JP2003231141A - Method for producing polycarbonate resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polycarbonate resin film which is good in dimensional stability and excellent in surface properties. <P>SOLUTION: The method for producing the polycarbonate resin film uses a polycarbonate resin solution, containing 10 to 40 mass % of a polycarbonate resin of a glass transition temperature (Tg) of 150°C or higher which is obtained by copolymerizing at least a fluorene framed bisphenol derivative and at least a non-fluorene framed bisphenol derivative, and having a flow casting viscosity of 10 to 200 Pa.s. The method comprises, a process to filter the resin solution at least once by a filter having average pore size of 1 to 50 μm, a flow casting process to form a web by flow casting the above solution on a metal backing, a process to remove the web off the metal backing, a drying process to obtain a film by drying the removed web at a drying air temperature of 60 to 250°C and a winding process to wind up the dried film. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
In detail, the ellipsoidal resin film manufacturing method
Suitable for polarizing plates, liquid crystal display panel substrates, and liquid crystal display devices
Phase difference film made of polycarbonate resin
The present invention relates to a method for producing rumm. [0002] 2. Description of the Related Art Surfaces of 1/4 or 1/2 of the optical wavelength
Λ / 4 plate characterized by showing internal retardation
And λ / 2 plates are related to antireflection films and liquid crystal display devices
It has many uses and is already used in many ways.
ing. However, it is conventionally used for liquid crystal display devices.
The λ / 4 plate and the λ / 2 plate are λ /
Most have achieved 4 and λ / 2 respectively.
Yes, the anti-reflection effect is sufficient over the entire wavelength range.
There was no. In addition, it is transparent for convenience of use in liquid crystal display devices.
Constraints such as thickness are added for reasons such as safety and weight reduction
However, it cannot be said that thinning has been achieved sufficiently.
There was a situation. Furthermore, the surface condition at the time of casting is insufficient.
Therefore, the improvement was desired. Also increase its productivity
Is important in terms of cost, and improvement of the manufacturing method is required.
It has been. JP-A-5-27118 and 5-27
Each publication of 119 has a large in-plane retardation.
Birefringent film and birefringence with low in-plane retardation
Product with refractive index film so that their optical axes are orthogonal
A layered retardation plate is disclosed. Of two films
In-plane retardation difference is λ / over the entire visible light range.
If it is 4, the retardation plate theoretically covers the entire visible light range.
It functions as λ / 4. JP-A-10-68816
The gazette states that the polymer is λ / 2 at a specific wavelength.
-It is made of the same material as the film and has the same wavelength.
With a polymer film of λ / 4
And a retardation plate capable of obtaining λ / 4 in a wide wavelength region.
It is. Japanese Patent Laid-Open No. 10-90521 also discloses two sheets
By laminating polymer films in a wide wavelength range
A retardation plate capable of achieving λ / 4 is disclosed. Only
However, these polymer films are basically
A stretched film of synthetic polymer like recarbonate
Since it is a configuration where two sheets are laminated, there is a limit to thinning,
It cannot sufficiently cope with the thinning of the device. Japanese Patent Laid-Open No. 2
000-137116 discloses a polymer film.
A broadband λ / 4 plate using a single sheet is disclosed. But,
This λ / 4 plate is also thick.
There was a problem. On the other hand, in recent years, liquid crystal displays have been used.
However, higher definition is required. Under such circumstances
Will slightly change the dimensions and optical properties of the retardation plate.
Liquid crystal display.
The display quality of A will be reduced. So in recent years
For retardation films, dimensional stability and optical characteristics
There is a growing demand for improved stability. Also liquid
From the viewpoint of the processing temperature of the crystal display, etc.
Therefore, heat resistance has also been required. for that reason
As retardation film, excellent optical isotropy and high
That have a high glass transition temperature (Tg)
It has become. Polycarbonate as a retardation film
Although it is widely used, it has the above problems at the same time.
That improvement was necessary. As a means of improvement
Various copolymer polycarbonates have been studied.
For example, a polycarbonate copolymerized with fluorene groups
Known as a material with improved heat resistance (US patent)
No. 3,546,165), and a fluorene group
Application of polycarbonate copolymerized to optical film
Is known (Japanese Patent Laid-Open No. 5-155998,
Kaihei 8-134198, JP-A-8-54615
Publication, Unexamined-Japanese-Patent No. 8-134198). With these,
Although there was a remarkable improvement in heat resistance, liquid crystal display devices
If it is used as a material for the
In many cases, the temperature is high even during use. Fluoresce
The above polycarbonate with improved heat resistance is used.
The phase difference characteristics change due to poor dimensional stability.
As a result, the display quality of the liquid crystal display device is degraded, or
If used for a long time, it will cause poor adhesion with other components.
There is a fear. As a method for improving these problems,
Polycarbonate phase difference film by casting film forming method
A method for producing a polycarbonate foam containing a solvent.
After peeling the film from the casting support,
The film is brought to room temperature through the steps (1) to (4) continuously.
JP-A-9-230316 discloses a method of cooling to
It is disclosed. In this method, first, the film is
(1) At an ambient temperature of 15 to 40 ° C.,
3-7kg tension per square centimeter in the conveying direction
Then, transport for 2 to 4 minutes, then (2)
The glass transition temperature of polycarbonate
The ambient temperature is (Tg-45) to Tg which is
At (Tg-5) ° C, the rail width of the pin tenter is increased.
In a state of being reduced by 2.5 to 7.5% from the film width,
Hold both edges of the film in the width direction
In the state where the cross section in the film width direction draws a catenary line,
Carry for 6 minutes and then (3) fill the roll suspension dryer.
Lum is fed and the ambient temperature is (Tg-10) to Tg ° C
Tension of 0.4 to 1.5 kg per square centimeter
Transport for 30-90 minutes, and finally (4)
Cool the film to room temperature. However, with this method,
This is because heat treatment is performed with the agent remaining.
The retardation film produced by this method is
Dimensional stability was insufficient. In addition, these
Polycarbonate resin film by casting
When manufacturing, it is insufficient in terms of the surface area of the film,
The improvement is desired. [0007] The present invention solves the above problems.
Considered, with respect to temperature and humidity
Poly with excellent method stability and surface properties
Provided is a method for producing a carbonate resin film.
This is the issue. Especially used as retardation film
In this case, a polycarbonate resin with excellent optical properties is made.
It is an object to provide a method of manufacturing. [0008] Means for Solving the Problems The present inventor has intensively studied.
As a result of the simulation, polycarbonate resin with a specific structure
Has a high glass transition point, high durability, and hygroscopicity
Has also been found to have a characteristic of low. Furthermore, melting
Production of polycarbonate resin film by liquid casting method
As a result of intensive research on the method,
Product, viscosity at casting of the resin solution, web drying
The temperature at which the film is produced by the solution casting method
It was found that the surface properties of the film are greatly affected. these
The present invention is completed by further examination based on the knowledge of
It came to. That is, in order to solve the above-mentioned problems, the present invention
Is a bisphenol having at least one fluorene skeleton.
A diol derivative and at least one non-fluorene skeleton?
Glass copolymerized with a bisphenol derivative
Polycarbonate tree with a transition point (Tg) of 150 ° C or higher
Contains 10 to 40% by weight of fat and has a viscosity at casting of 10
Polycarbonate resin solution of up to 200 Pa · s
At least with a filter having an average pore diameter of 1 to 50 μm
A filtration step of once filtration and casting on a metal support
A casting process for forming a web, and the web on the metal support
And the step of peeling off the web and the peeled web 60 to
Dryer to obtain a film by drying at a drying air temperature of 250 ° C
Winding up the wound film in a roll
A process for producing a polycarbonate resin including a process
To do. In addition, in this specification, it is obtained by a casting process.
"Web" consists of a polycarbonate resin solution
It is a membrane that contains solvent but can be peeled off.
A film having strength. Furthermore, as a preferred embodiment of the present invention,
Provided by the following polycarbonate resin film manufacturing method
Is done. (Aspect 1) Before and / or after the filtration step,
Has a concentration step to concentrate the polycarbonate resin solution
A method for producing the polycarbonate resin film
The (Aspect 2) The polycarbonate resin solution is
(1) to (4) polycarbonate resin solution
The above polycarbonate resin characterized by being a liquid
It is a manufacturing method of a film. (1) An organic solvent is mixed with the polycarbonate resin.
And a step of swelling at -20 to 55 ° C, and a mixture thereof
Is heated to 0-57 ° C and polycarbonate in an organic solvent
Polycarbonate prepared by the process of dissolving resin
To resin solution. (2) Mixing an organic solvent with the polycarbonate resin
Swell at -20 to 55 ° C.
Cooling to 00 to -20 ° C, and cooled mixture
Is heated to 0-57 ° C and polycarbonate in organic solvent
Polycarbonate prepared by the process of dissolving resin
To resin solution. (3) An organic solvent is mixed with the polycarbonate resin.
