylaminocarbonyloxy N—n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyl Oxy, n-octylcarpo Oxy), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, pmethoxyphenoxycarbonyloxy P-n hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino-containing methylamino, dimethylamino, ananilino, N —Methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylcarbonylamino group having 6 to 30 carbon atoms, For example, formylamino, acetylamino, bivalloyamino, lauroylamino, benzoylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Substituted aminocarbonylamino, for example, rubamoylamino, N, N dimethylaminocarbonylamino, N, N jetylaminocarbonylamino, morpholinocarbonylamino, alkoxycarbonylamino groups (preferably having 2 carbon atoms) To 30 substituted or unsubstituted alkoxycarbonylamino groups such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino ), Aryloxycarbonylamino groups (preferably substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino) , M— n octyloxy sifenyloxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino-containing N, N-dimethylaminosulfonylamino, N-noctyl Aminosulfonylamino), alkyl and arylsulfonylamino groups (preferably a substituted or unsubstituted alkylsulfonylamido having 6 to 30 carbon atoms, or a substituted or unsubstituted arylosnorephoninoreamino group having 6 to 30 carbon atoms). For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylaminomino, 2, 3, 5 trichlorophenylsulfonylamino, p methylphenylsulfonylamino), mercapto group, alkylthio group (preferably having 1 to 3 carbon atoms) 30 substituted or unsubstituted alkylthio groups such as methylthio, ethylthio n-hexadecylthio), arylthio groups (preferably substituted or unsubstituted arylates having 6 to 30 carbon atoms, such as pheninoretio, p-chlorophenenoretio, m-methoxypheninoretio), heterocyclic thio groups (Preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2 benzothiazolylthio, 1 phenyltetrazole-5 ylthio), a sulfamoyl group (preferably having 0 to 30 carbon atoms) Substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl, N— (3-dodecyloxypropyl) sulfanololfamoyl, N— (Ν′-phenylcarbamoinole) sulfamoinole), sulfo group, alkyl And arylsulfier groups (preferably substituted or unsubstituted alkylsulfier groups having 1 to 30 carbon atoms) 6 to 30 substituted or unsubstituted aryl sulfier groups, for example, methinolesnorefininore, ethinoresnorefininore, fenenoresnorefininore, ρ-me Tilphenylsulfonyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl) , Ethylsulfonyl, phenylsulfonylsulfonyl, p-methylphenylsulfonyl), isyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon group having 7 to 30 carbon atoms) An arylcarbonyl group such as acetyl, bivaloylbenzoyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxy Carbonyl, o Chlorophenoxycanore Boninole, m Nitrophenoxycanoleponino , P-t butynolephenoxycanoleponinole), ananoloxycarbonyl group (preferably a substituted or unsubstituted alkoxy group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl , N-octadecyloxycarbonyl), canolemomoyl group (preferably substituted or unsubstituted rubamoyl having 1 to 30 carbon atoms, eg, rubamoyl, N methylcarbamoyl, N, N dimethylcarbamoyl, N, N n octylcarbamoyl, N— (methylsulfonyl) force rubermoyl), aryl and heteroazo groups (preferably substituted or unsubstituted aralkylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted groups having 3 to 30 carbon atoms) Heterocyclic azo groups such as phenylazo, p-chlorophenazo, 5- Tilthio 1, 3, 4 thiadiazole-2 silazo), imide group (preferably N succinimide, N phthalimide), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethyl Phosphino, diphenylphosphino, methylphenoxyphosphino), phosphier groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphino Fieroxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphieroxy), phosphieramino group (preferably Is a substituted or unsubstituted phosphine having 2 to 30 carbon atoms. A nilamino group such as dimethoxyphosphinylamino, dimethylaminophosphieramino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethinoresilinole, t-butyldimethyl Cyril, phenyldimethylsilane Ril).

[0062] Among the above substituents, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

[0063] When there are two or more substituents, they may be the same or different. If possible, they can be linked together to form a ring.

More preferably, R ³ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 10 carbon atoms, an aryl group having 6 10 carbon atoms, ³ to carbon atoms, a cycloalkyl group having 10 carbon atoms, a cyan group, or 2 to carbon atoms; 10 is an alkoxy group, 2 to carbon atoms; an alkoxycarbonyl group having 10 carbon atoms, or a hydrogen atom.

[0065] L ² represents a single bond or a divalent linking group. However, alcohol is formed by the combination of L ² and OH. The divalent linking group is preferably an optionally substituted alkylene group, alkenylene group, alkynylene group, arylene group, or a group obtained by combining two or more of these divalent groups. When composed of two or more combinations, they may be linked by another divalent linking group. As such a divalent linking group, for example, —NR ⁹ (wherein R ⁹ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group), OS—SO —-SO— -CO-,-SO NR ⁹ — NR

twenty two

⁹ SO—CONR ⁹ NR ⁹ CO COO, and one OCO.

2

Here, as the substituent, the above-described examples of the substituent in R ³ can be applied.

[0066] L ² is more preferably a single bond or a carbon number;! To 10, more preferably a substituted or unsubstituted alkylene group having 16 carbon atoms.

[0067] p is an integer of 0 or 1, more preferably 0. q is an integer of 1 4, more preferably 1 2. R ³ L ² may be bonded to each other to form a 57-membered ring, more preferably a 6 to 6-membered ring. Moreover, it may be a carbocycle or a heterocycle, but a carbocycle is preferred.

[0068] Specific examples of the cyclic olefin represented by the general formula (4) are shown below. It is not limited to these.

[0069] [Chemical 9]

(4-13) (4-14) (4-15) (4-16)

[0071] [Chemical 11]

( ²⁴ ) (4-25) (4-26)

[0073] The cyclic olefin represented by the general formula (4) can be used singly or in combination of two or more.

[0074] R ³ in the general formula ^{(1), L 2, p} , for q, or of the general formula (4) R ^3,

Same as p and q.

[0075] The cyclic olefin-based polymer including each repeating unit represented by the general formula (1) is obtained by hydrolyzing or solvating the cyclic olefin-based polymer including the repeating unit represented by the following general formula (1B). You can also get it by being early.

General formula (1B)

[0076] [Chemical 13]

[0077] The repeating unit represented by the general formula (IB) can be formed by addition polymerization of a cyclic olefin represented by the following general formula (5).

[0078] [Chemical 14]

General formula (5)

[0079] General formula (5)

m and n are the same as those shown in the general formula (1).

.

[0080] R ¹ represents a hydrogen atom or a substituent. Preferred examples of the substituent are described in the general formula (4). Those mentioned in the example of the substituent R ³ can be applied.

R ² represents a substituent, preferably a substituent! /, For example, the force S described in the example of the substituent described in the general formula (4) can be applied S, preferably even if it has a substituent. Good, carbon number;! To 10 alkynole group, 6 to 10 carbon atom group, 1 to 10 alkoxy group, 6 to 10 carbon atom group, or 0 to 10 carbon atom group is there.

Preferred ranges of m and n are the same as the preferred ranges of L ² , p and q in the general formula (4), respectively.

[0081] The cyclic olefin-based polymer of the present invention may comprise only each repeating unit represented by the general formula (1), but contains the repeating unit represented by the general formula (2). You can also. In the case where the repeating unit represented by the general formula (2) is contained, a ratio of !! to 50 mol% in the polymer is desirable.

The repeating unit represented by the general formula (2) can be introduced by a specific cyclic polyolefin represented by the following general formula (6).

[0083] [Chemical 15] General formula (6)

[0084] In the general formula (6), R ⁴ , RR °, R ⁷ and r can be added to the same taste as in the general formula (2).

[0085] R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom or a substituent, and the substituent is preferred! /, For example, the same as the example of the substituent R ³ described in the general formula (4) It is. R ⁴ , R ⁵ , R ⁶ and R ⁷ are more preferably a hydrogen atom, a halogen atom, a carbon number of 1 to; an alkyl group of 10 to 10 carbon atoms, an aryl group of 10 to 10 carbon atoms, an alkoxy of 10 to 10 carbon atoms. Group, cyano group, carbon number 2 to; 10 acyloxy group, carbon number An alkoxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, or a carboxyl group; Further, if possible, they may be linked to each other to form a 5- to 7-membered ring, but a 5- or 6-membered ring is more preferable. Further, it may be a carbocyclic ring or a heterocyclic ring.

[0086] r represents an integer of 0 or 1, more preferably 0.

Specific examples of the cyclic olefin represented by the general formula (6) are shown below, but the present invention is not limited thereto.

[0088] [Chemical 16]

Ha ^

COOCH ₃ COOC ₂ H ₅

(5-1) (5-2) (5-3) (5-4

[0089] [Chemical 17]

(5-9) (5-10) (5-1 1)

(5-12) (5-13) (5-14) (5-15) [0090] [Chemical 18]

H ₃

(5-20) (5-21) (5-22) (5-23)

[0091] [Chemical 19]

The cyclic olefins represented by the general formula (1) can be used singly or in combination of two or more.

The cyclic olefins used in the present invention can be synthesized with reference to methods known in the literature. The Examples include the method described in Bull. Chem. Soc. Jpn., 48, 3641-3644 (1975), and the method described in J. Chem. Soc. Perkin Trans., 2, 17-22 (1974). The cyclic olefins of the present invention are not limited to these methods.

[0093] The cyclic polyolefin resin having a repeating unit represented by the general formula (1) is obtained by polymerizing the monomer represented by the general formula (5) and then hydrolyzing or desolvating the polymer. Can also be obtained. When the repeating unit represented by the general formula (2) is introduced into the cyclic olefin-based polymer, the monomer represented by the general formula (5) and the monomer represented by the general formula (6) are copolymerized. Later, the copolymer can be obtained by hydrolysis or solvolysis.

[0094] The hydrolysis and solvolysis described above are described, for example, in TWGREENE, RGMWUTS "PR0TE CTIVE GROUPSIN ORGANIC SYNTHESIS SECOND EDITI0N" (J0HN WILEY & S ONS, Inc., published in 1991), pages 87-113. Known methods such as acid-catalyzed hydrolysis, base-catalyzed hydrolysis, alcoholysis and aminolysis can be applied.

In the base-catalyzed hydrolysis method, for example, a polymer is dissolved in a hydrophilic solvent (eg, tetrahydrofuran), a basic aqueous solution (eg, sodium hydroxide aqueous solution) is added, and the mixture is heated and stirred. As a result, the acyl group can be partially converted into a hydroxyl group. The conversion rate of hydroxyl groups can be adjusted as appropriate depending on the reaction time, the amount of base, the amount of water, and the like. On the other hand, it is easy to perform solvolysis by dissolving the polymer in a soluble solvent and alcohol and adding a catalyst. For example, a cyclic olefin polymer is dissolved in a mixed solvent of methylene chloride and methanol and reacted using a metal alkoxide such as sodium methoxide as a catalyst. The reaction can be stopped by adding a taenity agent such as acetic acid after an appropriate time. As a result, the acyl group can be partially converted into a hydroxyl group. The conversion rate of the hydroxyl group can be appropriately adjusted depending on the reaction time, the amount of alcohol, the amount of catalyst, and the like.

[0095] The polymerization of the present invention can also be obtained by the following method.

[Pd (CH CN)] [BF], g mu chlorobis (6 methoxybicyclo [2.2.1]

3 4 4 2

Heptoe 2 end 1 5 σ, 2 π) — Pd (hereinafter abbreviated as “I”) and methylalumoxane (MAO), I and AgBF, 1 and AgSbF, [( ³ arninore) PdCl] and AgSbF, [( ³

4 6 2 6

) PdCl] and AgBF, [crotyl) Pd (cyclooctagen)] [PF], [( ³ Chinore) Ni (cyclooctagen)] [B ((CF) CH)], [NiBr (NPMe)] and MAO, N

3 2 6 4 4 3 4

i (photo) and MAO, Ni (photo) and B (C F) and AlEt, Ni (photo)

2 2 6 5 3 3 2

[ph C] [B (C F)], Ali—Bu, Co (neodecanoate), MAO, etc.

3 6 5 4 3

Ni, Pd. Co, and other cation complexes or catalysts that form cation complexes, cyclohexane solvents such as cyclohexane, cyclopentane, methylcyclopentane, pentane, hexane, heptane, octane Aliphatic hydrocarbon solvents such as toluene, benzene, xylene, etc., halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethylene, and black benzene, ethyl acetate, butyl acetate, γ — What can be obtained by (co) polymerizing a specific cyclic olefin compound in the range of 20-100 ° C in a solvent selected from polar solvents such as butyrolatatatone, propylene glycol dimethyl ether, nitromethane, etc. Monkey.

Macromolecules, 1996, 29, 2755, Macromolecules, 2002, 35, 8969, International Patent Publication No. WO2004 / 7564 Preferably used.

In the present invention, the ratio of X and y in the general formula (1) satisfies the relational expression of 0.03≤y / (x + y) ≤0.50. When y / (x + y) <0.3, that is, when the amount of OH is small, the cooling gelation ability (peelability) becomes low. On the other hand, y / (x + y)> 0.5, that is, if the amount of OH is large, it does not dissolve in the solvent. In order to make both properties suitable, it is necessary to satisfy 0.03≤y / (x + y) ≤0.50, preferably 0.05.5≤y / (x + y) ≤0.50 More preferably, 0.05 ≦ y / (x + y) ≦ 0.40, and most preferably 0.110 ≦ y / (x + y) ≦ 0.40. In order to set x and y in this range, it is possible to appropriately adjust the degree thereof by a known hydrolysis or solvolysis method.

[0097] In the general formula (1), y / (x + y), that is, the ratio of OH groups can be measured by a spectroscopic technique such as IR. Alternatively, the OH of the polymer can be benzoylated with an excess of base and benzoyl chloride, and its ¹ HNMR can be measured and calculated from the integral ratio of the benzoyl moiety to other moieties. Since this corresponds to the ratio of the original OH, the OH content of the original polymer, ie, y can be calculated.

[0098] The cyclic olefin-based polymer of the present invention is a gel permeant containing tetrahydrofuran as a solvent. The polystyrene-equivalent number average molecular weight measured by the Chillon chromatogram is 10,000-1, 000,000, preferably <50,000-500,000. The weight average molecular weight in terms of positive styrene is 15,000-1, 500,000, and preferably <70,000-700,000. If the polystyrene-equivalent number average molecular weight is less than 10,000 and the weight-average molecular weight is less than 15,000, the fracture strength may be insufficient, and the polystyrene-equivalent number average molecular weight exceeds 1,000,000. If the weight average molecular weight force exceeds 500,000, the molding processability as a sheet decreases, and the solution viscosity becomes high when used as a cast film and the like, which may be difficult to handle.

[0099] The glass transition temperature of the cyclic olefin-based polymer of the present invention is preferably 100 to 400 in the measurement with a scanning differential calorimeter (DSC). C, preferably 150-380. C, more preferably 200 to 350 ° C, and if it is less than 100 ° C, thermal deformation tends to occur when used as an optical material. In addition, when the temperature exceeds 400 ° C, the polymer may have a rapid heat splitting when heat forming.

[0100] The preferred tensile modulus of the cyclic olefin-based polymer of the present invention is preferably 1200 MPa or more, more preferably 1500 MPa or more. If the tensile modulus is low, the film may be insufficiently self-supporting and difficult to handle as an optical material such as a polarizing plate.