Step of swelling at -20 to 55 ° C, 0.2 to 30 MP
heating at 60 to 240 ° C. at high pressure and high temperature in a, and
The heated mixture is cooled to 0-57 ° C. and poured into an organic solvent.
Polycarbonate consisting of a process of dissolving a carbonate resin
Bonate resin solution. (4) In an organic solvent cooled to −100 to −20 ° C.
Add the carbonate resin, swell and cool, then cool
The rejected mixture was heated to 0 to 57 ° C. and dissolved in an organic solvent.
The podium prepared by the process of dissolving the carbonate resin
Recarbonate resin solution. (Aspect 3) The polycarbonate resin
Are represented by the following general formula (A) and general formula (B):
All constituent units represented by the general formula (A)
Including 5 to 80 mol% in the composition unit, the intrinsic viscosity is 0.15 to
The polycarbonate described above, which is 3 dl / g
This is a method for producing a resin-based resin film. General formula (A) [Chemical 1]Where R¹~ R^FourAre hydrogen and halo, respectively.
Gen atom (fluorine, chlorine or bromine), or each
C1-C5 alkyl group which may have a substituent, charcoal
Aryl group having 6 to 12 prime atoms, alkenyl having 2 to 5 carbon atoms
Group, an alkoxy group having 1 to 5 carbon atoms, or 7 to
Represents 17 aralkyl groups, both of which have
The substituent may be an alkyl group having 1 to 5 carbon atoms or an alkyl group.
A kenyl group, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom,
Any of chlorine, bromine and dimethylsiloxy groups
It is. However, R¹~ R²At least one of which is water
A group other than an elementary atom. m, n, p and q are each
The integer in any one of 1-4 is represented. General formula (B) [Chemical 2] Where R¹¹~ R¹⁸Are hydrogen atoms,
A halogen atom (fluorine, chlorine or bromine), or
C 1-5 alkyl each optionally having a substituent
Group, an aryl group having 6 to 12 carbon atoms, an alkyl group having 2 to 5 carbon atoms
Kenyl group, C1-C5 alkoxy group, or carbon
Represents an aralkyl group of formulas 7 to 17,
The substituent which may have is an alkyl group having 1 to 5 carbon atoms or
Is an alkenyl group, an alkoxy group having 1 to 5 carbon atoms, fluorine
Of atoms, chlorine atoms, bromine atoms and dimethylsiloxy groups
Either. X of the divalent group (C) shown below
Represents either. Divalent group (C) [Chemical 3] Where R⁹And R^TenAre respectively hydrogen fields
Children, halogen atoms (fluorine, chlorine or bromine), respectively
An alkyl group having 1 to 5 carbon atoms which may have a substituent, charcoal
An aryl group having 6 to 12 prime atoms or an aryl group having 2 to 5 carbon atoms
Lucenyl group or R⁹And R^TenIs directly combined with coal
Carbon rings other than non-fluorene rings having a prime number of 5 to 17 or complex
Represents a group that forms a ring and may be present in any of these groups.
The substituent is an alkyl group having 1 to 5 carbon atoms or alkeni
Group, alkoxy group having 1 to 5 carbon atoms, fluorine atom, chlorine
Any of atom, bromine atom and dimethylsiloxy group
is there. a and b are any integers from 0 to 20, and c is 1.
Represents an integer of ~ 500. (Aspect 4) Bi comprising the fluorene skeleton
The repeating unit of the sphenol derivative is 9,9-bis
From (4-hydroxy-3methylphenyl) fluorene
It is derived and consists of the non-fluorene skeleton
The repeating unit of the bisphenol derivative is 2,2-bis
Derived from (4-hydroxyphenyl) propane
Production of the above polycarbonate-based resin film
Is the method. (Aspect 5) The polycarbonate resin is mixed with a rotating blade
Stirrer, kneader kneader, homogenizer, dyno mill
And solvent using at least one of ultrasonic irradiation
Mix in and prepare the polycarbonate resin solution
The polycarbonate characterized by comprising the steps of:
It is a manufacturing method of a resin film. (Aspect 6) The polycarbonate resin solution is converted into the metal
When casting on a support, the solution temperature is -10-5.
7 ° C and the atmosphere is kept at -10 to 57 ° C.
And a metal support for casting the solution is -10 to 30.
Banded or drum-shaped gold with a surface temperature of ° C
The above polycarbonate characterized by being a genus support
It is a manufacturing method of a resin film. (Aspect 7) In the casting step, a plurality of polycarbonates
Sheet-type resin solution is simultaneously laminated and cast on the metal support.
Or sequential co-casting at remote locations
How to produce the above polycarbonate resin film
Is the law. (Embodiment 8) The casting speed of the casting step is 10
~ 200m / min, wound by the winding process
The wound form of the film taken is less in the longitudinal direction
Both are 100 m or more and 60 cm or more in the width direction,
Before the winding process, both ends of the film (width direction
Slitting both ends), and / or
Or knurling 1 to 200 μm at both ends of the film
A polycarbonate comprising the step of:
It is a manufacturing method of a resin film. (Aspect 9) Before and / or after the winding step,
Including a step of stretching the film in at least one direction,
Wavelength 550 of stretched film obtained by the stretching process
In-plane retardation value measured in nm is 40 to 350
nm, and the film is subjected to low-tension heat treatment after film formation.
The rate of thermal dimensional change at 100 ° C. is 0.0
The above range characterized by being in the range of 01% to 0.04%
It is a manufacturing method of a polycarbonate-type resin film. (Aspect 10) After the drying step, the film
0.04 kg / cm at a temperature of −50 ° C. to Tg + 80 ° C.
²~ 6kg / cm²Low tension to heat-treat while transporting at a high tension
The above polycarbonate having a force treatment step
It is a manufacturing method of a salt type resin film. (Aspect 11) After the winding step, roll into a roll
The film taken was heated to a temperature of Tg-50 ° C to Tg + 80 ° C.
0.04kg / cm at degree²~ 6kg / cm²Heat treatment with the tension of
Characterized by having a low-tension heat treatment step
It is a manufacturing method of a polycarbonate-type resin film. From another viewpoint, according to the present invention,
The following retardation film is provided. (Aspect 12) Polycar manufactured by the above manufacturing method
Consists of a Bonate resin film and measured at a wavelength of 550 nm.
The determined in-plane retardation value (Re550) is 110.
In-plane measurement measured at a wavelength of 450 nm.
The retardation value (Re450) is 100 to 125 nm.
In-plane letter measurement measured at a wavelength of 590 nm
Value (Re590) is 120 to 175 nm, and Re
590-Re450 ≧ 2 nm phase difference film satisfying the relationship
It is a film. (Aspect 13) Polycar manufactured by the above manufacturing method
Consists of a Bonate resin film and measured at a wavelength of 550 nm.
The determined in-plane retardation value (Re550) is 220.
In-plane recording measured at a wavelength of 450 nm.
The retardation value (Re450) is 200 to 250 nm.
In-plane letter measurement measured at a wavelength of 590 nm
Value (Re590) is 240 to 350 nm,
590-Re450 ≧ 4 nm satisfying the relationship
This is a retardation film. (Aspect 14) Polycar manufactured by the above manufacturing method
Consists of Bonate resin film with 1% residual solvent
% Or less, and its moisture content is 4% by mass or less.
Any one of the above retardation films is characterized. (Aspect 15) Polycar manufactured by the above manufacturing method
Made of bonate resin film, in crossed Nicol state
Placed between two placed polarizing plates, one polarizing plate side
When observing from the other polarizing plate side by directing light from
The number of bright spots having a diameter of 0.01 mm or more is 200 / cm²
Any one of the above phase difference features,
Rum. [0021] DETAILED DESCRIPTION OF THE INVENTION Polycarbonate resin of the present invention
A method for producing a film includes a polycarbonate having a specific structure.
Polycarbonate containing 10 to 40% by weight of a nate resin
Silicate resin solution (hereinafter sometimes referred to as “dope”)
Is a method for producing a film by a solvent casting method.
Before the solution is filtered under predetermined conditions, and during casting,
Maintain the temperature at which the viscosity of the solution is within the specified range, and cast
The web obtained by the above is dried in a predetermined temperature range.
The Hereinafter, each process and each process of the manufacturing method of the present invention
The materials used for the above will be described in detail. In the present invention, at least one fluorene is used.
Bisphenol derivative consisting of skeleton and at least one kind
A bisphenol derivative comprising a non-fluorene skeleton of
A copolymerized polycarbonate resin is used. Said po
There are no particular restrictions on the structure of the carbonate resin
From the fluorene skeleton represented by the following general formula (A)
At least 1 repeating unit of the bisphenol derivative
Species and non-fluorene skeleton represented by the following general formula (B)
Fewer repeating units of bisphenol derivatives consisting of
Polycarbonate resin consisting of only one kind is preferred
Yes. General formula (A) [Formula 4]Where R¹~ R^FourAre each independently a hydrogen atom,
Halogen atom, each of which may have a substituent, carbon number
1-5 alkyl groups, C6-C12 aryl groups, charcoal
Alkenyl group having 2 to 5 prime atoms and alkoxy having 1 to 5 carbon atoms
Represents a group or an aralkyl group having 7 to 17 carbon atoms,¹
And R²At least one of them represents a non-hydrogen atom
The R¹~ R^FourEach represents an alkyl group, an aryl group,
Substitution of alkenyl group, alkoxy group or aralkyl group
As the group, an alkyl group having 1 to 5 carbon atoms or an alkeni
Group, alkoxy group having 1 to 5 carbon atoms, fluorine atom, chlorine
Atom, bromine atom or dimethylsiloxy group
The m, n, p and q are each an integer of 1 to 4
Represents. R¹~ R^FourEach represents a halogen atom
Include fluorine, chlorine and bromine atoms.
The Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group and
An ethyl group is mentioned. Bi represented by the general formula (A)
Specific examples of sphenol derivatives include 9,9-bis
(4-hydroxy-3-methylphenyl) fluorene,
9,9-bis (4-hydroxy-3,5-dimethylphenol
Nyl) fluorene, 9,9-bis (4-hydroxy-3)
-Polycarbonate composed of chlorophenyl) fluorene, etc.
And 9,9-bis (4-hydroxy
-3-methylphenyl) fluorene polycarbo
Nate derivatives are preferred. General formula (B) [Chemical formula 5] Where R¹¹~ R¹⁸Each independently
Children, halogen atoms (fluorine, chlorine or bromine), respectively
An alkyl group having 1 to 5 carbon atoms, which may have a substituent,
C6-C12 aryl group, C2-C5 alkeni
Group, an alkoxy group having 1 to 5 carbon atoms, or 7 to 1 carbon atoms
7 represents an aralkyl group. The substituent has 1 carbon atom.
-5 alkyl group or alkenyl group, 1-5 carbon atoms
Alkoxy group, fluorine atom, chlorine atom, bromine atom or
Includes a dimethylsiloxy group. X is the following divalent
It represents any divalent group selected from the group (C). Divalent group (C) [Chemical 6] Where R⁹And R^TenAre each independently hydrogen
Atoms, halogen atoms (fluorine, chlorine or bromine), it
C 1-5 alkyl each optionally having a substituent
Group, an aryl group having 6 to 12 carbon atoms, or 2 to 5 carbon atoms
An alkenyl group, or R⁹And R^TenIs directly coupled
A carbocyclic ring other than a non-fluorene ring having a total carbon number of 5 to 17, or
Represents a group that forms a heterocyclic ring. Have in any of these
Suitable substituents include alkyl groups having 1 to 5 carbon atoms,
Is an alkenyl group, an alkoxy group having 1 to 5 carbon atoms, fluorine
Atom, chlorine atom, bromine atom or dimethylsiloxy group
Can be mentioned. a and b are each independently 0-20
Any integer of 1 to 500 is represented.
Represent. Bisphenone represented by the above general formula (B)
As specific examples of the thiol derivatives, 2,2-bis (4-hydro
Xylphenyl) propane, 1,1-bis (4-hydroxy)
Cyphenyl) cyclohexane, 1,1-bis (4-hydride)
Loxyphenyl) -3,3,5-trimethylcyclohex
Sun, 2,2-bis (4-hydroxy-3-methylphenol)
Nyl) propane, 2,2-bis (4-hydroxy-3,
5-dimethylphenyl) propane, 2,2-bis (4-
Hydroxy-3-chlorophenyl) propane and the like
It is. Among them, 2,2-bis (4-hydroxypheny
E) Propane (bisphenol A) is preferred. Method for producing the above polycarbonate resin
Is not particularly limited, but the usual interfacial polymerization method,
It can be produced by a melt polymerization method or the like. General formula above
(A) is a combination of two or more repeating units
The repeating unit represented by the general formula (B) may be
You may combine 2 or more types. Polycar used in the present invention
Bonate resins may be used in combination of two or more. Polycarbonate tree used in the present invention
The preferable aspect of fat is the structure represented by the said general formula (A)
A unit and a structural unit represented by the general formula (B)
Copolycarbonate resin having the general formula
The structural unit represented by (A) is 5 to 80 mo in all structural units.
Polycarbonate resin containing 1%. General formula
Content of the structural unit represented by (A) is the said range.
It is preferable because it has higher dimensional stability against humidity.
Yes. A preferred embodiment is a configuration represented by the general formula (A).
Polycarbonate containing 5 to 70 mol% of all structural units
The preferred resin is a general formula (A).
10 to 60 mol% of all structural units
Polycarbonate resin containing, most preferred embodiment is
20 of all structural units represented by the general formula (A)
A polycarbonate-based resin containing ˜50 mol%. Po
Represented by the general formula (A) in the carbonate-based resin
When the content of repeating units decreases, heat resistance is insufficient.
May be in the range of 20 to 50 mol%.
Higher is preferable. The polycarbonate tree used in the present invention
For fat, use an Ubbelohde viscometer, methylene chloride solvent,
The value of intrinsic viscosity [η] determined by extrapolation measured at 20 ° C.
Preferably it is 0.15-3.0 dl / g, 0.3
More preferably, it is -2.0 dl / g. Also poly
When using a mixture of two or more carbonate resins
Is a polycarbonate-based resin that exceeds the above intrinsic viscosity range.
Mix fat with polycarbonate resin within this range
A polycarbonate system having a preferable intrinsic viscosity range.
It is also possible to use a resin. The polycarbonate resin used in the present invention
Photoelastic coefficient is 80 × 10^-13cm²/ Dyne or less
It is preferable. The polycarbonate resin used in the present invention
The glass transition point (Tg) is 150 ° C. or higher, 150
-270 ° C is preferred, 180-26 ° C
Is more preferable. Glass transition point is less than 150 ° C
And the film as an optical film for a liquid crystal display device, etc.
When incorporating, alignment film formation process and electrode formation process
Makes handling difficult due to thermoplasticity
Tend. In addition, for applications used at high temperatures,
Degree of stability tends to decrease. In the present invention, at least one fluorene is used.
Bisphenol derivative consisting of skeleton and at least one kind
A bisphenol derivative comprising a non-fluorene skeleton of
Copolymerized polycarbonate resin solution (hereinafter referred to as
Sometimes called "polycarbonate resin solution")
Use. For the preparation of the polycarbonate resin solution
About the solvent to be used, the kind is not limited, but various
A solvent can be used. For example, dichloromethane,
Chlorinated organic solvents such as chloroform can be used
The In addition, non-chlorine organic solvent and chlorine organic solvent
Mixed organic solvents with non-chlorine organic solvents can also be used
The Examples of the non-chlorine organic solvent include carbon atoms.
3-12 ester, ketone, ether, alcohol
And a solvent selected from hydrocarbons and hydrocarbons.
Esters, ketones, ethers and solvents used as solvents
Alcohol may have a cyclic structure. Beauty treatment
, Ketone and ether functional groups (ie, —O
-, -CO- and -COO-)
The compound to be used can also be used as a solvent. Carbon atom
Examples of esters having a number of 3 to 12 include ethylforme
, Propyl formate, pentyl formate, methyl
Acetate, ethyl acetate and pentyl acetate
Can be mentioned. Examples of ketones having 3 to 12 carbon atoms
Acetone, methyl ethyl ketone, diethyl keto
, Diisobutyl ketone, cyclopentanone, cyclohexane
Xanone and methylcyclohexanone.
Examples of ethers having 3 to 12 carbon atoms include diisopropyl
Lopyl ether, dimethoxymethane, dimethoxyethane
1,4-dioxane, 1,3-dioxolane, teto
Listed are lahydrofuran, anisole and phenetole
It is done. Examples of organic solvents with two or more functional groups
Are 2-ethoxyethyl acetate, 2-methoxyethane
Nord and 2-butoxyethanol. In addition, alcohol used as a solvent
Can be linear, branched or cyclic
Of these, saturated aliphatic hydrocarbon alcohols are preferred
Yes. The hydroxyl group of the alcohol is any of primary to tertiary
There may be. Examples of alcohols include methanol, ethanol
Nord, 1-propanol, 2-propanol, 1-butyl
Thanol, 2-butanol, tert-butanol, 1
Pentanol, 2-methyl-2-butanol and
Clohexanol is included. As alcohol
Fluorine alcohol can also be used. concrete
Include 2-fluoroethanol, 2,2,2-trifluoro
Oroethanol, 2,2,3,3-tetrafluoro-1
-Propanol or the like can be used. Furthermore, melting
The hydrocarbon used as a medium is branched even if it is a straight chain.