[0101] The cyclic olefin-based polymer of the present invention includes a crosslinking agent such as a silane coupling agent containing a peroxide, disulfide, disulfide, polysulfide compound, dioxime compound, tetrasulfide and the like. 0.05 to 5 parts by weight with respect to parts by weight can be added and converted into a crosslinked product by heat or the like, or can be directly converted into a crosslinked product by light or electron beam.

[0102] [Physical properties of polymer]

(Determination of cooling gelation ability)

The cyclic olefin-based polymer of the present invention has a cooling gelling ability. In order to discriminate a polymer having cooling gelation ability, viscoelasticity can be measured with a rheometer or the like. This is because the polymer dope is cooled and has a temperature at which a sudden increase in viscosity is observed. However, the object of the present invention is to discriminate polymers that can be formed at high speed. Actually, it is preferable to make a judgment by examining cooling casting film formation. You can easily test on a small scale. The polymer dope can be cast on a small scale with a cooled metal plate, and the peelability can be confirmed. For example, the polymer is dissolved in a mixed solvent such as methylene chloride / methanol / butanol / water, and the resulting dope is converted to o ° c to

— Cast the film on an SUS plate set at 40 ° C using an applicator. If this film is peeled off and there is no residue on the SUS plate, it can be judged that high-speed film formation is possible.

[0103] [Polymer film]

The optical material of the present invention is characterized by using a cyclic olefin-based polymer, and the optical material is preferably in the form of a thin film, film or sheet. In the following, the film will be described as an example.

The film of the present invention refers to a film containing a cyclic olefin-based polymer. Films produced using the polymer include liquid crystal display element substrates, light guide plates, polarizing films, retardation films, liquid crystal backlights, liquid crystal panels, OHP films, transparent conductive films, and the like. Suitable for optical use film.

[0104] (Fine particles)

In the present invention, fine particles can be added to the resin composition. By adding fine particles, the dynamic friction coefficient on the film surface is lowered, so that the stress applied to the finem during film handling can be reduced. As fine particles that can be used in the present invention, organic or inorganic compound fine particles can be used.

[0105] As inorganic compounds, compounds containing silicon, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strongtium oxide, antimony oxide, tin oxide, tin oxide 'antimony, calcium carbonate , Talc, clay, calcining power oline, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate are preferred, and more preferably inorganic compounds and metal oxides containing potassium. However, since the turbidity of the film can be reduced, silicon dioxide is particularly preferably used. As fine particles of silicon dioxide, for example, Aerosil R972, R974, R812, 200, 300, R202, 0X50, TT600 (above Enomoto Aerosil Co., Ltd.) A commercial product having a trade name can be used. As the zirconium oxide fine particles, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

[0106] Examples of the organic compound include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch, and the like. A pulverized classification product is also mentioned. Alternatively, a polymer compound synthesized by a suspension polymerization method, or a polymer compound made spherical by a spray drying method or a dispersion method can be used.

[0107] The primary average particle diameter of these fine particles is preferably from !! to 20000, more preferably from! To lOOOOnm, and more preferably from the viewpoint of keeping haze low. OOOnm, particularly preferably 5 to 500 nm. The measurement of the primary average particle diameter of the fine particles is obtained by the average particle diameter of the particles with a transmission electron microscope. The purchased fine particles are often agglomerated and are preferably dispersed by a known method before use. The secondary particle size is preferably 200 to 1500 nm by dispersion, more preferably 300 to lOOOnm. The amount of fine particles added is preferably 0.01 to 0.3 parts by weight for 100 parts by weight of cyclic polyolefin. 0.05 to 0. 2 parts by weight is even more preferred. 0.08 to 12 parts by weight. Most preferred.

The preferred range of the cyclic polyolefin film to which fine particles are added! /, The haze range is 2.0% or less, 1.2% or less is more preferred, and 0.5% or less is particularly preferred. A preferable dynamic friction coefficient of the cyclic polyolefin film to which fine particles are added is 0.8 or less, and particularly preferably 0.5 or less. The dynamic friction coefficient can be measured using a steel ball according to the method specified by JIS or ASTM. Haze can be measured using a 1001DP haze meter manufactured by Nippon Denshoku Industries Co., Ltd.

Yes

[0108] (Solvent)

Next, the solvent that is contained in the cyclic polyolefin resin solution and in which the cyclic polyolefin is dissolved will be described. In the present invention, the solvent that can be used is not particularly limited as long as the object can be achieved as long as the cyclic polyolefin can be dissolved, cast, and formed into a film. Solvents used in the present invention are, for example, chlorinated solvents such as dichloromethane and black mouth form. The solvent is preferably a solvent selected from chain hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, esters, ketones and ethers having 3 to 12 carbon atoms. Esters, ketones, and ethers may have a cyclic structure. Examples of chain hydrocarbons having 3 to 12 carbon atoms include hexane, octane, isooctane and decane. Examples of cyclic hydrocarbons having 3 to 12 carbon atoms include cyclopentane, cyclohexane and derivatives thereof. Examples of the aromatic hydrocarbon having 3 to 12 carbon atoms include benzene, toluene and xylene. Examples of esters having from 3 to 12 carbon atoms include ethyl phenolate, propino phenolate, pentino ketone, methino acetate, etheno rare acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, jetyl ketone, diisoptyl 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 phenetole. Examples of the solvent having two or more kinds of functional groups include 2-ethoxycetyl acetate, 2-methoxyethanol and 2-butoxyethanol. The preferred boiling point of the solvent is 35 ° C or higher and 150 ° C or lower. The solvent used in the present invention can be used by mixing two or more kinds of solvents for adjusting the solution physical properties such as drying property and viscosity. Further, as long as the cyclic polyolefin is dissolved in the mixed solvent, it is a poor solvent. It is also possible to add.

A preferred poor solvent can be appropriately selected depending on the type of polymer used. When a chlorinated organic solvent is used as the good solvent, alcohols and water can be preferably used. The alcohols may be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbons are preferable. The hydroxyl group of the alcohol may be any of primary to tertiary. Examples of alcohols include methanol, ethanol, 1-prono, 2-prono, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol and cyclohexanol. It is. As the alcohol, fluorine-based alcohol is also used. For example, 2 fluoroethanol, 2, 2, 2 trifluoroethanol, 2, 2, 3, 3 tetrafluoro Examples include raw 1 propanol. Among the poor solvents, monohydric alcohols are particularly effective because they have an effect of reducing peeling resistance. The alcohols that are particularly preferred vary depending on the good solvent selected, but considering the drying load, alcohols with a boiling point of 120 ° C or lower are preferred, and monohydric alcohols with 1 to 6 carbon atoms are more preferred. Alcohols having 1 to 4 carbon atoms can be particularly preferably used. A particularly preferable mixed solvent for preparing the cyclic polyolefin solution is a combination in which dichloromethane is the main solvent and one or more alcohols selected from methanol, ethanol, propanol, isopropanol, or butanol are used as poor solvents.

[0110] (Additive)

In the resin composition of the present invention, various additive additives (for example, deterioration inhibitors, UV inhibitors, letter-dose (optical anisotropy) modifiers, release accelerators, plasticizers) according to the application in each preparation step. Agents, infrared absorbers, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of UV-absorbing materials with melting points of 20 ° C or lower and 20 ° C or higher, and mixing of deterioration inhibitors as well. Furthermore, infrared absorbing dyes are described, for example, in JP-A-2001-194522. In addition, the timing of the addition may be added to the cyclic polyolefin resin solution (dope) production process! /, And any addition may be used. However, the additive is added to the final preparation process of the dope preparation process. You may add and add the process to prepare. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. When the cyclic polyolefin film is formed from multiple layers, the type and amount of additives in each layer may be different.

[0111] (Deterioration inhibitor)

In the resin composition of the present invention, known deterioration (oxidation) inhibitors such as 2,6-di-tert-butyl, 4-methylphenol, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1, 1 '-Bis (4 hydroxyphenenole) cyclohexane, 2, 2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythrityl-tetrakis [3 — Phenolic or hydroquinone antioxidants such as (3,5-di-tert-butyl-4-hydroxyphenyl) propionate can be added. wear. In addition, tris (4-methoxy 3,5-diphenyl) phosphite, tris (noyulphenol) phosphite, tris (2,4 di-t-butylphenol) phosphite, bis (2,6-di-t-butyl-4-methylphenol) It is preferable to use a phosphorus-based antioxidant such as pentaerythritol diphosphite and bis (2,4 dibutylbutyl) pentaerythritol diphosphite. The addition amount of the antioxidant is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the cyclic polyolefin.

(UV absorber)

For the resin composition in the present invention, an ultraviolet absorber is preferably used from the viewpoint of preventing deterioration of a polarizing plate or liquid crystal. As the ultraviolet absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, hindered phenol compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylates. Compounds, nickel complex compounds, and the like. Examples of hindered phenolic compounds include 2, 6 di tert butyl-p crezo monole, pentaerythrityl tetrakis [3- (3,5-di tert butyl 4-hydroxyphenenole) propionate], N, N, mono Xamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethylenole 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzenole) benzene And tris (3,5-ditertbutyl-4-hydroxybenzyl) monoisocyanurate. Examples of benzotriazole compounds include 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2,2methylenebis (4- (1,1,3,3 tetramethylbutyl) -6- (2H Nzotriazole-2-phenol) phenol), (2,4 bis (n-octylthio) -6- (4-hydroxy) -3,5-di-tert-butylanilino) -1,3,5-triazine, triethyleneglycol monorubis [3- (3-tert-butyl 5-methyl-4-hydroxyphenol) probione], N, N 'hexamethylenebis (3,5-di-tert-butyl 4-hydroxymonohydr) , 5 Trimethylolene 2, 4, 6 Tris (3,5 di-tert-butyltinol 4-hydroxybenzyl) benzene, 2 (2,1-hydroxyl-3 ', 5'-di-tert-butylbutyl No. 1) 5 Chlorbenzotriazole, (2 (2, 1 Hydroxy 3, 5, 5'-Di-tert-Aminophenyl) 5 Chlorbenzotriazole, 2, 6 Di-tert Butyl-p-Talesol, Pentaerythrityl Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. The amount of addition of these UV inhibitors is from 1 ppm by weight to the cyclic polyolefin; The preferred range is 10 to 1000 ppm.

[0113] (Letter generation expression agent)

In the present invention, in order to express a letter value, a compound having at least two aromatic rings can be used as a letter expression enhancer. When using a letter expression developer, it is preferable to use it in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the cyclic polyolefin. More preferably, it is more preferable to use in the range of 0.5 to 5 parts by mass, and most preferable to use in the range of 0.5 to 2 parts by mass. Two or more letter expression enhancers may be used in combination.

The letter expression enhancer preferably has a maximum absorption in the wavelength region of 250 to 400 nm, and preferably has a substantial absorption in the visible region.

In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). Aromatic heterocycles are generally unsaturated heterocycles. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. The heteroatom is particularly preferably a nitrogen atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom. Examples of aromatic heterocycles include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, triazole, pyran, Pyridine ring, pyridazine ring, pyrimidine ring, virazine ring and 1,3,5-triazine ring are included. Aromatic rings include benzene, furan, thiophene, pyrrole, oxazole, thiazole, imidazole, triazole, pyridine, pyrimidine, pyrazine, and 1,3,5-triazine rings. Good In particular, 1,3,5 triazine ring is preferably used. Specifically, for example, compounds disclosed in JP-A No. 2001-166144 are preferably used.

[0115] The number of aromatic rings possessed by the letter expression enhancer is preferably 2 to 20.

2 to 12 is more preferable, and 2 to 8 is more preferable, and 2 to 6 is more preferable. The bond relationship between two aromatic rings can be classified as (a) when a condensed ring is formed, (b) when directly linked by a single bond, and (c) when linked via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The binding relationship may be any of (a) to (c)

[0116] Examples of the condensed ring of (a) (condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a funolenic ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenol. Diene ring, naphthacene ring, pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiene phen ring, indolizine ring, benzoxa xazonole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, Indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, force rubazole ring, atalidine ring, phenanthridine ring, xanthene ring, phenazine ring, Phenothiazine ring, phenoxathiin ring, phenoxazine ring and Include thianthrene ring. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be joined by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

[0117] The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, CO 2 NH—S or a combination thereof. Examples of linking groups consisting of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.

cl: CO— O—

c2: -CO-NH- c3:-Ano-Recylene O—

c4: NH—CO—NH—

c5: NH—CO—O—

c6: O— CO— O—

c7: o—anoleylene o—

c8: CO Anolekenylene

c9: — CO Anolekenylene NH—

clO ： —CO Anolekenylene O—

cl l ： ----------------------

cl2 ： One O Anoleylene CO— O Anoleylene O— CO Ananolene o cl3 ： One O— CO Anoleylene CO o—

cl4 ： —NH—CO Anolekenylene

cl5 ： One O—CO Anolekenylene

[0118] The aromatic ring and the linking group may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxynore, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, ananolenoyl group, alkenyl group, alkynyl group, aliphatic Acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group

, An aliphatic sulfonamido group, an aliphatic substituted amino group, an aliphatic substituted rubamoyl group, an aliphatic substituted sulfamoyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group.

The alkyl group preferably has 1 to 8 carbon atoms. A straight chain alkyl group is particularly preferred, with a chain alkyl group being preferred over a cyclic alkyl group. The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butynole, n-hexenole, 2-hydroxyethynole, 4-strength noroxybutynole, 2-methoxyethyl and 2-jetylaminoethyl. Is included.

[0119] The alkenyl group preferably has 2 to 8 carbon atoms! / ,. Cyclic alkenyl group A straight chain alkenyl group is particularly preferred, with a chain alkenyl group being more preferred. The alkenyl group may further have a substituent. Examples of alkenyl groups include bur, arinole and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. A linear alkynyl group is particularly preferred over a cyclic alkynyl group, with a chain alkynyl group being preferred. The alkynyl group may further have a substituent. Examples of alkynyl groups include echtur, 1-butur and 1-hexyl.

[0120] The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examples of the aliphatic isyl group include acetyl, propanol and butanol. The number of carbon atoms of the aliphatic acyloxy group is preferably 1 to 10. Examples of the aliphatic acyloxy group include acetoxy. The number of carbon atoms in the alkoxy group is preferably 1-8. The alkoxy group may further have a substituent (eg, alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxy ethoxy. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 10. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The number of carbon atoms of the alkoxycarbonylamino group is preferably 2 to 10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

[0121] The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio and octylthio. The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl. The number of carbon atoms in the aliphatic amide group is preferably 1 to 10. Examples of the aliphatic amide group include acetamide. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of aliphatic sulfonamido groups include methanesulfonamido, butanesulfonamido and n-octanesulfonamido. The number of carbon atoms of the aliphatic substituted amino group is preferably 1 to 10. Examples of aliphatic substituted amino groups include dimethylamido jettilamino and 2-carboxyethylamino.

[0122] The number of carbon atoms in the aliphatic substituent ruberamoyl group is preferably 2 to 10. fat Examples of group substituent rubermoyl groups include methylcarbamoyl and jetylcarbamoyl. The aliphatic substituted sulfamoyl group preferably has 1 to 8 carbon atoms. Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and jetinolesulfamoyl. The number of carbon atoms in the aliphatic substituted ureido group is preferably 2 to 10. Examples of the aliphatic substituted ureido group include methylureido.

Examples of non-aromatic heterocyclic groups include piperidino and morpholino. The molecular weight of the letter expression enhancer is preferably 300 to 800! /.