It may have a ring shape. Aromatic hydrocarbons and fats
Any of the aliphatic hydrocarbons can be used. Aliphatic charcoal
The hydride may be saturated or unsaturated. Carbonization
Examples of hydrogen include cyclohexane, hexane, benzene,
Toluene and xylene are included. Examples of specific organic solvents are shown below.
It is not limited to these. ・ Dichloromethane (100, parts by mass) Dichloromethane / methanol (95/5, parts by mass), Dichloromethane / ethanol (93/7, parts by mass), Dichloromethane / acetone / butanol (85/10
/ 5, parts by mass), ・ Dichloromethane / ethanol / cyclohexanone (9
0/5/5, parts by mass), ・ Dichloromethane / cyclopentanone / ethanol /
(85/10/5, parts by mass), ・ Dichloromethane / 1,3-dioxolane / methanol
/ Ethanol (70/20/5/5, parts by mass), ・ Dichloromethane / dioxane / acetone / methanol
/ Ethanol (60/20/10/5/5, parts by mass), ・ Dichloromethane / methyl acetoacetate / methanol / d
Tanol (75/10/10/5, parts by mass), ・ Dichloromethane / methyl acetate / methanol / ethanol
(65/20/10/5, part by mass), 1,3-dioxolane (100, parts by mass), 1,3-dioxolane / methanol (90/10, quality
Part), 1,3-dioxolane / butanol (93/7, mass
Part), ・ 1,3-Dioxolane / acetone / ethanol / pig
Nord (85/5/5/5, parts by mass), ・ 1,3-Dioxolane / Cyclohexanone / Methanol
Le / butanol (55/20/10/10/5, mass
Part), Dichloromethane / methyl acetate (80/20, mass
Part), 1,3-dioxolane / methyl acetate (90/10, quality
Part) Polycarbonate resin used in the present invention
The liquid is 10 to 10 in the organic solvent.
It is a solution prepared by dissolving 40% by mass. Preferably 1
It is a 3-30 mass% solution, Most preferably, it is 15-3
0% by weight solution. Concentration of polycarbonate resin
Is usually adjusted to the polycarbonate.
The concentration range is set when the resin is dissolved in a solvent.
Of course, a low concentration solution (for example, 9 to 20)
Mass%) solution is prepared, followed by the concentration step described below
By doing so, the concentration range may be adjusted. The
In addition, a highly concentrated polycarbonate resin solution is prepared in advance.
After adding the various additives, the concentration range
The concentration range may be adjusted by any method.
A carbonate resin solution may be prepared. The polycarbonate resin solution of the present invention
Group) the polycarbonate resin and the organic solvent.
It can be prepared by mixing in a medium and stirring. Stirring
Rotating blade stirrer, kneader kneader, homogenizer
-At least one of dynomill and ultrasonic irradiation
It is preferable to use one type. For example, the general method
As a polycarbonate resin at room temperature.
Can be prepared by stirring in a solvent
However, according to this method, although a solution is obtained,
take time. Moreover, it is difficult to prepare a concentrated solution. Efficient
In order to prepare a thick solution, the following (1) to (4)
The solution is preferably prepared by any preparation method. (1) Polycarbonate resin with organic solvent
And swell at −20 to 55 ° C., the mixture
Is heated to 0-57 ° C and polycarbonate in organic solvent
Polycarbonate resin consisting of a process of dissolving a resin
Method of preparing the solution; (2) Mixing an organic solvent with polycarbonate resin,
Swell at -20 to 55 ° C, the mixture is -100
Cooling to -10 ° C, and cooling the mixture to 0
Polycarbonate tree in organic solvent heated to ~ 57 ° C
Polycarbonate resin solution consisting of a process of dissolving fat
A preparation method of (3) Mixing an organic solvent with polycarbonate resin,
The step of swelling at -20 to 55 ° C, the mixture is 0.2 to
Heating at 60MPa to 30OMPa at high pressure and high temperature at 30MPa
And the heated mixture is cooled to 0-57 ° C. and organic
A step of dissolving a polycarbonate resin in a solvent.
A method for preparing a polycarbonate resin solution; (4) In an organic solvent cooled to −100 to −20 ° C.
Work to swell and cool by adding a carbonate resin
The cooled mixture was heated to 0-57 ° C. in an organic solvent.
Polycarbonate consisting of a process of dissolving polycarbonate resin in
Carbonate resin solution. Furthermore, the polycarbonate implemented in the present invention.
Specific description of dissolution of silicate resin in organic solvent
To do. In the above preparation method (1) (room temperature dissolution), the temperature −
Polycarbonate resins at 20-55 ° C as solvents and additives
Swell with stirring and mixing in a melting pot
And dissolve. However, the polycarbonate resin
The temperature during swelling is the temperature below the boiling point of the organic solvent used.
It is preferable to carry out at a degree. Regarding dissolution, polycar
Soak and swell the Bonate resin powder evenly with a solvent.
It is important that the so-called Mamako
Not generate polycarbonate resin powder)
It is important that Therefore, put the solvent in the stirring vessel.
Add in advance, and then depressurize the dissolution vessel to
It is preferable to add a carbonate resin. Also,
Conversely, polycarbonate resin is added to the stirring vessel in advance.
Then, add the solvent by evacuating the dissolution vessel
It is also preferable to do. Also, polycarbonate resin
Pre-wet with a poor solvent such as alcohol and then
In addition, chlorinated organic solvents or non-chlorinated organic solvents (for example,
For example, an ether, ketone or ester having 3 to 12 carbon atoms
It is also preferable to add a solvent. Use multiple solvents
In the case, the order of addition is not particularly limited. For example, the main solution
After adding polycarbonate resin to the medium,
Add a medium (for example, a gelling solvent such as alcohol)
It is also possible to pre-gelatinize polycarbonate resin
The main solvent may be added after moistening with
It is effective in preventing one dissolution. The polycarbonate resin is dissolved in a solvent.
In this case, it is preferable to stir. Thailand to start stirring
There is no particular limitation on the mixing, for example, polycarbonate
Immediately after mixing the nate resin and the solvent,
Is the polycarbonate resin fully swollen with a solvent?
Then, stirring may be started to obtain a uniform solvent. Next, the preparation method (2) (cooling dissolution)
Method) will be described in detail. First, at -20 to 55 ° C
Do not stir the polycarbonate resin in an organic solvent.
Gradually add. When using multiple solvents,
The order of addition is not particularly limited. For example, in the main solvent
After adding the bonate resin, other solvents (for example,
A gelling solvent such as rucol) may be added,
On the other hand, the polycarbonate resin is pre-moistened with a gelling solvent.
After the main solvent may be added, both of which are inhomogeneously dissolved
It is effective for prevention. The amount of polycarbonate resin is
Adjust so that the mixture contains 10 to 40% by mass.
The In addition, optional additives described below are added to the mixture.
You may keep it. Next, this mixture is -100 ° C to -20 ° C.
(Preferably -100 to -30 ° C, more preferably -1
00 to -40 ° C, more preferably -100 to -50
° C, most preferably -90 to -60 ° C). cold
The rejection is performed, for example, with a dry ice / methanol bath (−75
° C), using a mechanically cooled chlorofluorocarbon solution refrigerant
Yes. When cooled in this way, polycarbonate resin and
The mixture of organic solvents solidifies. Cooling rate is particularly limited
However, in the case of batch-type cooling, the
Viscosity of carbonate resin solution is increased and cooling efficiency is low.
Efficient dissolution to reach the predetermined cooling temperature
It is preferable to use a kettle. In addition, the place to cool in the liquid feed
The polycarbonate resin is swollen by a solvent.
After that, move it through the cooling device at the specified cooling temperature for a short time.
This can be achieved by sending. The faster the cooling rate, the better
Is the theoretical upper limit of 10,000 ° C./sec.
00 ° C / sec is the technical upper limit, 100 ° C / se
c is a practical upper limit. The “cooling rate”
The difference between the starting temperature and the final cooling temperature is
Time from the start of cooling to the final cooling temperature
The value divided by. In addition, the cooled mixture
00 ° C. (preferably 0 to 150 ° C., more preferably 0
~ 120 ° C, most preferably 0-50 ° C)
When the polycarbonate resin flows in the organic solvent,
One solution. Just raise the temperature at room temperature
It may be heated in a warm bath. At this time, the pressure is 0.3 ~
Although it may be 30 MPa, there is no particular problem.
In that case, it is preferable to carry out in as short a time as possible,
Within 0.5-60 minutes is preferred, especially 0.5-2 minutes short
Heating for hours is recommended. If the dissolution is insufficient, cooling,
The temperature operation may be repeated. Whether dissolution is sufficient
Whether or not is determined by simply observing the appearance of the solution visually
be able to. In the cooling dissolution method, condensation during cooling
Use airtight containers to avoid moisture contamination
desirable. Also, pressurization during cooling in the cooling and heating operation,
Dissolution time can be shortened by reducing the pressure during heating.