[0123] In the present invention, a rod-shaped compound having a linear molecular structure can be preferably used in addition to a compound using a 1,3,5-triazine ring. The linear molecular structure means that the rod-shaped compound has a linear molecular structure, which is the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculations can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to determine the molecular structure that minimizes the heat of formation of compounds. The linear molecular structure means that in the thermodynamically most stable structure obtained by calculation as described above, the angle of the main chain constituting the molecular structure is 140 degrees or more.

[0124] The rod-shaped compound having at least two aromatic rings is preferably a compound represented by the following general formula (IV).

Formula (IV): Ar'-L'-Ar ²

In the general formula (IV), 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 a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocycle of an aromatic heterocycle group is generally unsaturated. The aromatic heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. The heteroatom is more preferably a nitrogen atom or a sulfur atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom. The aromatic ring of the aromatic group includes benzene ring, furan ring, Particularly preferred are benzene rings, preferably ophene, pyrrole, oxazole, thiazole, imidazole, triazole, pyridine, pyrimidine and pyrazine rings.

[0126] In the general formula (IV), L ¹ represents an alkylene group, an alkenylene group, an alkynylene group, O

A divalent linking group selected from the group consisting of CO and combinations thereof. The alkylene group may have a cyclic structure. As the cyclic alkylene group, 1,4-cyclohexylene is particularly preferred, where xylene is preferred. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 8, and most preferably 1. Thru 6.

[0127] The alkenylene group and the alkynylene group preferably have a linear structure rather than a branched chain structure, which preferably has a chain structure rather than a cyclic structure. The number of carbon atoms of the alkkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, further preferably 2 to 6, and further preferably 2 to 4, most preferably Preferably 2 (vinylene or ethynylene). The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 16, and still more preferably 6 to 12. In the molecular structure of the general formula (IV), the angle formed by Ar ¹ and Ar ² across L ¹ is preferably 140 degrees or more.

As the rod-like compound, a compound represented by the following formula (V) is more preferable. Formula (V): Ar'-L'-X-L'-Ar ²

In the general formula (V), Ar ¹ and Ar ² are each independently an aromatic group. The definition and examples of the aromatic group are the same as those of Ar ¹ and Ar ^{2 in} the general formula (IV).

In general formula (V), L ² and L ³ are each independently an alkylene group, —O

It is a divalent linking group selected from the group consisting of CO and combinations thereof. More preferably, the alkylene group has a linear structure rather than a chain structure having a branch, which preferably has a chain structure rather than a cyclic structure. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6 More preferably 1 to 4 and most preferably 1 or 2 (methylene or ethylene). L ² and L ³ are particularly preferably O—CO or mono-CO—O. In the general formula (V), X is 1,4-cyclohexylene, vinylene or ethynylene. Two or more rod-shaped compounds having a wavelength shorter than the maximum absorption wavelength (λ max) force of ¾50 nm may be used in combination with the ultraviolet absorption spectrum of the solution. The addition amount of the letter expression enhancer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the amount of cyclic polyolefin.

[0129] (Peeling accelerator)

As additives for reducing the peeling resistance of a cyclic polyolefin resin film, many additives having a remarkable effect on surfactants have been discovered. As preferred release agents, phosphate ester surfactants, carboxylic acid or carboxylate surfactants, sulfonic acid or sulfonate surfactants, and sulfate ester surfactants are effective. . In addition, a fluorine-based surfactant in which a part of hydrogen atoms bonded to the hydrocarbon chain of the above-mentioned surfactant is substituted with a fluorine atom is also effective. Examples of the release agent are given below.

[0130] RZ-1 C H 0-P (= 0)-(OH)

8 17 2

RZ-2 C H 0-P (= 0)-(OK)

12 25 2

RZ-3 C H OCH CH 0-P (= 0)-(OK)

12 25 2 2 2

RZ-4 C H (OCH CH) O— P (= 0) — (OK)

15 31 2 2 5 2

RZ-5 {C H 0 (CH CH O)} P (= 0) — OH

12 25 2 2 5 2

RZ-6 {C H (OCH CH) O} P (= 0) — ONH

18 35 2 2 8 2 4

RZ-7 (t-C H) — C H — OCH CH O— P (= 0) — (OK)

4 9 3 6 2 2 2 2

RZ-8 (iso-C H — C H — O— (CH CH O) P (= 0) — (OK) (OH)

9 19 6 4 2 2 5

RZ-9 C H SO Na

12 25 3

RZ-10 C H OSO Na

12 25 3

RZ-11 C H COOH

17 33

RZ-12 C H COOH-N (CH CH OH)

17 33 2 2 3

RZ-13iso-C H — C H — O— (CH CH O) One (CH) SO Na

8 17 6 4 2 2 3 2 2 3

RZ-14 (iso CHO— (CH CH O) (CH) SO Na RZ-15 Sodium triisopropyl naphthalene sulfonate

RZ—16-tri-t-butyl naphthalene sulfonate

RZ- 17 C H CON (CH) CH CH SO Na

17 33 3 2 2 3

RZ— 18 C H — C H SO -NH

12 25 6 4 3 4

[0131] The addition amount of the release accelerator is preferably 0.05 to 5% by mass with respect to the cyclic polyolefin 0.5; more preferably 2 to 2% by mass 0.;! To 0.5% by mass Most preferred.

[0132] (Plasticizer) In general, cyclic polyolefin resin is susceptible to cracking and the like when it is subjected to bending stress or shear stress S on a film that is less flexible than cellulose acetate. In addition, when processing as an optical film, cracks are easily generated in the cut portion and chips are easily generated. The generated chips contaminated the optical film and caused optical defects. In order to improve these problems, a plasticizer can be added. Specifically, phthalic acid ester, trimellitic acid ester, aliphatic dibasic acid ester, orthophosphoric acid ester, acetic acid ester, polyester 'epoxidized ester, ricinoleic acid ester, polyolefin, Mention may be made of polyethylene glycol compounds.

[0133] It is preferable to select a plasticizer that can be used at room temperature, normal pressure, in a liquid state and has a boiling point of 200 ° C or higher. Specific examples of compound names include the following. Examples of the aliphatic dibasic acid ester system include dioctyl adipate (230 ° C / 76 OmmHg), dibutinorea dipate (145 ° C / 4mmHg), di-2-ethinorehexinorea dipeto (335 ^o G / 760mm: Hg) , Dif, Chinoresiguri Monoreji page (230 ~ 240 ^o G / 2 mmHg), G2 hexylhexylaselate (220 ~ 245 ° C / 4mmHg), G2-Ethylhexyl sebacate (377 ° C / 760mmHg), etc. Phthalic acid esters include, for example, jetyl phthalate (298 ° C / 760mmHg), diheptyl phthalate (235 to 245 ° C / 10mmHg), di noctino phthalate (210 ° C / 760mmHg), diisodecyl phthalate (420 ° C / 760mmHg) etc .; Polyolefins include paraffin waxes such as normal paraffin, isoparaffin, cycloparaffin (average molecular weight 330-600, melting point 45-80 ° C), liquid paraffin (JIS standard K2231ISOVG8, the same) VG15, V G3 2, VG68, VG100, etc.) Raffin pellets (melting point 56-58.C, 58-60.C, 60 ~ 62 ° C), chlorinated paraffin, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, squalane, etc.

[0134] The plasticizer is added in an amount of 0.5 to 40.0 mass% with respect to the cyclic polyolefin-based resin from the viewpoint of plasticizing effect, processing suitability, optical unevenness, contamination of other parts, and the like. Preferably 1.0 mass ⁰ /. To 30.0 mass ^_0/0, more preferably 3 · 0% to 20 · 0 Weight ^_0/0.

[0135] (Dope preparation)

Next, with respect to the preparation of the cyclic polyolefin resin solution (dope) of the present invention, after stirring the polymer at room temperature and swelling the polymer by cooling at room temperature, it was cooled from −20 ° C. to −100 ° C. and again. A cooling dissolution method that melts by heating from 20 ° C to 100 ° C, a high temperature dissolution method that melts at a temperature above the boiling point of the main solvent in a closed container, and a high temperature and high pressure to the critical point of the solvent. There are ways to do it. The solubility is good! / The polymer is preferably dissolved at room temperature, but the poorly soluble polymer is preferably dissolved by heating in a closed container. When dichloromethane is chosen as the main solvent, many cyclic polyolefins can be dissolved by heating from 20 ° C to 100 ° C.

[0136] The viscosity of the cyclic polyolefin resin solution of the present invention is preferably in the range of lPa's to 500Pa's at 25 ° C. More preferably, it is in the range of 5 Pa ′s to 200 Pa ′s. The viscosity was measured as follows. Sample solution lmL is 4cm / 2 in diameter on a rheometer (CLS 500). Steel Cone (both manufactured by TA Instrumennts). Measurement was started after the sample solution was kept warm at the measurement start temperature until the liquid temperature became constant.

[0137] In order to facilitate dissolution, it may be dissolved at a low concentration and then concentrated using a concentration means. The concentration method is not particularly limited. For example, a low-concentration solution is introduced between the cylinder and the rotation trajectory of the outer periphery of the rotating blade rotating in the circumferential direction, and between the solution and the solution. A method of obtaining a high-concentration solution while evaporating the solvent by giving a temperature difference (for example, JP-A-4-259511), a heated low-concentration solution is blown into the container from the nozzle, and the solution is injected from the nozzle into the container inner wall In addition, the solvent is flash-evaporated and the solvent vapor is extracted from the container and the high-concentration solution is extracted from the container bottom (for example, U.S. Pat.No. 2,541,012, U.S. Pat. 229, U.S. Pat.No. 4,414,34 1 and the methods described in US Pat. No. 4,504,355, etc.

[0138] Prior to casting, it is preferable to filter off foreign matters such as undissolved matter, dust, and impurities using a suitable filter medium such as a wire mesh or flannel. For the filtration of the cyclic polyolefin solution, a filter with an absolute filtration accuracy of 0 ·; 1 m to 100 m is preferably used, and a filter with an absolute filtration accuracy of 0.5 to 2511 m is more preferably used. The thickness of the filter is preferably 0.1 mm to 10 mm, and more preferably 0.2 mm to 2 mm. In that case, the filtration pressure is preferably 1.6 MPa or less, more preferably 1.3 MPa or less, further 1. OMPa or less, particularly preferably 0.6 MPa or less. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, fluororesin such as tetrafluoroethylene resin can be preferably used, and ceramics, metals and the like are also preferably used.

The viscosity of the cyclic polyolefin resin solution immediately before film formation should be within the range that can be cast at the time of film formation, and usually it should be adjusted within the range of 5 Pa's to lOOOPa 's. s to 500 Pa's force S is more preferable, and 30 Pa's to 200 Pa's force S is more preferable. The temperature at this time is not particularly limited as long as it is the temperature at the time of casting, but is preferably 5 ° C to 70 ° C, more preferably 5 ° C to 35 ° C.

In the present invention, attention is paid to the storage elastic modulus and loss elastic modulus constituting the complex elastic modulus as an index representing the self-supporting property of the viscoelastic body.

When the storage modulus is E 'and the loss modulus is E' ', the relationship between these logarithms and temperature is shown in Fig. 2. (Non-patent literature: "Rheology and optics and its applied technology", Publisher: Fuji Techno System)

In order for the viscoelastic body, i.e., the film in the present invention, to have self-supporting properties, the force that is necessary for the solution to gel on the casting support is a necessary gelling temperature, that is, the gel point is stored. This is equivalent to the intersection of the logarithm of the elastic modulus E 'and loss elastic modulus E'. Therefore, when the solution is cast on the casting support as in the present invention, the temperature of the casting support is adjusted to an appropriate temperature, and the gel is formed while the dope is on the casting support. The storage elastic modulus E ′ and loss elastic modulus E ′ ′ of the dope should be adjusted in advance to reach the turning point. Figure 3 shows this relationship. [0140] In the present invention, the cyclic polyolefin resin solution described above reaches the gel point TO before being peeled off after being cast on the endless support. This gel point is the temperature at which the magnitude relationship between the values of E 'and E''is reversed, where E' is the storage modulus of the solution and E '' is the loss modulus. (See Fig. 3) When this viscoelastic property is not satisfied, for example, when E 'is always smaller than E''from casting to peeling, the resulting cyclic polyolefin resin film is obtained. The surface shape, transparency, optical uniformity, and mechanical strength of the film are uneven, and the effects of the present invention cannot be achieved.

In order to give this viscoelastic property, (1) 0.01% to 2% by weight of water is mixed with the total amount of solvent, (2) the alcohol addition ratio is optimized, (3) high For example, the stirring time for adjusting the concentrated molecular solution may be 30 minutes or more and 5 hours or less. These means may be combined or may be used alone.

When adding the poor solvent described in (1) or (2) above, the gelation does not occur sufficiently or the dissolution failure does not occur, the foreign matter is generated in the film and the surface condition does not deteriorate, It is preferably 4% or more and 20% or less with respect to the total amount of the dissolved medium. Further, it is more preferably 6% or more and 15% or less. The gel point may be achieved between the start of casting and peeling, but is preferably set to 40 ° C or higher and 0 ° C or lower.

[0141] In the present invention, the storage elastic modulus E ′ and the loss elastic modulus E ′ ′ are values measured in a solution state by a viscoelasticity measuring device for solution (“Rheometer”, manufactured by Thysica). means. Measurement is at a strain of 0.01, at a frequency of 1 Hz and at a constant measurement temperature for at least 5 minutes and over 40 points, and the average value when measured under measurement conditions such that the variation of each measurement point is within ± 5% It is adopted as E ', E', at each temperature. When the temperature is changed, the temperature is changed from the high temperature side to the low temperature side, and at each measurement temperature, the measurement system is held for at least 10 minutes before reaching a certain temperature (equilibrium temperature).

In the present invention, the temperature dependence of E ′ and E ′ ′ from 50 ° C. to 10 ° C. is expressed as E ′ = A * exp (—B * T), E ′ ′ = C * exp ( — D * T) [where A to D are constants and T is temperature (° C)], it is preferable to satisfy the relationship 0≤D <B.

As shown in Fig. 4, the measured data indicates that the horizontal axis represents temperature and the vertical axis represents the logarithm of storage elastic modulus E 'and the logarithm of loss modulus E''satisfy a linear relationship. Read from As a result, the storage elastic modulus E 'and loss elastic modulus E''can be expressed as E' = A * exp (— B * T), E ', = C * exp (— D * Τ), respectively. The values A to D are adjusted so that they have intersections within a predetermined temperature range.

[0143] (Solution casting film forming method)

Solution casting film forming methods are described in many literatures. In the recent solution casting film forming method, the time required from the casting of the dope onto the support to the peeling of the molded film on the support is shortened, and the productivity of the film-controlling worker is improved. Is a problem. For example, Japanese Patent Publication No. 5-17844 proposes shortening the time until casting after casting by casting a high-concentration dope onto a cooling drum. In film formation in the present invention, it is preferable to use this drum film formation method. The drum film forming method is explained below.

Yes

[0144] Fig. 5 shows a schematic view of a film-forming line 10 used for carrying out the solution casting film-forming method according to the present invention. FIGS. 6 and 7 are schematic views of the main part of the film production line 10. In the mixing tank 11, the dope 12 prepared by the above-described method is charged and stirred by the stirring blade 13 to be uniform. The dope 12 is sent to the filtration device 15 by the pump 14 to remove impurities. After that, it is sent to a casting die 21 installed in the casting chamber 20 at a constant flow rate. The casting die 21 is disposed on the rotating drum 22. The rotating drum 22 is rotationally driven by a driving device (not shown). A casting bead 23 is formed by casting the dope 12 from the casting die 21 on the rotating drum 22. In the present invention, the position where the casting bead 23 has landed on the rotating drum 22 is indicated by a landing line (see FIG. 6, since the figure is shown from a direction orthogonal to the running direction of the film). Called 22a. The casting bead 23 is gelled on the rotating drum 22 as a support to become a gel film 24. When the gel film 24 moves as the rotary drum 22 travels, gelation further proceeds due to cooling. When the gel film 24 reaches the peeling line (see FIG. 6) 22b, it is peeled off from the rotating drum 22 by the peeling roller 25 to become a film 26. In addition, it is more preferable to blow the dry air 19 in the direction opposite to the rotation direction of the rotary drum 22 from the blower (not shown! /) Force and the force S.

As shown in FIG. 7, the rotating drum 22 has a support rotating shaft (hereinafter referred to as a rotating shaft) 40, 4 1 is attached, and bearings 42 and 43 are attached to the rotary shafts 40 and 41, not shown in FIG. The rotating shaft 40, the rotating drum 22, and the rotating shaft 41 are provided with a medium flow path (not shown) therein. A cooling medium (hereinafter referred to as a refrigerant) 44 that is an antifreeze heat medium is supplied from the refrigerant supply device 45 to the flow path, whereby the rotary drum 22 is cooled. In the present invention, the surface temperature of the rotating drum 22 is preferably 10 ° C. or less, more preferably 5 ° C. or less, and most preferably −20 ° C. or less. However, the present invention is not limited to these temperature ranges.

[0146] As the refrigerant 44, a glycol refrigerant, a fluorine refrigerant, an alcohol refrigerant, or the like is used. Most preferably, Fluorinert (registered trademark) FC-77, HFE7100, cold brine (registered trademark) FP60 is used. Certain forces are not limited to those refrigerants. Further, the cooling method of the rotating drum used in the present invention is not necessarily limited to the method of passing the refrigerant as shown in FIG.

[0147] Furthermore, when the rotating drum 22 used in the present invention is made of a low-temperature brittle material, the physical strength against the impact of the equipment and the repeated load is prevented when cooled at a low temperature. It is more preferable because it is possible. Specifically, those made of SUS, SLA, STPL, etc. are preferred! /, But are not limited to these! /.

[0148] As shown in Fig. 6, the casting die 21 is preferably provided with a gas conduit 27a connected to the gas supply device 27 on the bead back surface 23b side. By blowing gas (hereinafter also referred to as the first gas) 28 through the gas pipe line 27a to the bead back surface 23b, the gas concentration on the bead back surface 23b can be lowered and the dew point can be lowered. Thereby, dew condensation on the surface of the rotating drum 22 can be prevented, and deterioration of the surface quality of the film 26 is suppressed. Furthermore, when condensation occurs on the surface of the rotating drum 22 where condensation has occurred, if the gel film 24 is formed, the gel film 24 falls from the rotating drum 22 between the landing line 22a and the stripping line 22b, which hinders continuous operation. . According to the present invention, the condensation on the surface of the rotating drum 22 can be prevented, so that the gel film 24 can be prevented from falling off. Gas 28, such as nitrogen gas or helium gas (usually called an inert gas) does not affect the characteristics of the film! /, And it is preferable to use a gas 28 /.

[0149] Gas 28 is supplied so that the dew point is 1 ° C or more lower than the surface temperature of the rotating drum 22. It is preferable to blow air after the temperature is adjusted by the device 27. Note that the temperature of the surface of the rotating drum 22 can be measured using a well-known! /, Or a misalignment device! / (The thermometer is not shown). Below this temperature differential force, condensation may occur due to slight variations in process conditions. Furthermore, it is preferable that the wind speed of the gas 28 is in the range of 0.5 m / s to 2 m / s. When the wind speed is less than 0.5 m / s, the effect of reducing the gas concentration near the casting bead 23 is small. If the wind speed is higher than 2 m / s, uneven wind may occur in the casting bead 23, and the surface quality of the film may deteriorate. The temperature of the first gas 28 is preferably in the range of 30 ° C to 50 ° C. However, in the present invention, the wind speed and temperature of the gas (first gas) are not limited to the above ranges by changing other experimental conditions.

Yes

[0150] The dope 12 cast on the surface of the rotating drum 22 increases the strength (film strength) of the gel film 24 by cooling gelation, and further promotes drying until stripping. However, the strength (film strength) of the gel film 24 increases. If the stress (film stress) due to stretching of the gel film 24 at the time of stripping is less than 450,000 Pa, the strength as a film is insufficient, and the self-supporting property necessary for stripping may not be obtained. In the present invention, the stress value due to stretching is preferably 450,000 Pa or more, more preferably 600,000 Pa or more, and most preferably 750,000 Pa or more. In the present invention, the value measured by stretching using a load cell is used as the stress value by stretching the film.

[0151] When the gel film 24 is peeled off as the film 26, the speed ratio V1 / V0 between the peripheral speed (V0) of the rotary drum 22 and the peripheral speed (VI) of the peeling roller 25 is 1 · 001≤ (V1 /V0)≤1.5 Force to be in range S S, more preferably 1.002≤ (V1 / V0) ≤1.3, most preferably 1.005≤ (V1 / V0 ) ≤1.2. By setting the ratio of (V1 / V0) within the range described above, the stretching force applied to the film 26 is increased, and the stripping becomes stable. If the speed ratio is less than 1.001, the stretching force of the film is insufficient, the peel line 22b rises, and it becomes difficult to remove the film uniformly. On the other hand, if the speed ratio is greater than 1.5, the film (soft film) immediately after stripping with a high volatile content may cause problems such as “tear” and “stressing” from the edge of the ear due to rapid stretching. In the present invention, the speed ratio (V1 / V0) is not limited to the above-described range. [0152] If the clearance CI between the rotating drum 22 and the stripping roller 25 is narrowed, the stretching speed increases, so the stretching force increases and the stripping becomes stable. However, if the clearance C1 is less than lm m, the film may be cut due to the film debris and other foreign matter being caught. In addition, if the clearance C1 is larger than 100 mm, the effect of increasing the stretching force of the film is reduced, the stripping position is raised, and stripping may become unstable. Therefore, in the present invention, the clearance C 1 is preferably in the range of lmm ≦ Cl ≦ 100 mm, but is not limited to this range. In the present invention, the clearance C1 means the interval between the intersection points where the lines a connecting the centers of the rotary drum 22 and the peeling roller 25 intersect with the outer periphery when the rotary drum 22 and the peeling roller 25 are arranged on the same plane. Further, the peeling roller 25 has a reference line of the rotating drum 22 (the reference line means a line vertically upward from the center of the rotating drum as shown in the figure). 180 ° is preferred, more preferably 60 ° to 120 °.

[0153] In order to facilitate the peeling of the gel film 24 from the rotating drum 22, the difference force between the surface tension of the rotating drum 22 and the surface tension of the dope 12 is S, 3 X 10_ ² (N / m) or more. The rotating drum 22 becomes wet with the solvent and the contact area between the gel film 24 and the rotating drum 22 is reduced. As a result, the peeling resistance at the time of peeling can be lowered, so that the peeling is stable. In the present invention, any known method can be used for measuring the surface tension. In the present invention, the difference in surface tension is not limited to that described above! /.

[0154] The gel film 24 does not exist on the rotating drum 22 between the stripping line 22b and the bead landing line 22a shown in FIG. In the present invention, this surface is referred to as a gel-free film surface 22c. As described above, the rotary drum 22 is cooled by supplying the refrigerant therein. Therefore, if the surface temperature of the gel-free film surface 22c reaches the dew point, condensation may occur on this surface. Also, the rotating drum 22 travels endlessly, so water drops or condensed solvent adheres to it, and when the dope 12 is cast on the surface, the surface shape of the film to be formed is reduced. May cause deterioration. Therefore, a gas (hereinafter also referred to as second gas) 30 is blown onto the gel-free film surface 22c using a blower 29, and the temperature of the gel-free film surface 22c is higher by 1 ° C or more than the dew point near the casting bead 23. By doing so, adhesion of water droplets and liquefied solvent can be prevented. The temperature of the gas (second gas) 30 is preferably in the range of 50 ° C. to 100 ° C. and the wind speed is 2 m / s to 10 m / s. Is not limited to those ranges.

As shown in FIG. 7, the refrigerant 44 is also passed through the rotary shafts 40 and 41. Therefore, when the atmosphere in the vicinity of the rotating shafts 40 and 41 and the bearings 42 and 43 is cooled and reaches the dew point, water vapor contained in the atmosphere is condensed and water droplets are generated. Further, the casting chamber 20 contains vaporized solvent volatilized from the dope 12, and the vaporized solvent may be liquefied and adhere to the rotating shafts 40 and 41 and the bearings 42 and 43. If the adhesion becomes violent, rotation failure may occur, which may hinder continuous film formation. Therefore, in the present invention, the fans 46 and 47 are provided in the vicinity of the rotating shafts 40 and 41 and the bearings 42 and 43 so that the gases (hereinafter also referred to as third gases) 48 and 49 are respectively connected to the rotating shafts 40 and 41 and the bearings 42 and 42. By blowing air to 43, it is possible to prevent condensation on the rotating shafts 40 and 41 and the bearings 42 and 43. The gas 48, 49 to be blown is not particularly limited as long as the temperature in the vicinity of the rotary shafts 40, 41 is not below the dew point, but specifically, a range of 20 ° C to 30 ° C is preferable. The wind speed is preferably in the range of 2 m / s to 10 m / s, but is not limited to this range. In the present invention, the embodiment of the blower is not limited to that shown in FIG. For example, in FIG. 7, gas may be blown to both shafts of the rotary shafts 40 and 41 using a single blower having the fans 46 and 47 installed on the rotary shafts 40 and 41, respectively.

[0156] When the solution casting film-forming method according to the present invention is performed, if the casting die 21 and the rotating drum 22 are provided in the casting chamber 20, a random wind is applied to the casting bead 23. This is preferable because a film 26 having a uniform surface shape can be obtained. However, if condensation occurs in the casting chamber, water droplets or the like may adhere to the surface of the gel film 24, causing defects such as streaks on the surface of the film. If liquid adheres to the rotating shafts 40 and 41 and the bearings 42 and 43 (see FIG. 7) and condenses, it may be difficult to control the rotational speed of the rotating drum 24. It may even get stuck at all. Therefore, there is a recovery device 31 for condensing and recovering the vaporized solvent in the casting chamber 20!

[0157] The recovery device 31 includes a condensing surface 31a that condenses water vapor contained in the atmosphere in the casting chamber 20 and the vaporized solvent vaporized by the solvent in the gel film 24. The temperature of the condensing surface 31a is defined by the type of solvent constituting the dope 12 and is not particularly limited. However, in the present invention, the surface temperature of the film 26 may be lower by 1 ° C or more. More preferably, it is preferably 1 ° C. to 20 ° C. lower than the surface temperature of the film 26. If the temperature differential force is less than ° C, liquids such as water droplets may adhere to the surface of film 26 when the conditions of the casting process slightly change. Moreover, if it is lower than 20 ° C, it is disadvantageous in terms of cost. In the present invention, the film surface temperature is preferably measured using a non-contact thermometer 32 in the vicinity of the measurement point 26a shown in FIG. 6, but the temperature measurement method is not limited thereto. Absent. More preferably, the recovery device 31 adjusts the temperature of the condensing surface 31a based on the temperature measured by the thermometer 32.

In order to further dry the film 26, a tenter chamber 60 and a drying chamber 61 are installed on the downstream side of the casting chamber 20 (see FIG. 5). Drying while stretching the width direction of the film by the tenter dryer 62 in the tenter chamber 60 is preferable in order to make the surface shape of the film 26 uniform. Further, the film 26 is fed into the drying chamber 61 where a large number of rollers 63 are arranged. The film 26 is dried while being conveyed while being wound around the rollers 63. Further, the film 26 is preferably cooled to about room temperature in the cooling chamber 64. Then, it is preferable to wind with a winder 65 S. In addition, before winding in the present invention, the ear may be cut off or knurled. Further, the film forming line 10 used in the solution casting film forming method according to the present invention is not limited to the one shown in FIGS.

[0159] The solution casting film-forming method of the present invention is most suitable for the film-forming method of a film (thin film) formed to a thickness in the range of 20 m to 120 m because the film stress at the time of peeling is large. Is suitable. The film thickness of the film is more preferably 20 m to 65 m, and most preferably, the solution casting film forming method of the present invention is applied to film formation of a film of 20 am to 45 am.

[0160] In FIG. 5, force showing a form in which one kind of dope is cast in a single layer. The present invention is not limited to the illustrated form! /. For example, a co-casting method in which a feed block is attached upstream of the casting die, a large number of dopes are fed into the feed block, and the dopes are cast together in the feed block. It is possible to apply. In the figure, the rotary drum 22 is used as a support. However, the present invention is not limited to the illustrated form. For example, the dope is cast on a casting belt that runs endlessly by a rotating roller. It can also be applied to the solution casting film forming method.

[0161] (Thickness of cyclic polyolefin resin film)

The thickness of the final (after drying) cyclic polyolefin resin film of the present invention varies depending on the intended use. Usually, it is in the range of 5 am to 500 am, and the range of 15 m to 150 μm is particularly preferred. For display devices it is preferably 30 m to 1 10 m. The film thickness is adjusted by adjusting the solid content concentration in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, etc. so that the desired thickness and thickness distribution are obtained. Adjust it. The width of the cyclic polyolefin-based resin film obtained as described above is preferably 0.5 to 3 m force S, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2 m. 2m. The length is 100 m to 1 ronole; it is more preferable to wind up at 10000 m <is 500 m to 7000 m, and more preferably <1000 m to 6000 m. The variation in the Re value of the full width is preferably ± 5 nm, and more preferably ± 3 nm. Further, the dispersion of the Rth value is preferably ± 5 nm, more preferably ± 5 nm. In addition, the variation in the Re value and the Rth value in the length direction is preferably within the range of the variation in the width direction.

[0162] (Optical properties of cyclic polyolefin resin film)

The preferable optical properties of the cyclic polyolefin resin film of the present invention vary depending on the application of the film. In the case of a polarizing plate protective film, the in-plane letter retardation (Re) is preferably 5 nm or less, more preferably 3 nm or less. The thickness direction letter decision (Rth) is preferably 50 nm or less, more preferably 35 nm or less, and particularly preferably lOnm or less.

When a cyclic polyolefin resin film is used as an optical compensation film (retardation film), the range of Re and Rth differs depending on the type of retardation film, and there are various needs. Onm≤Re≤100nm, 40nm≤ Rth≤400 nm is preferable. TN mode 0nm≤Re≤20nm, 40nm≤Rth≤80nm, VA mode 20nm≤Re ≤80nm, 80nm≤Rth≤400nm is more preferred Especially in VA mode, the preferred range is 30nm≤Re≤75nm, 120nm≤ Rth ≤ 250nm, 50nm≤Re≤75nm, 180nm≤Rth≤250nm when compensating with one retardation film, 30nm≤Re≤50nm, 80nm when compensating with two retardation films ≤ Rth ≤ 140 nm In the case of a compensation film, this is a more preferable aspect in terms of color shift during black display and the viewing angle dependence of contrast.