The In order to carry out pressurization and decompression,
It is desirable to use it. About the above cooling dissolution method
Are disclosed in JP-A-9-95544 and JP-A-10-958.
No. 54 and JP-A-10-95854 for details
It is described in. Next, the preparation method of (3) above is described in detail.
Explained. This preparation method is preferred in the present invention.
This is one of the preparation methods. First, at a temperature of -20 to 55 ° C,
The bonate resin is swollen with an organic solvent. Polica
-Bonate resin may be added gradually with stirring.
In some cases, after pre-swelling with a specific solvent,
Add the combined solvent and mix to make a uniform swelling solution.
Furthermore, after swelling with two or more solvents, the remaining
A solvent may be added and is not particularly limited. Duplicate
When using several solvents, the order of addition is not particularly limited.
Yes. For example, adding polycarbonate resin in the main solvent
After other gels such as alcohol
Medium) may be added, while polycarbonate
After pre-wetting the resin with a gelling solvent, add the main solvent.
Both of them are effective in preventing non-uniform dissolution. Next, this mixture is mixed with 0.2 MPa to 30 MPa.
60-240 ° C. (preferably 80-2) under pressure of MPa
20 ° C, more preferably 100-200 ° C, most preferred
Or 100 to 190 ° C.). For example, heating
It may be high-pressure steam or an electric heat source. High pressure resistance
A pressure vessel or pressure line is required, but iron or stainless steel
Made of less or any other metal pressure vessel or line
Well, not particularly limited. In addition, these high-temperature and high-pressure solutions
Carbon dioxide is sealed in the liquid to make a so-called supercritical solution.
May be. In that case, the ratio of carbon dioxide to solvent is 5 /
95-70 / 30 is preferable, Furthermore, 10 / 90-6
0/40 is preferred. The obtained heated solution can be applied as it is.
Therefore, it cannot be used for the subsequent casting process.
The obtained heated solution is cooled to -20 to 55 ° C,
Return to normal pressure. Built-in polycarbonate resin solution for cooling
Leave high-pressure and high-temperature containers and lines at room temperature
More preferably, a coolant such as cooling water is used.
The apparatus may be cooled. In order to promote dissolution
In addition, the heating and cooling operations may be repeated. Enough dissolution
Is to observe the appearance of the solution visually
Can be judged. In high pressure and high temperature melting method
Use a sealed container to avoid evaporation of the solvent. Ma
Furthermore, in the swelling process, further pressure or pressure reduction
Dissolution time can be shortened. Apply pressure and decompression
In order to apply, a pressure-resistant container or line is essential.
The Next, the preparation method of (4) above is described in detail.
Explained. First, it is cooled to -100 to -20 ° C.
Add polycarbonate resin to the machine solvent and
The carbonate resin is swollen and cooled. cold
The rejection temperature is preferably −100 ° C. to −10 ° C., more preferably
Or −90 to −20 ° C., particularly −90 ° C. to −25
° C. The mixture is then warmed and poured into an organic solvent.
Dissolve the carbonate-based resin. As temperature to heat
Is preferably −10 ° C. to 190 ° C., more preferably 0
° C to 150 ° C, particularly 30 ° C to 130 ° C.
If the heating temperature is above the minimum boiling point in the organic solvent,
Although it is heated under pressure, in that case, 0.1-30 MPa
Preferably, it is 0.2-20 Mpa. The polycarbonate resin solution contains
The purpose is to improve the mechanical properties of film
Or for the purpose of improving the drying speed
An agent can be added. The plasticizer is not particularly limited
There is no addition, but it is not essential, for example, phosphate ester
Or carboxylic acid esters are used. Phosphate S
Examples of tellurium include triphenyl phosphate (TPP)
And tricresyl phosphate (TCP)
The Carboxylic acid esters include phthalic acid esters and
And citrate esters are typical. Phthalate Este
Examples of dimethyl phthalate (DMP), diethyl
Phthalate (DEP), dibutyl phthalate (DB)
P), dioctyl phthalate (DOP), diphenylphenol
Talate (DPP) and diethylhexyl phthalate
(DEHP) is included. Examples of citrate esters include
O-acetyl triethyl citrate (OACTE) and
Contains tributyl O-acetylcitrate (OACTB)
It is. Examples of other carboxylic acid esters include olein
Butyl acid, methyl acetyl ricinoleate, di sebacate
Butyl, various trimellitic acid esters are included. F
Tartrate plasticizer (DMP, DEP, DBP, D
OP, DPP, DEHP) are preferably used. DE
P and DPP are particularly preferred. Add plasticizer in particular
It is not necessary, but if added, the amount is polycarbonate
0.1 to 25% by weight based on the content of the resin
It is preferably 1 to 20% by weight.
Preferably, it is most preferably 3 to 15% by weight. The polycarbonate resin solution is inferior.
Antioxidants (eg, antioxidants, peroxide decomposers, radicals)
Inhibitors, metal deactivators, acid scavengers, amines)
May be. Regarding the deterioration preventing agent, JP-A-3-1992.
No. 01, No. 5-1907073, No. 5-194789
No., No. 5-271471, No. 6-107854
There is description in the gazette. The amount of deterioration inhibitor added is the amount of the solution.
It is preferably 0.01 to 1% by weight based on the total mass.
More preferably 0.01 to 0.2% by weight.
That's right. When the amount added is less than 0.01% by weight, deterioration is prevented.
The effect of the agent is hardly recognized. Add 1% by weight
If exceeded, the bleed-out of the deterioration inhibitor on the film surface
(Exudation) may be recognized. Especially preferred
Examples of degradation inhibitors include butylated hydroxytoluene
(BHT), tribenzylamine (TBA)
You can. Polycarbonate tree used in the present invention
A preferred embodiment of the fat solution is at least one liquid
Or solid plasticizer against polycarbonate resin
Polycarbonate resin solution containing 0.1-20% by mass
Liquid, at least one liquid or solid UV absorber
0.001 to 5% by mass based on polycarbonate resin
Contains at least one polycarbonate-based resin solution
The average particle size of which is 5 to 3000 nm
The fine particle powder is 0.00% with respect to the polycarbonate resin.
Polycarbonate resin solution containing 1-5% by mass, small amount
Polycarbonate with at least one fluorosurfactant
Polycarbonate containing 0.001 to 2 mass% with respect to resin
Bonate resin solution and at least one release agent
-0.0001-2% by mass based on bonate resin
Polycarbonate resin solution, at least one inferior
Antioxidation agent is 0.000 against polycarbonate resin
Polycarbonate resin solution containing 1-2% by mass, low
At least one optical anisotropy control agent
Poly containing 0.1 to 15% by mass with respect to the nate resin
Carbonate resin solution and / or at least
One type of infrared absorber for polycarbonate resin
Polycarbonate resin solution containing 0.1 to 5% by mass
Is mentioned. In the present invention, the polycarbonate resin solution
Before being subjected to the casting process.
And Hereinafter, the filtration step will be described in detail. Main departure
In Ming, the polycarbonate resin solution is cast prior to casting.
Because it is filtered. By filtration, undissolved matter in the solution,
Remove foreign matter such as dust and impurities by filtration. Filtration is absolutely
Less with a filter with a filtration accuracy of 50 μm or less
Both are implemented once. Preferably, the absolute filtration accuracy is 0.
1-30 μm filter is used, more preferably
Uses a filter with an absolute filtration accuracy of 0.2 to 20 μm
It is done. The thickness of the filter is preferably 0.1-10mm
Moreover, 0.2-2 mm is more preferable. Filter thickness
Is within the above range, the filtration pressure is 16 Pa or less.
Is more preferable, 10 Pa or less is more preferable,
The pressure is particularly preferably 8 Pa or less. Filtration flow rate is 5 liters
Torr / mm²-Hr or more is preferable, 50 liters / m
m²-Hr or more is more preferable. The filter material is particularly limited.
However, common filter media can be used.
Glass fiber, cellulose fiber, filter paper, ethylene tetrafluoride tree
It is preferable to use materials such as fluororesins such as fat.
In particular, ceramics, metals and the like are preferably used.
Filter media can be used in both surface and depth types
However, the depth type is relatively clogged.
It is difficult to use. The filtration of the polycarbonate resin solution
The viscosity of the melt containing the carbonate resin is filtered
At a temperature of 1000 Pa · s or less
Preferably, it is more preferably performed at 500 Pa · s or less.
More preferably 200P or less.
It is particularly preferable to carry out at 00P or less. Solution during filtration
The temperature is preferably 0 to 57 ° C., and 10 to 50 ° C.
More preferably. Furthermore, it is the most used solvent
The solution temperature is below the boiling point, which is a low boiling point solvent.
preferable. By carrying out this filtration step,
Generation of foreign matter in the polycarbonate resin film
As a result, the protective film for the polarizing plate, etc.
When used in a product, the product value is significantly improved
be able to. Specifically, the polycarbonate produced
To be recognized in crossed Nicols state
Foreign matter with a size exceeding 50 μm, area 250 mm
²It can be substantially zero per hit, and further 5 to 5
0 μm foreign matter has an area of 250 mm²Less than 200 per
In particular, it can be 100 or less. Evaluation at this time
The polarizing plate used for is composed of a protective film free from bright spot foreign matter.
Glass to protect the polarizer
Those using a plate are preferably used. Bright spot foreign matter
Unacetylated cellulose contained in the carbonate resin
One of the causes, a polycar with few bright spots
Use of bonate resin and molten polycarbonate
To remove and reduce the salt resin.
You can. Also, the unit area decreases as the film thickness decreases.
The number of bright spot foreign materials per hit is reduced and included in the film
The brighter point the lower the content of polycarbonate resin
Foreign matter tends to be reduced. Measurement of the number of bright spot foreign materials
The method will be described in detail in the examples below. In the present invention, before and / or before the filtration step.
Later, the polycarbonate resin solution is concentrated.
A concentration step may be performed. Hereinafter, regarding the concentration step,
This will be described in detail. The above-described preparation methods (1) to (4) can be used.
By using high-concentration polycarbonate resin.
Liquid can be prepared, but the poly
In order to prepare a carbonate resin solution,
After preparing the solution, it can be concentrated to the desired concentration.
preferable. The concentration method is not particularly limited,
For example, a low-concentration solution is rotated in the circumferential direction inside the cylinder
Between the rotation trajectory of the outer periphery of the rotating blade and the solution
A high temperature solution while evaporating the solvent.
A method for obtaining a liquid (for example, JP-A-4-259511)
Etc.) Blowing the heated low-concentration solution from the nozzle into the container
The solvent between the nozzle and the inner wall of the container.
Evaporate the solvent vapor from the container
Extraction and extraction of high-concentration solution from the bottom of the container (for example,
USP 2,541,012, USP 2,85
8,229, USP 4,414,341, USP
(Method described in each specification of No. 4,504,355)
Etc. . Next, the polycarbonate resin solution is mixed with gold.
A casting step of casting on a genus support is performed. In the present invention
Is the polycarbonate resin solution at the casting temperature
The casting step is carried out at a viscosity of 10 to 200 Pa · s.
When the viscosity at the temperature at the time of casting of the solution is too low,
Spills easily from the solution extrusion port, but too high
Then, it becomes difficult to send the solution. At the temperature at the time of casting
The viscosity of the polycarbonate resin solution is 10 to 200 Pa.
・ If it is s, such a problem does not occur, and the doping is stable.
Can be cast. Polycarbonate resin solution
The liquid has a viscosity at the casting temperature of 10 to 200 Pa · s.
And a dynamic storage elastic modulus at −5 ° C. of 10,000 to
1,000,000 Pa is preferred, when casting
The viscosity at a temperature of 10 to 150 Pa · s, and −
Dynamic storage elastic modulus at 5 ° C. is 50,000 to 500,00
More preferably, it is 0 Pa. Polycarbonate
The temperature at which the resin solution is cast depends on the type of solvent used.
The preferred range is also different, but in general, when casting
-10 to 57 ° C (preferably 25 to 50 ° C)
Adjusted to Therefore, the polycarbonate resin solution
The liquid has a viscosity of 10 to 200 P at -10 to 57 ° C.
a · s, and the dynamic storage modulus at −5 ° C. is 10,
000 to 1,000,000 Pa is preferred,
At the temperature, the viscosity is 10 to 150 Pa · s.
And a dynamic storage elastic modulus at -5 ° C of 50,000 to 5
More preferably, it is 00,000 Pa. Incidentally, casting of the polycarbonate resin solution
The temperature of the hour is maintained at a temperature that falls within the viscosity range.
For example, store the solution before sending it to the die.
In the liquid feed tank, the viscosity of the solution is within the viscosity range.
It is only necessary to be maintained within the temperature range. Necessarily casting
The temperature of the atmosphere at the time does not have to match the temperature
However, before casting on a metal support, the viscosity of the solution changes.
In order not to move, the temperature of the casting atmosphere
A, before piping and feed block for liquid feeding
The temperature of the member through which the solution passes is also maintained at the same temperature.
It is preferable. The viscosity of the polycarbonate resin solution
And dynamic storage modulus, rheometer for 1 mL of sample solution
(CLS 500) Steel with a diameter of 4cm / 2 °
Cone (both manufactured by TA Instruments)
Can be measured. Measurement conditions are Oscillatio
4 in n Step / Temperature Ramp
Measure by changing the range from 0 ° C to -10 ° C at 2 ° C / min.
Static non-Newtonian viscosity n at the same temperature as the solution temperature just before rolling
^*(Pa · s) and storage elastic modulus G ′ (Pa) at −5 ° C.
Can be requested. Note that the sample solution is pre-measurement start temperature.
Start the measurement after keeping the solution at a constant temperature until the solution temperature is constant.
The In the casting step, a polycarbonate tree is used.
Cast the fat solution onto a drum or band metal support
Then, the solvent is evaporated to obtain a web. Drum or van
The metal support surface of the mirror must be finished in a mirror state
preferable. For example, the surface is mirror-finished with chrome plating.
Mirror finish by raised drum and surface polishing
Stainless steel belt (may be called a band)
It is preferable. Surface temperature of metal support before casting
If the degree is below the boiling point of the solvent used for the dope
It may be any number of times, but generally it is -50 to 130 ° C
The In the present invention, in the casting step, the temperature −
The polycarbonate resin maintained at 10 to 57 ° C.
The solution is flowed onto a metal support with a surface temperature of −10 to 30 ° C.
And maintain the casting portion atmosphere at -10 to 57 ° C.
Is preferred. The polycarbonate resin is used as a metal support.
The method of casting on top and producing a film of uniform thickness
For example, the solution is uniformly pushed from the pressure die onto the metal support.
After casting the solution on a metal support,
Doctor that adjusts the thickness of the solution layer on the holder with a blade
-Blade method; casting the solution onto a metal support
After that, the thickness of the solution layer on the support is adjusted to the reverse rotation.
Using a reverse roll coater that is adjusted with a roll; etc.
However, a method using a pressure die is preferable. For pressure die
There are coat hanger type and T die type etc.
These can also be preferably used. Also mentioned here
In addition to the method, cellulose triacetate known in the past
Various methods for casting a solution solution (for example, JP-A 61-61)
No. 94724, JP-A-61-148013,
JP-A-4-85011, JP-A-4-286611
No. 5, JP-A-5-185443, and JP-A-5-1.
No. 85445, JP-A-6-278149,
The method described in Kaihei 8-207210) is preferred.
Consider the difference in the boiling point of the solvent used.
By taking into account each condition,
The same effect as the contents described can be obtained. The pressure die is a metal support
One or more can be installed above the holder
The Preferably 1 or 2 groups. Install two or more
The amount of the solution to be cast in each die.
It can be divided into various proportions and the solution can be
Send the liquid from the metered gear pump to the die at each ratio.
Also good. In carrying out the casting process, a metal support is included.
The casting section is partitioned as a chamber, and the temperature of the casting section is kept constant.
Can be set to temperature. About the space temperature of the casting section
The polycarbonate resin is not particularly limited.
It is preferable to match the temperature of the solution. In general
It is −50 to 50 ° C., more preferably −30 to 40 ° C.
Preferably, it is -20-30 degreeC. Flow
If the space temperature of the extension is low, the polycarbonate tree
The fat solution is instantly cooled on the metal support and the gel strength is reduced.
Improves organic solvent even after casting
The film can be held as it is. As a result,
In a short time from the metal support without evaporating the mechanical solvent
Film can be peeled off and high-speed casting is achieved
it can. The space cooling means is not particularly limited.
Use air, nitrogen, argon or helium
Cooling means can be used. Also, the humidity of the casting part
Is preferably 0 to 70% relative humidity, and 0 to 50 relative humidity.
% Is more preferable. To keep the casting at the temperature of the present invention
May be achieved by introducing a cooled gas into the casting part,
Or even if a cooling device is placed in the casting section to cool the space
Good. At this time, it is important to make sure that water does not adhere.
It can be implemented by a method such as using dry gas.
Yes. In the present invention, the casting process includes a conventional process.
Film production method by known solvent casting method
Various casting processes carried out in can be applied. Sol
Casting and drying method in bent-cast method.
U.S. Pat. No. 2,336,310, U.S. Pat.
3, US Pat. No. 2,429,078, US Pat. No. 24,929
77, US Pat. No. 2,492,978, US Pat. No. 2,607
704, U.S. Pat. No. 2739069, U.S. Pat.
9070, British Patent 640731, British Patent 736
No. 892 specifications, Japanese Examined Sho 45-4554, Shoko Sho
49-5614, JP-A-60-176834, JP
Sho-60-203430, JP-A-62-115035
Can be applied to the present invention.