The cyclic polyolefin film of the present invention can achieve desired optical characteristics by appropriately adjusting the process conditions such as the polymer structure to be used, the kind and amount of additives, the draw ratio, the residual volatile content at the time of peeling. . For example, by adjusting the residual volatile content at the time of peeling within 40 to 85 mass%, it is possible to widely control the thickness-direction letter Rth from 180 to 300 nm. In general, the greater the residual volatile content at the time of stripping, the smaller the Rth, and the smaller the residual volatile content at the time of stripping, the greater Rth. For example, by shortening the drying (single-sided drying) time on the metal support and increasing the residual volatile content at the time of peeling, the surface orientation can be relaxed and Rth can be freely lowered, and the process conditions are adjusted. Therefore, it is possible to express various letterings according to various applications.

In the present specification, Re (E) and Rth () respectively represent in-plane letter deposition at the wavelength and letter direction in the thickness direction. Re (λ) is measured with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) by irradiating light with a wavelength of nm in the film normal direction.

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth () is calculated by the following method.

1¾1 (e) is the above-mentioned 1¾3 (e) with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) Measured at a total of 6 points by injecting light of wavelength nm from each inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction Then, KOBRA 21ADH or WR calculates based on the measured letter value, the assumed average refractive index, and the input film thickness.

In the above case, in the case of a film having a direction where the in-plane slow axis is the rotation axis from the normal direction and the letter value is zero at a certain tilt angle, letter data at a tilt angle larger than the tilt angle is used. The Chillon value is calculated by KOBRA 21 AD H or WR after changing the sign to negative.

Note that the slow axis is the tilt axis (rotation axis). Measure the letter value from any two tilted directions, based on the calculated value, the assumed average refractive index, and the input film thickness. ) And equation (B) can also be used to calculate Rth.

[0164] [Equation 1] Formula (A)

[0165] However, the above Re (Θ) represents the direct retardation in the direction inclined by the angle Θ from the normal direction.

In the formula (A), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. Represents the ratio. d represents thickness.

Rth = ((nx + ny) / 2-nz) X d formula (B)

If the film being measured cannot be represented by a uniaxial or biaxial refractive index ellipsoid, that is, a film without a so-called optic axis, Rth () is calculated by the following method.

Rth () is defined as Re (), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis). Until then, light of a wavelength of nm is incident from each tilted direction in 10 degree steps, and one point measurement is performed. The measured letter value, the assumed average refractive index, and the input film KOBRA 21ADH or WR is calculated based on the thickness value.

In the above measurement, the values of the polymer handbook (JOHN WI LEY & SONS, INC) and various optical film catalogs can be used as the assumption of the average refractive index. For those whose average refractive index is not known, it can be measured with an Abbe refractometer. Examples of average refractive index values of main optical compensation films are shown below: Cellulose Sylate (1 · 48), cycloolefin polymer (1.52), polycarbonate (1 · 59), polymethylmethacrylate (1 · 49), polystyrene (1.59). KOBRA 21ADH or WR calculates nx, ny, and nz by inputting these assumptions of average refractive index and film thickness. From this calculated nx, ny, nz, Nz = (nx—nz) / (nx—ny) is further calculated.

[0166] (Polarizing plate)

The polarizing plate usually has a polarizer and two transparent protective films disposed on both sides thereof. It is possible to use the cyclic polyolefin resin film of the present invention as both or one transparent protective film. For the other transparent protective film, a normal cellulose acetate film or the like may be used. Polarizers include iodine-type polarizers, dye-type polarizers using dichroic dyes, and polyene-type polarizers. Iodine polarizers and dye polarizers are generally manufactured using polyvinyl alcohol films. When the cyclic polyolefin resin film of the present invention is used as a polarizing plate transparent protective film, the film is preferably subjected to a surface treatment as described later, and then the film treated surface and a polarizer are preferably bonded using an adhesive. Examples of the adhesive to be used include polybulal alcohol-based adhesives such as polybulualcohol and polybutylbutyral, bural latex such as butyl acrylate, and gelatin. The polarizing plate is composed of a polarizer and a transparent protective film that protects both sides of the polarizer, and further comprises a protective film on one surface of the polarizing plate and a separate film on the other surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipment of the polarizing plate and product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. The separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the surface side of the polarizing plate to be bonded to the liquid crystal plate.

[0167] The method of laminating the cyclic polyolefin resin film of the present invention to the polarizer is to force the shell to occupy the transmission axis of the polarizer and the slow axis of the cyclic polyolefin resin film of the present invention. S is preferred. In addition, when the polarizing plate produced under polarizing plate crossed Nicols was evaluated, orthogonal accuracy between the slow axis of the cyclic polyolefin resin film of the present invention and the absorption axis of the polarizer (axis orthogonal to the transmission axis) If the angle is larger than 1 °, the polarization performance under the polarizing plate crossed Nicols will decrease and light leakage will occur. In this case, combined with the liquid crystal cell In such a case, a sufficient black level and contrast cannot be obtained. Therefore, it is preferable that the deviation between the direction of the main refractive index nx of the cyclic polyolefin resin film of the present invention and the direction of the transmission axis of the polarizing plate is within 1 °, preferably within 0.5 °.

UV3100PC (manufactured by Shimadzu Corporation) can be used to measure the single plate transmittance TT, parallel transmittance ΡΤ, and orthogonal transmittance CT of the polarizing plate. In the measurement, measurement is performed in the range of 380 nm to 780 nm, and the average value of 10 measurements can be used for both single plate, parallel and orthogonal transmittance. The polarizing plate durability test can be carried out in the following two forms with (1) the polarizing plate alone and (2) the polarizing plate attached to the glass with an adhesive. To measure only the polarizing plate, prepare two orthogonal and the same ones in combination so that the optical compensation film is sandwiched between the two polarizers. For samples with glass attached, make two samples (approx. 5cm x 5cm) with a polarizing plate on the glass so that the optical compensation film is on the glass side. For single-plate transmittance measurement, set the film side of this sample facing the light source. Measure each of the two samples, and use the average value as the single plate transmittance. The preferred range of polarization performance is as follows: single-plate transmittance TT, parallel transmittance ΡΤ, orthogonal transmittance CT, 40.5 ≤ TT ≤ 45, 32 ≤ ΡΤ ≤ 39.5, CT ≤ 1.5 There are more preferable ranges: 41.0 ≤ TT ≤ 44.5, 34 ≤ ΡΤ ≤ 39.0, CT ≤ 1.3. In the polarizing plate durability test, the amount of change is smaller! /, More preferred! /.

(Surface treatment of cyclic polyolefin resin film)

In the present invention, in order to improve the adhesion between the polarizer and the transparent protective film, the surface of the cyclic polyolefin resin film is preferably surface-treated. As the surface treatment, any method may be used as long as the adhesiveness can be improved. Preferred examples of the surface treatment include glow discharge treatment, ultraviolet irradiation treatment, corona treatment and flame treatment. The glow discharge treatment referred to here is so-called low temperature plasma that occurs under low pressure gas. In the present invention, plasma treatment under atmospheric pressure is also preferable. The details of the glow discharge treatment are described in US Pat. No. 3,462,335, US Pat. No. 3761299, US Pat. No. 40 72769, and British Patent 891469. The method described in Japanese Patent Publication No. 59-556430 is also used, in which the discharge atmosphere gas composition is changed to only the gas species generated in the container by the discharge treatment of the polyester support itself after the start of discharge. It is. In addition, the method described in Japanese Patent Publication No. 60-16614, in which the discharge treatment is performed with the surface temperature of the film at 80 ° C. or higher and 180 ° C. or lower during the vacuum glow discharge treatment, can also be applied.

Yes

[0169] The degree of vacuum during the glow discharge treatment is preferably 0.5 Pa to 3000 Pa, more preferably 2 Pa to

300Pa. The voltage is preferably between 500V and 5000V, more preferably between 500V and 3000V. The discharge frequency to be used is from DC to several thousand MHz, more preferably 50 Hz to 20 MHz, still more preferably 1 kHz to 1 MHz. Discharge treatment intensity, 0. OlkV.A. min / m ² ～5KV'A min / m more preferably ² preferably instrument 0. 15KV'A min / m ² ~;. In IkV'A 'fraction m. is there.

[0170] In the present invention, it is also preferable to perform an ultraviolet irradiation method as the surface treatment! For example, it can be carried out by the processing methods described in JP-B-4 3-2603, JP-B 43-2604, and JP-B 45-3828. The mercury lamp is a high-pressure mercury lamp made of a quartz tube and preferably has an ultraviolet wavelength power of Sl 80 to 380 nm. As for the method of ultraviolet irradiation, a high pressure mercury lamp with a main wavelength of 365 nm can be used if the surface temperature of the protective film rises to around 150 ° C if there is no problem in the performance of the support. If low temperature treatment is required, a low pressure mercury lamp with a dominant wavelength of 254 nm is preferred! /. It is also possible to use ozone-less high-pressure mercury lamps and low-pressure mercury lamps. Regarding the amount of processed light, the greater the amount of processed light, the better the adhesion between the thermoplastic saturated alicyclic structure-containing polymer resin film and the polarizer, but the problem is that the film becomes colored and becomes brittle as the amount of light increases. appear. Accordingly, a high pressure mercury lamp for a 365nm main wavelength, the irradiation light quantity ^{20mj / cm 2 ~; 10000mj /} cm 2 force S may, more preferably ^{^{50mj / cm 2 ~2000mj / cm 2}} . In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light quantity lOOmj / cm ² to 1 OOOOmj / cm ² is good, more preferably 300 mj / cm ² to 1500 mj / cm ² .

[0171] Furthermore, in the present invention, it is also preferable to perform a corona discharge treatment as the surface treatment. For example, it can be carried out by the processing methods described in JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114. As the corona discharge treatment device, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETA PHON type treatment machine or the like can be used. Processing can be done at normal pressure in air The The discharge frequency during the treatment is 5 kV to 40 kV, more preferably 10 kV to 30 kV, and the waveform is preferably an AC sine wave. The gap transparent lance between the electrode and the dielectric roll is 0.1 mm to 10 mm, more preferably 1.0 mm to 2. Omm. The discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.34 kV'A 'min / m ^{2 to} 0.4 k v · Α · min / m ² , more preferably 0. From 344 kV'A 'min / m ^{2 to} 0.38 kV'A' min / m ² .

[0172] In the present invention, it is also preferable to perform a flame treatment as the surface treatment. The gas used may be natural gas, liquefied propane gas, or city gas, but the mixing ratio with air is important. This is because the effect of surface treatment by flame treatment is considered to be brought about by plasma containing active oxygen, and how much the activity (temperature) of plasma and oxygen are important properties of flame. The point is. The governing factor of this point is the gas / oxygen ratio. When reacting without excess or deficiency, the energy density is the highest and the plasma activity is increased. Specifically, the preferred mixing ratio of natural gas / air is 1/6 to 1/10, preferably 1/7 to 1/9 by volume. Also, for liquefied propane gas / air, 1/14 ~; 1/22, preferably 1/16 ~; 1/19, for city gas / air 1/2 ~; 1/8, preferably 1 / 3 to 1/7. Further, the flame treatment amount may be in the range of lkcal / m ^{2 to} 50 kcal / m ² , more preferably 3 kcal / m ^{2 to 20} kcal / m ² . The distance between the tip of the burner's internal flame and the film should be 3 cm to 7 cm, more preferably 4 cm to 6 cm. PANANA Nozzle shape: Ribbon type by Flynn Burner (USA), Multi-hole type by Wise (US), Ribbon type by Aerogen (UK), Staggered multi-hole type by Kasuga Electric (Japan), Koike Oxygen (Japan) staggered multi-hole type is preferred. The backup roll that supports the film for flame treatment is a hollow roll, which should be cooled with water through cooling water and always treated at a constant temperature of 20 ° C to 50 ° C.

[0173] As for the degree of surface treatment, the preferred range depends on the type of surface treatment and the type of cyclic polyolefin resin. Contact angle with pure water on the surface of the transparent protective film that has been surface treated as a result of the surface treatment. Is preferably less than 50 °. The contact angle is more preferably 25 ° or more and less than 45 °. When the contact angle between the surface of the transparent protective film and pure water is within the above range, the adhesive strength between the transparent protective film and the polarizer is improved.

[0174] (Adhesive) When laminating a polarizer made of polybulal alcohol and a transparent protective film made of a surface-treated cyclic polyolefin resin film, it is preferable to use an adhesive containing a water-soluble polymer. Examples of the water-soluble polymer preferably used for the adhesive include N-Burpyrrolidone, Atalinoleic acid, Methacryloleic acid, Maleic acid, Atalinoleic acid / 3-Hydroxyethyl, Methacryloleic acid / 3-Hydroxyethyl, Bull Alconole, Methyl Bull Homopolymers or copolymers containing ethylenically unsaturated monomers such as ether, butyl acetate, attalinoleamide, methacrylolamide, diacetone acrylamide, buryumidazole, polyoxyethylene, polyoxypropylene, poly-2 —Methyloxazoline, methenoresenorelose, hydroxyethinoresenorelose, hydroxypropenoresenorelose gelatin, and the like. In the present invention, among these, polybulal alcohol (PVA) and gelatin are preferable.

[0175] The preferable PVA characteristics when PVA is used for the adhesive are the same as the preferable characteristics of the PVA used for the polarizer described above. In the present invention, it is preferable to use a crosslinking agent in combination. Examples of the cross-linking agent that is preferably used in combination with PVA as an adhesive include boric acid, polyhydric aldehyde, polyfunctional isocyanate compound, polyfunctional epoxy compound, and the like, but boric acid is particularly preferred in the present invention. When gelatin is used for the adhesive, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin can be used. Of these gelatins, lime-processed gelatin and acid-processed latin are preferably used. When gelatin is used as the adhesive, the preferred bridging agent is an active halogen compound (2, 4 dichloro 6 hydroxy-1, 3, 5 triazine and its sodium salt) and an active bur compound (1, 3). —Bisvinylsulfonanol 1-propanol, 1,2-bisvininolesnorephoninoacetamido) ethane, bis (vininole sulfonylmethyl) ether! / Is a bur system having a vinylsulfonyl group in the side chain Polymers), N-strength rubamoylpyridinium salts (such as (1—morpholinocarbonyl 3-pyridinio) methanesulphonate) and haloamidinium salts (1- (1-crodione 1-pyridinomethylene) pyrrolidinium 2 —Naphthalene sulfonate, etc.). In the present invention, active halogen compounds and active bur compounds are particularly preferably used.

[0176] When the above-mentioned crosslinking agent is used in combination, the preferred addition amount of the crosslinking agent is water solubility in the adhesive. It is 0.1% by mass or more and less than 40% by mass, and more preferably 0.5% by mass or more and less than 30% by mass with respect to the polymer. Apply an adhesive to at least one surface of the transparent protective film or polarizer to form an adhesive layer, and then apply the adhesive to the surface treatment surface of the transparent protective film It is preferable to form an adhesive layer and bond it to the surface of the polarizer. The thickness of the adhesive layer is preferably from 0 · 01 111 to 5 111 m after drying, and particularly preferably 0 · 05 ^ m−3〃m.

[0177] (Antireflection layer)

It is preferable to provide a functional film such as an antireflection layer on the transparent protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell. In the present invention, the functional film is formed on the cyclic polyolefin resin film of the present invention to form an optical film, which can be used as a polarizing plate. In particular, in the present invention, at least a light scattering layer and a low refractive index layer are stacked in this order on the transparent protective film, or a medium refractive index layer, a high refractive index layer, and a low refractive index layer are formed on the transparent protective film. An antireflection layer laminated in this order is preferably used. Preferred examples are described below. The antireflection layer may be provided on the cyclic polyolefin resin film of the present invention, or may be provided on a transparent protective film other than the cyclic polyolefin resin film of the present invention.

[0178] A preferred example of an antireflection layer in which a light scattering layer and a low refractive index layer are provided on a transparent protective film will be described. It is preferable that the matte particles are dispersed in the light scattering layer. The refractive index of the material other than the mat particles in the light scattering layer is preferably in the range of 1.50 to 2.00. The refractive index of the refractive index layer is preferably in the range of 1.35 to; 1.49. The light scattering layer may have both antiglare properties and hard coat properties, or may be composed of a single layer or a plurality of layers, for example, 2 to 4 layers.

[0179] The antireflection layer has an uneven surface shape, centerline average roughness Ra is 0.08 to 0.40 μm, 10-point average roughness Rz is less than 10 times Ra, and average mountain valley distance Sm is 1 ~; 100 m, the standard deviation of the height of the convex part from the deepest part of the concavo-convex is 0.5 111 or less, the standard deviation of the average mountain valley distance Sm based on the center line is 20 m or less, and the inclination angle is 0-5 Designing the surface to be 10% or more is preferable because sufficient antiglare property and visual uniform mat feeling can be achieved.

Also, the ratio of the minimum and maximum reflectances within the range of a * value 2 to 2, b * value 3 to 3, and 380 nm to 780 nm, under the light source C. By being 0.9, the reflected light The color becomes neutral, which is preferable. In addition, it is preferable that the b * value of the transmitted light under the C light source is 0 to 3 because the yellow color of white display when applied to a display device is reduced.

The standard deviation of the luminance distribution when the luminance distribution is measured on the film by inserting a grid of 120 mm × 111 mm × 40 mm between the surface light source and the antireflection film of the present invention is 20 or less. The glare when the film of the present invention is applied to a high-definition panel is preferably reduced.

[0180] The optical properties of the antireflection layer are such that the specular reflectance is 2.5% or less, the transmittance is 90% or more, and the 60 ° glossiness is 70% or less. Is preferable. In particular, the specular reflectance is more preferably 1% or less, and most preferably 0.5% or less. Haze 20% ~ 50%, internal haze / total haze value (ratio) is 0.3 ~; 1, haze value after formation of low refractive index layer from haze value to light scattering layer within 15%, On a high-definition LCD panel, the transmission image clarity is 20% to 50% at a comb width of 0.5 mm, and the transmittance ratio of the vertical transmitted light / at 2 degrees from the vertical is 1.5 to 5.0. This is preferable because it prevents glare and reduces blurring of characters.

[0181] (Low refractive index layer)

The refractive index of the low refractive index layer of the antireflective film is in the range of 1.20 to; 1.49 is more preferred than 1.30 to 1.44. Further, the low refractive index layer preferably satisfies the following mathematical formula from the viewpoint of low reflectance.

(/ 4) Χ 0.7 <nldl <(m l / 4) X I. 3

Where m is a positive odd number, nl is the refractive index of the low refractive index layer, and dl is the film thickness (nm) of the low refractive index layer. In addition, λ is a wavelength, which is a value in the range of 500 nm to 550 nm.

[0182] The material for forming the low refractive index layer is described below.

The low refractive index layer preferably contains a fluorine-containing polymer as a low refractive index binder. The fluorine polymer is preferably a fluorine-containing polymer which is crosslinked by heat or ionizing radiation having a coefficient of dynamic friction of 0.03-0.20, a contact angle with water of 90 ° to 120 °, and a sliding angle of pure water of 70 ° or less. When the optical film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a sticker or memo, preferably 500 gf or less, more preferably 300 gf or less. Most preferred is less than lOOgf. Also The higher the surface hardness measured with a microhardness meter, the harder it is to scratch, preferably 0.3 GPa or more, more preferably 0.5 GPa or more.

[0183] Hydrofluoric polymers used in the low refractive index layer include hydrolysis of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). In addition to the dehydration condensate, there may be mentioned a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as constituent components.

[0184] Specific examples of the fluorine-containing monomer include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoroethylene). 2, 2-dimethyl-1,3-dioxole, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (Osaka Organic Chemical) and M-2020 (Daikin)), complete or force as the partially fluorinated Bulle ethers ^s, preferably per full O Roo reflex ynes, refractive index, solubility, transparency, hexa to particularly preferred in view of availability and the like

[0185] As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups Monomers having a hydroxy group, amino group, sulfo group, etc. (eg (meth) acrylic acid, methylol (meth) acrylate, hydro

Alinorea Talelate.

, Hydroxybutyl butyl ether, maleic acid, crotonic acid, etc.), and structural units obtained by introducing a bridge reactive group such as (meth) acryloyl group into these structural units by polymer reaction ( For example, it can be introduced by a technique such as making acrylic acid chloride on the hydroxy group).

[0186] In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, from the viewpoint of solubility in a solvent, transparency of the film, etc., fluorine atoms should not be appropriately contained! / You can also There are no particular limitations on the monomer units that can be used in combination, such as olefins (ethylene, propylene, isoprene, butyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) — Ruhexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene derivatives (styrene, dibutylbenzene, butyltoluene, α-methylstyrene, etc.), Butyl ethers (such as methyl vinylenoatenore, ethinolevinoleatenore, cyclohexenolevininoreatenore), vinyl esters (such as butylacetate, butyrate propionate and butyrate), acrylamides (N-tert) -Butylacrylamide, N-cyclohexylacrylamide, etc.), metharylamides, acrylonitrile derivatives and the like. As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

[0187] (Light scattering layer)

The light scattering layer is generally formed for the purpose of contributing to the film a light diffusibility due to surface scattering and / or internal scattering and a hard coat property for improving the scratch resistance of the finer. Therefore, it generally contains a binder for imparting hard coat properties, mat particles for imparting light diffusibility, and inorganic fillers for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength as necessary. It is formed. The thickness of the light scattering layer is preferably from 1 am to 10 m from the viewpoint of imparting hard coat properties and suppressing the occurrence of curling and brittleness. Masi.

[0188] The binder of the light scattering layer is more preferably a polymer having a saturated hydrocarbon chain as the main chain, preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain. The binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as a main chain and a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable. In order to increase the refractive index of the non-polymer, at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom is included in the monomer structure. You can also choose to include.

[0189] Monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, butanediol). Rudi (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexane diathalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol propane tri (meta) ) Atarylate, trimethylol ethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol monopenta (meth) acrylate, dipentaerythritol hex (meth) acrylate, penta erythritol Hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, and modified ethylene oxide, butylbenzene and its derivatives (eg, 1,4-dibuluenebenzene, 4-vinylbenzoic acid 2-atarylloethyl ester, 1,4-dibulucyclohexanone, vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide Can be mentioned. Two or more of these monomers may be used in combination.

[0190] Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenenyl) sulfide, urnaphthalene, burenylsulfide, 4-methacryloxyphenyl 4'-methoxyphenylthioether, and the like. Can be mentioned. Two or more of these monomers may be used in combination.

[0191] Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

Yes

Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support after ionizing radiation or It can be hardened by a polymerization reaction by heat to form an antireflection film. As these photo radical initiators, known ones can be used.

[0192] The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with 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, matte particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionized. The antireflection film can be formed by curing by a polymerization reaction by radiation or heat.

[0193] Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and A cross-linked structure may be introduced into the binder polymer by reaction. Examples of crosslinkable functional groups include isocyanato groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.

These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

[0194] For the purpose of imparting antiglare properties, the light scattering layer has an average particle size larger than that of the filler particles from 1 am to 10 m, preferably 1.5 ^ 111-7.0 m, for example, It is preferable to contain inorganic compound particles or resin particles!

Specific examples of the mat particles include particles of inorganic compounds such as silica particles and TiO particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferred. The shape of the mat particles can be either spherical or irregular.

[0195] Two or more kinds of mat particles having different particle diameters may be used in combination. Anti-glare properties can be imparted with mat particles having a larger particle size, and different optical characteristics can be imparted with mat particles having a smaller particle size.

[0196] Further, as the particle size distribution of the mat particles, it is more preferable that the particle sizes of the particles most preferably monodisperse are closer to each other. For example, when a particle having a particle size 20% or more larger than the average particle size is defined as a coarse particle, the coarse particle The total content is preferably 1% or less of the total number of particles, more preferably 0.1% or less, and still more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and fine particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

[0197] The matte particles have a light scattering layer in which the amount of matte particles in the formed light scattering layer is preferably 10 mg / m ² to 1000 mg / m ² , more preferably 10011¾ / 111 ^{2 to} 70011¾ / 111 ^2. Contained in tongue layer. The particle size distribution of the matte particles is measured by the Coulter counter method, and the measured distribution is converted into a particle number distribution.

[0198] In order to increase the refractive index of the light scattering layer, in addition to the above mat particles, at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony is used. It is preferable to contain an inorganic filler having an average particle diameter of 0.2 m or less, preferably 0.1 l or less, more preferably 0.06 m or less. Conversely, in order to increase the difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the light scattering layer using the high refractive index mat particles low. Sile,. The preferred particle size is the same as that of the inorganic filler described above.

Specific examples of the inorganic filler used in the light scattering layer include TiO, ZrO, Al 2 O, In 2 O 3, ZnO, SnO, Sb 2 O, ITO, and SiO. TiO and ZrO are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to silane coupling treatment or titanium force coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used. The amount of these inorganic fillers added is preferably 10% to 90% of the total mass of the light scattering layer, more preferably 20% to 80%, and particularly preferably 30% to 75%. . Such a filler does not scatter because the particle diameter is sufficiently smaller than the wavelength of light, and the dispersion in which the filler is dispersed in the binder polymer behaves as an optically uniform substance.

[0199] The refractive index of Balta of the mixture of binder and inorganic filler in the light scattering layer is 1.48 ~

More preferably, it is 1.00, more preferably 1.50-1.80. In order to make the refractive index within the above range, the type and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance. [0200] In order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc., the light scattering layer is formed by forming either a fluorine-based surfactant or a silicone-based surfactant, or both. It is preferable to contain it in the coating composition. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears at a smaller addition amount. The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity.

[0201] Next, an antireflection layer in which a middle refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order on a transparent protective film will be described.

An antireflection film comprising a layer structure of at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the substrate is designed to have a refractive index satisfying the following relationship: This is preferred. The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer. Further, a hard coat layer may be provided between the transparent support and the medium refractive index layer. Further, it may comprise a medium refractive index hard coat layer, a high refractive index layer, and a low refractive index layer (for example, JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP 2002-243906 A, JP 2000-111706 A, etc.). Further, other functions may be given to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (eg, JP-A-10-206603, JP 2002-2439 06 publication).

The haze of the antireflection layer is preferably 5% or less, more preferably 3% or less. The strength of the film is most preferably 2H or higher, more preferably 3H or higher, more preferably H or higher in the pencil hardness test according to JIS K5400.

[0202] (High refractive index layer and medium refractive index layer)

The layer having a high refractive index of the antireflection film is preferably composed of a curable film containing at least an ultrafine organic compound particle having a high refractive index having an average particle size of lOOnm or less and a matrix binder.

Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1 · 9 or more. Examples include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms. It is.

In order to obtain such ultrafine particles, the surface of the particles is treated with a surface treatment agent (for example, silane coupling agents, etc .: JP-A-11-295503, JP-A-11-153703, JP2000-9908). , Anionic compounds or organometallic coupling agents: JP 2001-310432 A, etc., core-shell structure with high refractive index particles as a core (JP 2001 1661042001-310432 JP, etc.), specific (For example, JP-A-11 1537 03, A report, US Patent No. 6210858, JP-A-2002-2776069 report A, etc.).

[0203] Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films.

Further, a composition containing a polyfunctional compound having at least two radically polymerizable and / or cationically polymerizable groups, an organometallic compound having a hydrolyzable group, and a partial condensate thereof. At least one composition selected from the above is preferred. Examples thereof include the compositions described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, 2001-296401, and the like.

A curable film obtained from a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred. For example, JP 2001-29381 A

It is described in No. 8 publication.

[0204] The refractive index of the high refractive index layer is generally 1.70-2.20. The thickness of the high refractive index layer is 5n

It is more preferable that it is 111-10111, and it is further more preferable that it is lOnml ^ m. The refractive index of the middle 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. The refractive index of the medium refractive index layer is preferably 1.50 to 1.70. The thickness is preferably 51 111 to 10111, more preferably lOnm l ^ um.

[0205] (Low refractive index layer)

In the above configuration, the low refractive index layer is sequentially laminated on the high refractive index layer. The refractive index of the low refractive index layer is preferably 1.20-1.55, more preferably 1.30-1.50.

It is preferable to construct as the outermost layer having scratch resistance and antifouling property. Great scratch resistance It is effective to impart slipperiness to the surface as a means for improving, and a conventionally known thin film means comprising introduction of silicone, introduction of fluorine or the like can be applied.

The refractive index of the fluorine-containing compound is 1.35-1.50. More preferably, it is 1.36-1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing a fluorine atom in a range of 35 to 80% by mass. For example, paragraph numbers [0018] to [0026] of JP-A-9 22 2503, paragraph numbers [0019] to [0030] of JP-A-11 38202, paragraph numbers of JP-A-2001-40284 [0027] to [0028], and compounds described in JP-A No. 2000-284102.

The silicone compound is a compound having a polysiloxane structure, and preferably contains a curable functional group or a polymerizable functional group in the polymer chain and has a crosslinked structure in the film. For example, reactive silicone (eg, manufactured by Silaplane Gesso Co., Ltd.), silanol group-containing polysiloxane (Japanese Patent Laid-Open No. 11-258403, etc.) at both ends, etc.

[0206] Crosslinking or polymerization reaction of a fluorine-containing and / or siloxane polymer having a crosslinkable or polymerizable group is performed by applying a coating composition for forming an outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating at the same time or after coating.

Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.

For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, JP-A-9-157582, 11-106704, etc.), silyl compounds containing poly (perfluoroalkyl ether) groups, which are fluorine-containing long-chain groups (JP 2000-117902 A, 2001-48590) Gazette, 2002-53804, etc.).

[0207] The low-refractive index layer is a primary particle flat such as a filler (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. Low-refractive index inorganic compound having a uniform diameter of lnm to 150 nm, organic fine particles described in paragraph Nos. [0020] to [0038] of JP-A-11 3820), silane coupling agent, slip agent, surfactant Etc. can be contained.

When the low refractive index layer is located in the lower layer of the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost. The film thickness of the low refractive index layer is preferably 30 nm to 2 OO nm, more preferably 50 nm to 150 nm, and most preferably 60 nm to l 20 nm! /.

[0208] (Other layers)

Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer or a protective layer may be provided.

[0209] (Hard coat layer)

The hard coat layer is usually provided on the surface of the transparent support in order to impart physical strength to the transparent protective film. In particular, when the antireflection layer is provided, the hard coat layer is preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.