The Furthermore, Japanese Patent Laid-Open No. 2000-301555
The casting process in the solution coating method described in the
In other words, the resin solution is discharged in the form of a film from the tip of the casting die.
When casting on a metal support that moves below the tip,
By adjusting the exit speed to 0.5-9.0 m / min,
Casting process capable of improving film thickness accuracy;
Useful for the film forming method described in Japanese Patent No. 0-301558.
Casting process used, that is, metal from the tip of the casting die
The resin solution extruded into a film on the support is in contact with the metal support.
The surface to be touched is melted by vacuum suction using a vacuum chamber.
In the liquid film forming method, the discharge speed is 7 to 38 m / min.
Adjust the degree of vacuum in the pressure chamber to -1 to -50 mmAg
Can improve the thickness accuracy of the film
Can be applied to the present invention. Japanese Laid-Open Patent Publication No. 07-032391
As described, dope the temperature of the die body by circulating hot water
Boiling point -7 ° C under normal pressure of (polycarbonate resin solution)
The temperature is kept at -1 ° C, and the lip portion is under normal pressure of the dope A (boiling)
Point) Maintained at ℃ ~ (boiling point +30) ℃, under normal pressure of the dope
Dope B maintained at (boiling point) ° C. to (boiling point + 30) ° C.
Filling from loop A and finally casting from lip;
As described in JP-A-03-193316,
Casting polymer solution of mechanical solvent from die to metal support
And a vacuum chamber that sucks that part from the back of the die
-Keep the inner wall temperature above the condensation point of the organic solvent
Without solvent vapor condensing in the vacuum chamber
The method of casting can be applied to the present invention. Ma
Further, it is described in Japanese Patent Laid-Open No. 05-086212.
In the casting film that prevents dripping by dripping the liquid on both ends
And the solvent is a poor solvent with respect to the good solvent for the solute.
Casting method containing 0 to 90% by mass;
Cellulose triacetate described in No. 113
In the manufacturing method of G, solid content is 18-35 mass%,
Resin whose non-methylene chloride solvent is 13 to 25% by mass
The solution is cast on a metal support having a surface temperature of 10 ° C. or less.
Can be applied to the present invention. Furthermore, Japanese Patent Laid-Open No. 02-276607.
The unit near the side edge described in
Discharge amount per dander is smaller than the average discharge amount in the center
Casting die having such a shape; JP-A-55-01420
No. 1 of cellulose acylate
7-30 mass% of solvent and methylene chloride as solvent
The resin solution used was cast on the band surface, and after casting, 3
Heat to 30-42 ° C within minutes and less
In both methods, the temperature is maintained for 15 seconds;
The metal support described in No. 11 is exposed.
Fill the area with a gas with a dew point lower than the metal support surface temperature.
Also described in JP-A-02-208650
Cellulose tria on both ends of the binder
A method of flowing down a soluble solvent of cetate;
It can also be applied to. In the present invention, the polycarbonate resin
The solution can be applied to a metal support (eg, a smooth band or
1) Flow one polycarbonate resin solution once
To form a single-layer film,
Can also apply different types of polycarbonate resin solutions simultaneously.
May be cast separately to form two or more layers of film
Yes. When forming a single-layer film, the required film thickness
Polycarbonate system with high concentration and high viscosity
It is necessary to extrude the resin solution, in which case
The stability of the bonate resin solution is poor and solids are generated.
There is a tendency that unevenness occurs or the flatness is poor. Po
By co-casting the carbonate resin solution,
A solution of viscosity can be simultaneously extruded onto a metal support,
The planarity is improved and an excellent planar film can be produced. The
In addition, the drying load can be reduced and film production
Can be improved. For co-casting, inside and outside
The thickness is not particularly limited, but preferably the outside is the total film thickness
1 to 50%, more preferably 2
~ 30% thickness. Here, there are three or more layers of co-casting
The tota of the layer in contact with the metal support and the layer in contact with the air side
The film thickness is defined as the outer thickness. A film having two or more layers is produced by casting.
A plurality of metal supports that are spaced apart in the direction of travel of the metal support.
From each casting port, polycarbonate resin solution
You can also make a film while casting and laminating
Yes. This method is disclosed in, for example, JP-A-61-158414.
No. 1, JP-A-1-122419, JP-A-11-
198285, etc., and is described in the present invention.
Can be applied. In addition, polycarbonate
-Film by casting Bonate resin solution
About this method, for example, JP-B-60
-27562, JP-A-61-94724,
JP-A 61-947245, JP-A 61-104
No. 813, JP 61-158413, JP
Hei 6-134933, and the present invention
Can be applied to. Also, JP-A 56-1626.
High viscosity cellulose acylate solution described in No. 17 publication
The flow of water with a low viscosity cellulose acylate solution
The cellulose acylate solution with high and low viscosity
The cellulose acylate film casting method to be extruded into
It can be applied to the invention. In addition, an apparatus having two casting ports is used.
The resin solution is cast on the metal support from the first casting port.
To make a film, then peel off the film,
Cast from the second casting port on the side that was in contact with the support surface.
By doing so, you can also make a laminated film,
For example, it is described in Japanese Patent Publication No. 44-20235
Also used in the method. Casting polycarbonate resin
The solution can be the same solution or different polycarbonates
A resin resin solution may be used and is not particularly limited. Multiple polices
-In order to give the Bonate resin layer a function, its function
Cast polycarbonate resin solution according to
Extrude from the mouth. Further, the polycarbonate system
Resin solution and other functional layers (eg adhesive layer, dye layer, belt
Antistatic layer, antihalation layer, UV absorption layer, polarizing layer
Etc.) The forming solution may be cast simultaneously. Casting to form a web consisting of two or more layers
The various additive concentrations (for example, plasticizer, UV absorption)
Polycarbonate resin solutions with different agents and matting agents)
Using multiple layers of polycarbonate resin
Rum can also be made. For example, skin layer / core
Layer / skin layer of polycarbonate resin film
Films can be made. For example, the matting agent is
To be contained in the skin layer in a large amount or only in the skin layer
Can do. Plasticizers and UV absorbers from skin layers
Can be put in the core layer a lot, and only in the core layer
Also good. Also, the plasticizer and ultraviolet rays in the core layer and skin layer
You can also change the type of absorbent, for example on the skin layer
Contains low volatility plasticizer and / or UV absorber
In the core layer, a plasticizer with excellent plasticity or UV absorption
It is also possible to add an ultraviolet absorber excellent in yield. Ma
In addition, the release agent should be included only in the skin layer on the metal support side.
Both are preferred embodiments. In addition, the metal drum is supported by the cooling drum method.
In order to cool the holder and gel the solution,
Add more alcohol, which is a poor solvent, than the core layer
Is also preferable. Even if the skin layer and core layer have different Tg
It is preferable that the Tg of the core layer is lower than the Tg of the skin layer.
Good. Also includes polycarbonate resin during casting
The viscosity of the solution may also be different between the skin layer and the core layer,
It is preferred that the viscosity of the skin layer is smaller than the viscosity of the core layer
Even if the viscosity of the core layer is smaller than the viscosity of the skin layer,
Good. Casting to form a web consisting of two or more layers
The same polycarbonate resin solution
A plurality of different types may be used. Use
Multiple polycarbonate resin solutions
Either the composition of the medium is the same or different
The additive is one type or more than two types
The same type of additive, which is either
In the additive solution, either one or different
The concentration of the same or different
On the other hand, the molecular weight of the aggregate is the same or different
The temperature of the solution is either
Either the same or different temperatures, and each
Viscosity with either the same or different application amount
The degree of dryness is either the same or a different viscosity
Either the film thickness after drying is the same or different
Certain, even if the material is in the same state or distribution
The physical properties of each layer formed are the same or distributed.
Either one or different physical properties,
Distribution of physical properties with uniform or different physical properties of each layer formed
Any polycarbonate tree that is either
A fat solution can also be used. Here, physical properties are the invention
Association Technical Report (Public Technical Number 2001-1745, 2001
Detailed description on pages 6-7 of the March 15 issue, Japan Association of Inventions)
Listed in Physical Properties of Cellulose Acylate Films
For example, haze, transmission
Rate, spectral characteristics, retardation Re, Rth, molecule
Orientation axis, misalignment, tear strength, bending strength, tensile strength, winding
Rt difference between inside and outside, Kishimi, dynamic friction, alkaline hydrolysis, car
Value, moisture content, residual solvent amount, heat shrinkage, high humidity dimensional evaluation,
Moisture permeability, base flatness, dimensional stability, heat shrinkage start temperature
Degree, elastic modulus, and bright spot foreign matter measurement, etc.
Includes impedance and surface shape used for base evaluation
It is rare. In addition, the Japan Society for Invention and Innovation Technical Report (Public Technical Number)
2001-1745, issued on March 15, 2001, invention
Yellow Inn described in detail on page 11
Dex, transparency, thermophysical properties (Tg, heat of crystallization), etc.