Specific examples of these compounds are the same as those exemplified for the high refractive index layer. Specific examples of the constituent composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.

The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to form fine particles dispersed in the hard coat layer using the method described for the high refractive index layer.

The hard coat layer can also serve as an anti-glare layer (described later) provided with particles having an average particle size of 0.2 m to 10 m to provide an anti-glare function (anti-glare function).

The film thickness of the hard coat layer can be appropriately designed depending on the application. Hard coat layer The film thickness is preferably 0.2 μm to 10 μm, and more preferably 0.5 μm to 7 μm.

The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, most preferably 3H or higher, in a pencil hardness test according to JIS K5400. In addition, in the Taber test according to JIS K5400, it is preferable that the wear amount of the test piece before and after the test is small.

[0210] (Antistatic layer)

Rukoto force to impart conductivity of the volume resistivity of 10- ⁸ Ω cm- ³ or less in the case of providing an antistatic layer S preferred. Hygroscopic substance, a water-soluble inorganic salts, certain surfactants, cationic poly-mers, § anion polymer, although imparting a volume resistivity of 10- ⁸ Ω cm- ³ by the use of such colloidal silica is possible, temperature There is a problem that sufficient conductivity cannot be secured at low humidity, which is highly dependent on humidity. Therefore, a metal oxide is preferable as the conductive layer material. It is preferable to use a metal oxide that is colored! /, N! /, As the conductive layer material, since the coloring of the entire film is suppressed. Zn, Ti, Al, In, Si, Mg, Ba, Mo, W, or V can be cited as the metal that forms a metal oxide without coloration. The ability to use a metal oxide based on this metal oxide S is preferred. Specific examples include ZnO, TiO, SnO, AlO, InO, SiO, MgO, BaO, MoO, VO, etc.

TiO and SnO are preferred. Examples of containing different atoms include, for example, additives such as A1 and In for ZnO, addition of Sb, Nb, halogen elements, etc. for SnO, and addition of Nb, TA, etc. for TiO. Is effective. Furthermore, a material obtained by adhering the above metal oxide to other crystalline metal particles or fibrous materials (for example, titanium oxide) as described in JP-B-59-6235 may be used. The volume resistivity and surface resistivity can not be simply compared is another physical property values, in order to ensure 10_ ⁸ Q cm_ ³ less conductive volume resistivity, the conductive layer is generally and have a 10- ^1Q Ω / mouth below the surface resistance value! /, more preferably it may be that is 10_ ⁸ Ω / □ or less. The surface resistance value of the conductive layer needs to be measured as a value when the antistatic layer is the outermost layer, and can be measured in the middle of forming the laminated film described in the above publication.

[0211] (Liquid crystal display device) The cyclic polyolefin resin film of the present invention, an optical film comprising the film, and a polarizing plate using the film can be used for liquid crystal cells and liquid crystal display devices in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal) AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned) and Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. Of these, the power S is preferred for OCB mode or VA mode.

[0212] The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is. The OCB mode liquid crystal cell is disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also called OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device, there is advantage force ^s that the response speed is fast.

[0213] In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

The VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. (2) Liquid crystal cell (SID97, Digest of tech. Papers) (Preliminary report) 28 (1997) 845 (3) A liquid crystal cell (n—ASM mode) in which rod-like liquid crystalline molecules are aligned vertically when no voltage is applied, and twisted multi-domain alignment is applied when a voltage is applied. -59 (1998)) and (4) SURV AIVAL mode liquid crystal cells (announced at LCD International 98).

The VA mode liquid crystal display device includes a liquid crystal cell and two polarizing plates arranged on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates. Liquid of the present invention In one embodiment of the crystal display device, one retardation film of the present invention is disposed between the liquid crystal cell and one polarizing plate, or two sheets are disposed between the liquid crystal cell and both polarizing plates. .

As described above, in the liquid crystal display device of the present invention, the optical film made of the cyclic polyolefin resin film of the present invention can be used as the transparent protective film of the polarizing plate disposed between the liquid crystal cell and the polarizer. . The above optical film may be used only for the transparent protective film (between the liquid crystal cell and the polarizer) of one polarizing plate, or the two polarizing plates (between the liquid crystal cell and the polarizer) of both polarizing plates. You may use said optical film for a transparent protective film of a sheet. When the above optical film is used only for one polarizing plate, it is particularly preferable to use it as a liquid crystal cell side transparent protective film of a backlight side polarizing plate of a liquid crystal cell. For the lamination to the liquid crystal cell, the cyclic polyolefin resin film of the present invention is preferably on the liquid crystal cell side. The other transparent protective film may be a normal cell acrylate film. For example, a commercially available KC4UX2M (40 μm manufactured by Konica Caputo Co., Ltd.), KC5UX (60 H m manufactured by Konica Caputo Co., Ltd.), TD80 (80 m manufactured by Fuji Photo Film Co., Ltd.) is preferred. ) And the like, but is not limited thereto.

[0214] (Optical compensation film)

In OCB mode liquid crystal display devices and TN liquid crystal display devices, optical compensation films are used to expand the viewing angle. The optical compensation film for the OCB cell is provided with an optically anisotropic layer in which a discotic liquid crystal is hybrid-aligned and fixed on an optically uniaxial or biaxial film. As the optical compensation film for TN cell, a film in which an optical anisotropic layer in which a discotic liquid crystal is fixed in a hybrid orientation is fixed on a film having an optical isotropy or an optical axis in the thickness direction. The cyclic polyolefin resin film of the present invention is useful for producing the optical compensation film for OCB cell and TN cell.

The preferred letter value of the optical compensation film is as described above. Example

[0215] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. [0216] <Synthesis of Cyclic Polyolefin Polymer PP-1>

100 parts by mass of purified toluene and 100 parts by mass of norbornenecarboxylic acid methyl ester were charged into the reaction kettle. Next, ethyl hexanoethyl ether dissolved in toluene, Ni 25 mmol% (based on monomer mass), tri (pentafluorophenyleno) boron 0.225 mol% (based on monomer mass) and triethyl aluminum dissolved in toluene 0.25 mol% (based on Monomer mass) was charged into the reaction kettle. The reaction was allowed to proceed for 18 hours at room temperature with stirring. After completion of the reaction, the reaction mixture was put into excess ethanol to produce a polymer precipitate. The polymer (PP-1) obtained by purifying the precipitate was vacuum dried at 65 ° C. for 24 hours.

[Example 1]

Polymer PP- 1 30 mass ^_0/0 methylene chloride 64.4 mass ^_0/0 Metanonore 5.4 mass ^_0/0 Water 0.2 wt%

[0218] Dope A-1 was prepared by dissolving and filtering the polymer solution having the above composition by the high-temperature dissolution method described in Japanese Unexamined Patent Publication No. 2001-1745.

[0219] <Dope B l>

The following substances were further added to the composition of Dope A-1A, and the solid content was diluted to 28.5 mass%.

Silicon oxide matting agent (primary particle size 20nm) 0.1% by mass

[0220] A polymer solution having the above composition was dissolved and filtered by a high-temperature dissolution method described in Japanese Unexamined Patent Publication No. 2001-1745 to prepare Dope B-1.

[0221] <Viscoelastic properties of Dope A-1>

The viscoelastic properties of Dope A-1 were measured at a frequency of 1Ηζ and a strain of 1%. At a temperature of 5 ° C, the storage elastic modulus E 'was 510Pa, the loss elastic modulus E''was 990Pa, and the temperature was 40 ° C. 400Pa, E '' force was 060Pa. Also, measure the temperature dependence of E ', E', -50 ° C ~; 10 ° C, E '= A * exp (_B * T), E''= C * exp (_D * T) (A to D: Constant, T represents temperature) Constant B is 0.0420, D is 0.0250, 50 ° C to 10 ° C, around 5 ° C Then E 'is a smaller value than E''. At around 40 ° C, E' showed a larger value than E ''.

[0222] <Manufacture of Finorem>

As the casting die, a multi-hold type coat hanger type is used, and as the casting support, a hard chrome plating is applied, and the diameter is mirror-finished so that the central average roughness becomes 0.03. A rotating drum with a width of 2000 mm and a width of 2500 mm was used. The rotating drum passed water inside the rotating drum to maintain the average surface temperature at 40 ° C, and the temperature distribution on the rotating drum surface at this time was within 5 ° C.

[0223] Then, the dope A-1 was co-cast so that a core layer having a thickness of 70 m after drying and the dope B-1 each forming a double-layered outer layer having a thickness of 5 m after drying were formed.

[0224] The cast Dope A-1 and Dope B-1 dried for 1 second immediately after casting at a wind speed of 0.5 m / s or less, and thereafter, the wind speed was 15 m facing the drum rotation direction. Dry at / s. The temperature of the drying air was 50 ° C.

[0225] The residual solvent amount of the film when peeled off the rotary drum is 250 mass ^_0/0, the temperature of the film was 6 ° C. The average drying rate from casting to stripping was 730% by mass / min.

[0226] The peeled film was transported to a pin tenter by a pass roller whose surface temperature was adjusted to 5 ° C through the coolant, and both ends (thickness 70 μm) were supported by the pin tenter. Drying and conveyance were performed while applying tension. Three stripped pass rollers were used, and all were placed so as to wrap on the opposite side of the film. In addition, these pass rollers can be set to draw ratios from 0.5 to 15% with respect to the drum rotation speed, and were operated at draw ratios of 1%, 2%, and 4%, respectively. The lap angle was set to 5 degrees or less. The distance from the stripping to the pintenter crease was 1.2 m.

[0227] When the film was supported by a pin tantalator and stretched by 10%, the temperature of the pin tenter was 25 ° C, the temperature of the supported film was 5 ° C, and most of the residual solvent in the film was It was methylene chloride. The saturation temperature of the gas in the drying zone was 15 ° C and the oxygen concentration was 6%.

[0228] The temperature of the drying air is 120 ° C, the temperature distribution in the width direction of the film is 5 ° C or less, the average wind speed of drying is 5m / s, and the average value of the heat transfer coefficient is 25kcal / m ² 'Hr' ° C The distribution in the width direction of the film was all within 5%. In addition, the pintainer carrying part in the drying zone was prevented from being directly exposed to hot dry air by a wind shield. In order to maintain the flatness of the film, the film during conveyance of the pin tenter was dried while maintaining the tension in the width direction at 98 N / m (10 kg / m).

[0229] Further, the pin tenter was cooled at a total heat transfer coefficient of 150 kcal / m ² .Hr '° C with cooling air of 5 ° C until the film was newly loaded after the film was detached. The length of the part cooled by the cooling device was 50% of the total.

[0230] The time to be supported and dried by the pin tenter was 10 minutes, and during that time the amount of solvent evaporated was 97% of the total amount of solvent evaporated between stripping and winding. The evaporated solvent was condensed and recovered by a condenser, and this recovered solvent was dehydrated by distillation to a water content of 0.4%, and then used again as a raw material for the dope preparation process.

[0231] The film dried with a pin tenter is further dried for 15 minutes with a drying air of 145 ° C in a drying process in which the film is transported by a roller, and the residual solvent amount at the time of winding is adjusted by adjusting the humidity and temperature. It was wound up at 50% by mass, a moisture content of 0.7% by mass and a temperature of 35 ° C. The conveyance tension in the drying zone was 20 to 150 N / m, and the absolute value of the charge amount of the film was kept below 3 kV. The solvent gas concentration in the drying zone was 20% or less of the lower limit of solvent explosion, and the dew point of high-boiling components other than the solvent was 80 ° C or higher.

[0232] The film produced by the method as described above was able to be stably conveyed without problems such as slippage in the drying process after peeling off from the casting die. In addition, the flatness and transparency of the wound film were good, and Re was 55 nm and Rth was 200 nm.

Yes

[0233] [Comparative Example 1]

The composition of the dope A-1 in Example 1 was changed to the following.

Polymer PP- 1 25 wt% methylene chloride 75 mass ^_0/0

[0234] <Viscoelastic properties of Dope A-2>

The viscoelastic properties of Dope A-2 were measured at a frequency of 1Ηζ and a strain of 1%. The storage elastic modulus E 'was 500 Pa, the loss elastic modulus E''was 900 Pa, the temperature was 50 ° C, the E' force was 900 Pa, and the E '' force was 200 Pa. Measure the temperature dependence of E ', E', -50 ° C ~; 10 ° C, E '= A * exp (B * T), E''= C * exp (— D * T ) (A to D: constant, T represents temperature), constant B is 0 · 22020, D is 0.0210, and is always within the temperature range of 50 ° C to 10 ° C. E 'force showed a smaller value.

[0235] When cast and dried under the same conditions as in Example 1, the film could not be peeled from the rotating drum. This is due to the fact that it always shows a smaller value than the E 'force, which is the viscoelastic property of Dope A-2, and it was not self-supporting.

[0236] [Comparative Example 2]

Polymer PP- 1 55 wt% methylene chloride 45 mass ^_0/0

[0237] <Viscoelastic properties of Dope A-3>

When the viscoelastic properties of Dope A-3 were measured at a frequency of 1Ηζ and a strain of 1%, the storage elastic modulus E 'was 600 Pa at a temperature of 5 ° C, the loss elastic modulus E' 'was 1000 Pa, and E' was 50 ° C. 2000Pa, E '' was 3400Pa. Also, measure the temperature dependence of E ', E', -50 ° C ~; 10 ° C, E '= A * exp (— B * T), E' '= 1 * 6 (-0 * (8 to 0: constant, T represents temperature), constant Βί or 0.0240, D (or 0.0205, 50. C to 10) within the temperature range of C ( Normally ίE E 'showed a smaller value than E' '.

[0238] When the film was cast and dried under the same conditions as in Example 1, the film could not be peeled from the rotating drum. This is due to the fact that E ', which is the viscoelastic property of Dope A 3, always shows a smaller value than E' ', as with Dope Α 2, and was not self-supporting. Become.

[Example 2]

Polymer PP- 1 30 mass ^_0/0 methylene 61 mass chloride ^_0/0 methanol 8.2 mass ^_0/0 [0240] Dope A-4 was prepared by dissolving and filtering the polymer solution having the above composition by the high-temperature dissolution method described in Japanese Unexamined Patent Publication No. 2001-1745.

[0241] <Dope B— 2>

The following substances were further added to the composition of Dope A-4, and the solid content was diluted to 28.5% by mass.

Silicon oxide matting agent (primary particle system 20nm) 0.1% by mass

[0242] Dope B-2 was prepared by dissolving and filtering the polymer solution having the above composition by a high-temperature dissolution method described in JP-A-2001-1745.

[0243] <Viscoelastic properties of dope A-4>

When the viscoelastic properties of Dope A-4 were measured at a frequency of 1Ηζ and a strain of 1%, the storage elastic modulus E 'was 250Pa at a temperature of 5 ° C, the loss elastic modulus E' 'was 510Pa, and E' was 15 ° C. 860Pa, E '' was 660Pa. Also, measure the temperature dependence of E ', E' '— 50 ° C ~; 10 ° C, E' = A * exp (— B * T), E '' = C * exp (— D * T) (A to D: constant, T represents temperature), constant B is 0 · 0598, D is 0.0120, 50 ° C ~; within 10 ° C, 5 ° Near C, E 'had a smaller force S than E' ', and around –15 ° C E' showed a larger value than E ''.

[0244] <Film production>

Dope A-4 and Dope B-2 were cast and dried under the same conditions as in Example 1 except that the average surface temperature of the rotating drum was set to 15 ° C. At this time, the temperature distribution on the rotating drum surface was within 2 ° C.

[0245] At this time, when the film was peeled off from the rotating drum, the residual solvent amount of the film was 240% by mass, and the temperature of the film was 5 ° C. The average drying rate from casting to stripping was 740% by mass / min. Residual solvent amount (%) = ((film weight before drying) (film weight after drying)) / (film weight after drying) X 100 However, the above drying conditions are 120 ° C for 2 hours. Use an ordinary precision balance for mass measurement.

[0246] In this example, it was possible to convey stably without problems such as slippage. Further, the flatness and transparency of the wound film were good. Re 56nm, Rth force 90nm Met. The average value of the slow axis angle in the film width direction was 0.2 degree, and the standard deviation of the slow axis variation was as small as 0.4 degree. This is probably because the temperature distribution on the surface of the rotating drum was narrowed to within 2 ° C by setting the rotating drum temperature to -15 ° C compared to Example 1, and as a result, the axial variation in the film surface was reduced. Compared with Example 1, Example 2 was able to raise the temperature of the rotating drum, and it was possible to produce a film with high productivity and low environmental impact.

[0247] [Evaluation of film surface]

When peeling a dry film from a metal support, the peeling resistance (peeling load) is large, and the film is irregularly stretched in the direction of film formation, resulting in optical anisotropy unevenness (stripping step unevenness). In order to evaluate this, a sample was inserted between the polarizing plates arranged in crossed Nicols parallel or at 45 degrees to the absorption axis of the polarizing plate, and visually evaluated according to the following criteria. The results are shown in Table 1.

A: The film surface is smooth.

A: The film surface is smooth. Very weak and irregularities are observed.

Δ: Weak unevenness is observed on the film surface, but it may be usable depending on the application. X: Unevenness is seen on the film surface and it is difficult to use as an optical film.

[0248] [Table 1] Table 1

[0249] (Preparation of polarizing plate)

A polarizer was prepared by adsorbing iodine to a stretched polybulal alcohol film. Fruit The cyclic polyolefin resin film produced in Example 2 was subjected to a glow discharge treatment (frequency 3000 Hz, high frequency voltage of 4200 V applied between upper and lower electrodes, treatment for 20 seconds), and a commercially available 80 am cellulose triacetate film ( TD80UF) was subjected to the following hatching treatment, and then adhered to both sides of the polarizer using a polybulal alcohol adhesive, and dried at 70 ° C. for 10 minutes or more to produce polarizing plate A. The hatching treatment conditions were as follows.

1. A 5N aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.1N dilute sulfuric acid solution was prepared and kept at 35 ° C. TD80UF was immersed in the above aqueous sodium hydroxide solution for 2 minutes and then immersed in water to thoroughly wash away the aqueous sodium hydroxide solution. Finally, the sample was thoroughly dried at 120 ° C. The produced polarizing plate A is obtained by attaching the cyclic polyolefin resin film prepared in Example 2 on one side of the polarizer and a commercially available cellulose triacetate film (TD80UF) on the other side. The transmission axis of the polarizer and the slow axis of the cyclic polyolefin resin film prepared in Example 2 were arranged in parallel. The transmission axis of the polarizer and the slow axis of TD80UF were arranged so as to be orthogonal.

[0250] <Production of VA liquid crystal cell>

The liquid crystal cell has a cell gap between substrates of 3.6 m, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. This was prepared by forming a liquid crystal layer. The letter layer of the liquid crystal layer (ie, the product of the liquid crystal layer thickness dm) and the refractive index anisotropy Δη was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned. A commercially available super high contrast product (for example, HLC2-5618 manufactured by Sanlitz Co., Ltd.) was used on the upper side (observer side) of the vertical alignment type liquid crystal cell. The prepared polarizing plate A was attached to the lower side (backlight side) of the liquid crystal cell via an adhesive so that the cyclic polyolefin resin film was on the liquid crystal cell side. The crossed Nicols were arranged so that the transmission axis of the upper polarizing plate was in the vertical direction and the transmission axis of the lower polarizing plate was in the horizontal direction.

As a result of observing the manufactured liquid crystal display device, neutral black display in both the front direction and the viewing angle direction could be realized in all gradations. Even after the environmental humidity was changed, the display along the image was not uneven and was good.

[0251] The following materials, amounts used, ratios, processing details, processing procedures, etc. depart from the spirit of the present invention. As long as it is not, it can be changed appropriately. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0252] (Example 3)

200 parts by mass of purified toluene and 96 parts by mass of 5-norbornene-2-yl acetate were charged into the reaction kettle. Next, palladium (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 · 03 parts by mass, tricyclohexylphosphine (manufactured by STRE M) 0 · 03 parts by mass and dimethyl dissolved in 10 parts by mass of methylene chloride 0.17 parts by mass of aluminum tetrakis (pentafluorophenylene) borate (manufactured by STREM) was charged into the reaction kettle. The reaction was allowed to proceed for 18 hours while stirring at 90 ° C. After completion of the reaction, the reaction mixture was poured into excess methanol to generate a precipitate of the polymer. The polymer (P-1) obtained by purifying the precipitate was dried at 110 ° C. for 8 hours by vacuum drying.

The obtained polymer was dissolved in tetrahydrofuran, and the molecular weight was measured by gel permeation chromatography. The number average molecular weight in terms of polystyrene was 68,500, and the weight average molecular weight was 212,000.

[0253] To a 3 L separable flask containing 100 parts by mass of THF, 10 parts by mass of P-1 was added and stirred for a while to dissolve uniformly. Next, an aqueous KOH solution in which 0.8 parts by mass of potassium hydroxide was dissolved in 0.5 parts by mass of water was prepared and dropped into the stirred homogeneous solution. Thereafter, the internal temperature was raised to 65 ° C. and stirred for 2 hours, and then the reaction solution was put into 700 parts by mass of methanol to precipitate a polymer. Furthermore, it was purified by continuous washing with 40-50 ° C water and methanol. After filtration, it was vacuum-dried to obtain 9 parts by mass of the cyclic olefin copolymer P-2 of the present invention.

[0254] [Chemical 20]

[0255] The resulting P- 2, from the infrared absorption spectrum, it was found that 10 mole ^_0/0 of the repeating units are those which are hydrolyzed. The obtained polymer was dissolved in tetrahydrofuran and the molecular weight was measured by gel permeation chromatography. The number average molecular weight in terms of polystyrene was 68,000, and the weight average molecular weight was 212,000.

[0256] <Film production>

In the same manner as in Example 2, except that the polymer PP-1 in Example 2 was changed to P-2, the dope was

It was cast and dried in the same manner as in Example 2 except that A-4 and Dope B-2 were adjusted and the surface average temperature of the rotating drum was changed to -10 ° C.

[Example 4]

200 parts by weight of purified tonorene, 77.6 parts by weight of 5 norbornene-2-yl acetate, and 13.9 parts by weight of 5 norbornene-2 methanol were charged into the reaction kettle. Next, palladium (II) acetylylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 10 parts by mass of methyl chloride 0.03 parts by mass, tricyclohexylphosphine (manufactured by STREM) 0.03 parts by mass, Further, 0.17 parts by mass of dimethylaluminum tetrakis (pentafluorophenyl) borate (manufactured by STREM) was charged into the reaction kettle. The reaction was allowed to proceed for 18 hours with stirring at 90 ° C. After completion of the reaction, the reaction mixture was poured into excess methanol to form a polymer precipitate. The polymer (P-3) obtained by purifying the precipitate was dried at 110 ° C. for 8 hours by vacuum drying.

[Examples 5-8, Comparative Examples 3-7]

In the same manner as in the above method P-2, except that the monomer corresponding to the target polymer was appropriately selected and that the amounts of potassium hydroxide and water were appropriately changed during the hydrolysis treatment, the table was obtained. Polymers of Examples 5 to 8 and Comparative Examples 6 and 7 shown in 2 were obtained. In addition, the polymer used for Comparative Examples 3-5 is not hydrolyzed.

The polymers of Examples 4 to 8 and Comparative Example shown in Table 2 were dissolved in a methyl chloride / methanol mixed solvent having the composition shown in Example 2. However, the polymer of Comparative Example 6 in which y in the general formula (1) was 57 was insoluble in this mixed solvent.

Subsequently, the solutions of Examples 4 to 8 and Comparative Examples 3 to 5 and 7 were cast using a drum casting machine in the same manner as in Example 2. At this time, the surface temperature of the drum was kept at the support temperature shown in Table 2.

Yes [0260] [Evaluation of peelability]

◯: The film could be peeled off from the support without any film residue. X: When the film was to be peeled off from the support, the film remained unremoved partially or entirely on the support, and the film could not be peeled cleanly.

The evaluation results are shown in Table 2 together with the results of Example 3.

[0261] [Table 2]

As can be seen, when the film is peeled from the drum, the copolymer composition is 50≤x≤ When a cyclic polyolefin polymer with 99 and l≤y≤50 was used and the support temperature was 10 ° C or lower (Examples 3 to 8), it could be removed without any problem. On the other hand, in Comparative Examples 3 to 5, the support temperature is 10. Even when the film is C or less, when the film is peeled off from the support, the film is agglomerated and broken, and a part of the film remains on the support, and the film cannot be peeled cleanly from the support. The desired film could not be obtained. Further, even when a cyclic polyolefin polymer having a copolymer composition of 50≤x≤99 and l≤y≤50 is used, the support temperature is 10. Similarly, when it is not less than C (Comparative Example 7), when the film is peeled off from the support, the film may cause cohesive failure, and a part of the film may remain on the support. The desired film could not be obtained.

[0263] (Example 9; 1 ^2: stretching)

The film obtained in Examples 4, 5, 6, and 7 was heated to 220 using an automatic stretching machine manufactured by Imoto Seisakusho. In C, 20% fixed-end stretching was performed to obtain a stretched film. The letter decision at a wavelength of 590 nm was measured. The thickness of the film was measured at three points on any part using a digital micrometer, and the average value d was taken. From this, Re and Rth of a film thickness of 80 Hm were obtained by the following formula. The results are shown in Table 3.

Re = measured Re / d X 80

Rth = measured Rth / d X 80

[0264] [Table 3]

(Example 13: Production and evaluation of polarizing plate)

Examples 9 to; Films Fl to F3 prepared in 11 and Fuji TAC (manufactured by Fuji Film Co., Ltd.) were immersed in an aqueous solution of sodium hydroxide 1.5N at 60 ° C. for 2 minutes. Thereafter, it was immersed in a 0.1N aqueous sulfuric acid solution for 30 seconds, and then passed through a water-washing bath and hatched. [0266] According to Example 1 of Japanese Patent Laid-Open No. 2001-141926, a peripheral speed difference was given between two pairs of nip rolls to obtain a polybulal alcohol film "9X75RS" {manufactured by Kuraray Co., Ltd.} having a thickness of 75 111, The film was stretched in the longitudinal direction to obtain a polarizing film.

[0267] The polarizing film thus obtained and the hatched F1 to F3 were mixed with PVA "PVA-117H" (manufactured by Kuraray Co., Ltd.) using a 3 mass% aqueous solution as an adhesive, and the longitudinal direction of the film was 45 °. Thus, polarizing plates Pol ;! to 3 were prepared by laminating together with a layer configuration of “F1-F3 / Polarized film / Fuji TAC after incubation”. The shells were in good condition and there was no sledge after drying.

[Example 14: Production and evaluation of liquid crystal display device]

Among two pairs of polarizing plates installed with a liquid crystal layer sandwiched between 26-inch and 40-inch liquid crystal display devices (manufactured by Sharp Corporation) using VA type liquid crystal cells, a polarizing plate on one side on the viewer side is used. It peeled off and the adhesive was used, and the said polarizing plate Pol-;! ~ 3 was stuck instead. A liquid crystal display device was manufactured by arranging the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side to be orthogonal to each other. The film of the present invention was placed on the viewer side. Color unevenness of the obtained liquid crystal display device was observed. The liquid crystal display device incorporating the polarizing plate Pol— ;! to 3 of the present invention was very excellent with no color unevenness.

[0269] Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. It is.

This application is based on a Japanese patent application filed on September 29, 2006 (Japanese Patent Application 2006-269810) and a Japanese patent application filed on April 27, 2007 (Japanese Patent Application 2007-119852). Incorporated herein by reference.

Claims

The scope of the claims

[1] A film in which a cyclic polyolefin resin resin solution containing at least 10 to 50% by mass of a resin composition containing at least a cyclic polyolefin resin is cast on an endless support and peeled to form a film. The cyclic polyolefin resin film is characterized in that the cyclic polyolefin resin film reaches the gel point before being peeled off after being cast on an endless support.

[2] The cyclic polyolefin resin solution force and the temperature dependence of E ′ and E ′ ′ are expressed as E ′ = A * exp (—B * T), E ′, = C * exp (—D * T) [ Wherein A to D are constants, and T is temperature (° C)], the relationship 0≤D <B is satisfied. Resin film.

[3] The cyclic polyolefin resin film according to claim 1 or 2, wherein the solvent in the cyclic polyolefin resin solution contains 4 to 20% by mass of a poor solvent.

[4] The cyclic polyolefin resin solution is continuously cast on an endless support, and then the formed film is peeled off from the endless support, and the peeled film is dried and wound up. The cyclic polyolefin resin film according to claim 1 or 2, wherein the temperature of the endless support is set to 150 ° C to 10 ° C.

[5] When the cooling rate from when the cyclic polyolefin-based resin solution is cast on the endless support to peeling is expressed as (temperature difference / hour), 3 to 5 (° C / sec) The cyclic polyolefin resin film according to claim 4, wherein:

[6] The cyclic polyolefin resin film according to [4] or [5], wherein the film is stretched during drying until the film is wound after being peeled from the endless support.

[7] A polarizing plate having a transparent protective film on both sides of a polarizer, wherein at least one of the transparent protective films is the cyclic polyolefin resin film according to any one of claims 1 to 6. A polarizing plate.

8. The polarizing plate according to claim 7, wherein at least one of a hard coat layer and an antireflection layer is provided on the surface of one transparent protective film of the polarizer.

[9] The cyclic polyolefin resin film according to any one of claims 1 to 6 and claim

A liquid crystal display device comprising any one of the polarizing plates according to 7 or 8.

[10] An OCB or VA mode liquid crystal display device, wherein the polarizing plate according to claim 7 or 8 is used on at least one of upper and lower sides of a liquid crystal cell.

[11] A VA mode liquid crystal display device comprising the polarizing plate according to claim 7 or 8 on a backlight side.

[12] A method for producing a cyclic polyolefin resin film in which a cyclic polyolefin resin solution is formed by solution casting, wherein the gelation point is reached after casting on an endless support until peeling. A cyclic polyolefin resin solution having viscoelastic properties to reach an endless support of a casting machine adjusted to 50 ° C. to 10 ° C., and the cyclic polyolefin resin solution is the endless support The cyclic polyolefin resin film is characterized in that the cooling rate from casting to peeling is 3 to 5 (° C / sec) in terms of (temperature difference / hour). Production method.

[13] Before casting the cyclic polyolefin resin solution on an endless support of a casting machine, 4 to 20% by mass of a poor solvent is added to the solvent in the cyclic polyolefin resin solution. Item 13. A method for producing a cyclic polyolefin resin film according to Item 12.