Gender values are also applicable. In the casting step, polycarbonate
After casting the resin solution on the metal support,
The solution may be dried. Dry is generally gold
The surface side of the genus support (drum or belt), that is, metal
A method of applying hot air from the surface of a web on a support;
Method of applying hot air from the back of the ram or belt; temperature
The controlled liquid is cast on the belt or drum.
Contact from the back side, which is the opposite side of the surface,
Heating the belt or belt to control the surface temperature
The liquid heat transfer method;
Of these, the backside liquid heat transfer method is preferred. Cast
The surface temperature of the metal support before use is the same as that used for the resin solution.
As long as it is below the boiling point of the solvent being used, it can be dried any number of times.
In order to promote the resin solution on the metal support.
In order to reduce the fluidity of the liquid, of the solvents used
1-10 ° C below the boiling point of the lowest boiling solvent
It is preferable to set. In the present invention, the casting work
Strip the web obtained in the process from the metal support,
Can be transferred to the drying process on the metal support.
Drying is not essential. According to the manufacturing method of the present invention, polycarbonate
The rate at which a sheet resin film is manufactured is
Metal support size (eg belt length), dry
Drying method in the process and polycarbonate resin
Depending on the solvent composition of the solution, etc.
The amount of residual solvent at the time of peeling from the support depends on the production rate.
Greatly affects. In other words, support in the thickness direction of the web
By effectively reducing the solvent concentration near the body surface
Thus, the manufacturing speed can be improved. When peeling
The amount of residual solvent contained in the tank greatly affects the productivity.
For example, if the web has too much solvent, it will peel off
When a part of the web remains on the support,
It interferes with the casting performed. The web also has money
Strength to withstand the force applied when peeling from the genus support
is required. When moving from the casting process to the peeling process,
Residual solvent volume reduced to the extent that the web is self-supporting
Need to be. Reduce solvent volume to an appropriate level
The time required for reduction depends on the drying method on the metal support.
Depending on the surface of the web, dry it with wind.
Rather than using a method, the back of a metal support (belt or drum)
The method of transferring heat from the surface effectively and quickly reduces the amount of residual solvent
can do. The web produced by the casting process is made of gold
It peels off from a genus support body and uses for the following drying processes. Next, the drying process of the present invention will be described in detail.
Light up. In the drying step, the metal support was peeled off.
The web is dried at a temperature of 60-250 ° C. 60-180
It is more preferable to dry at a temperature. Drying is within the temperature range
This is done by blowing on the web from which the dry air is stripped
Is preferred. After drying in the temperature range,
In order to remove the solvent remaining in the web, 100-16
It is preferable to dry at 0 ° C. For example, the temperature of the drying air
It is preferable to change the temperature gradually until the residual solvent evaporates.
That's right. This method can reduce the drying time.
Noh. Depending on the solvent used, the drying temperature and air flow
Depending on the type and combination of solvents used.
Can be selected as appropriate. Residual solvent amount of the final film
Is preferably 2% by mass or less, and 0.4% by mass or less
Is preferred for obtaining a film with good dimensional stability.
That's right. For the measurement of the amount of residual solvent, in the examples described later
This will be described in detail. In the drying step, in the casting step
Peel the web formed on the metal support from the support
After drying, the web will be
Try to shrink in the direction. Shrinkage increases with drying at higher temperatures
I'm angry. Drying while suppressing shrinkage as much as possible
Is preferable because it can improve the flatness of the film.
Yes. Web shrinkage is achieved by clicking on both edges of the peeled web.
Tenter system that performs the drying process while maintaining the width with the
Can be suppressed. For example, JP-A 62-4
Japanese Patent No. 6625 discloses the entire drying process or a part of the drying process.
And dry the web while holding both ends of the web with the clip.
Are disclosed and can be applied to the present invention.
The In addition to the tenter method, JP-A-4-0850
The cellulose acylate solution described in No. 11 publication
The liquid is cast on a metal support cooled to 20 ° C. or lower, and cooled solid
When the solvent is 40% by mass or more
The surface material of the transport roller at 20 ° C
A process for producing an energy of 80 mN / m or less;
-90946, the dope is a metal
In the process of casting on a support to form a web, the solvent
Is peeled from the metal support containing 60% by mass or less
Removing step, and the peeled web is 120 to 135 ° C.
A manufacturing method in which the heat treatment is performed at a temperature of 4 minutes or more according to the present invention
And can be dried while suppressing web shrinkage
The In the present invention, the drying temperature is within the above range.
As long as the various methods listed below in the drying step
Conditions can be applied. For example, JP-A-07-
No. 108547 discloses cellulose triacetate buffer.
A film production method is described, and the solid content is 15 to 35% by mass.
Formed using a resin solution of volatile matter X (%), surface
When the film of temperature Y (° C.) is 20 ≦ X ≦ 60, Y
> −0.5X + 70, or 0 ≦ X ≦ 20, Y
Dry the film under conditions satisfying> -6X + 180
Speed up the production of cellulose triacetate film
Improve mechanical strength such as tear strength and processability.
It is described that it can be. Dryer of the present invention
However, it is possible to carry out drying according to the above conditions.
Yes. Japanese Patent Application Laid-Open No. 07-112446 discloses a sensor.
The volatile content in the roulose triacetate film is X%,
When film surface temperature is Y ° C, 0 <X <20
When Y> −6X + 1802 or 0 ≦ X ≦ 60, Y>
Polarizing plate protective film obtained by drying at -0.5X + 70
The birefringence is extremely small, and the degree of polarization of the polarizing plate can be improved.
In the drying process of the present invention, before
Drying can be carried out according to the conditions described above. Also, in Japanese Patent Laid-Open No. 61-1000042
Polycarbonate resin metal support temperature, dope
The maximum temperature above the gelation temperature is 30 ° C-foaming
Keep the temperature below the temperature, and remove the poly at the temperature of the stripping part.
A carbonate-based resin production method is also disclosed in JP-A-08-1183.
No. 78 discloses a tear strength temperature of -20 ° C to + 23 ° C.
With a slope of 0.3 or less and a film thickness of 115 to 135 μm.
About roulose triacetate film 15-35
Mass% dope with drying air temperature T, dry tear strength W, T
To-15 <T <for W inflection point temperature To
A technique for drying at a drying air temperature is disclosed, and the temperature is low.
Polycarbonate resin film that is less likely to break down
The polycarbonate resin film of the present invention.
It can also be applied to film production. Also, Japanese Patent Laid-Open No. 61-110520 discloses
The band portion where the dope is cast is described.
A windshield with a U-shaped cross section is provided to cover the endless band.
Cellulose acetate dope on a metal support consisting of
Casting and forming a film by sending hot air to the windshield and volatilizing the solvent
Method that enables high-speed production without foaming;
Final work described in Japanese Patent Laid-Open No. 04-286611
The residual solvent immediately before entering the process is 10% by mass or less, and the final dry
In the drying process, the surface temperature is (glass transition temperature +40) ° C.
And the surface temperature is higher than the temperature before the final process.
Manufacturing method of polycarbonate resin that lowers by 15 ° C or more;
Poly, which is described in Kaihei 05-185443
Metal support in which carbonate resin solution is cooled to below 20 ° C
When it is cast on a holder, cooled, solidified, peeled off and dried, a solvent is used.
Is 40% by mass or more, 3% from the film end.
Cool the surface temperature to the inside of 0cm or more to 20 ℃ or less
The number of cleaning operations to prevent foreign matter growth on the transport rollers.
Made of reduced cellulose triacetate film solution
Can be applied to the production method of the present invention.
The Further, JP 2000-002809 A
In the report, the hot air is changed from high temperature to low temperature on the surface of the coating liquid layer.
By spraying, in the drying process of the coating liquid layer
Alignment film forming material that is maintained at a surface temperature of 30 to 60 ° C.
A method for producing a long flexible sheet having a material layer is disclosed,
Flexibility without alignment defects for liquid crystal panels or optical compensation sheets
There is a possibility that the adhesive sheet can be easily manufactured in a continuous process. Also,
Japanese Patent Laid-Open No. 04-001009 discloses surface temperature and volatilization.
Cellulos has a good flatness with excellent tearing and folding resistance by specifying a quantity formula
Suacylate production method; JP-A 62-046626
The gazette states that after peeling the cellulose acylate, the film
Carry while pulling the side edge in the width direction with a force that does not stretch
By sending and drying, the cellulose acylate film
Improvement of the surface shape of the rum;
No. 86611 discloses first and second drying chambers and a final drying chamber.
In the drying chamber, the residual solvent of the film is 10% or less and the film
Make the surface temperature 15 ° C lower than the final drying chamber and dry
In the chamber, the surface temperature of the film ranges from Tg to Tg + 40 ° C.
By the method of transporting the film wound around the roll while maintaining
It is described that streaking is prevented. these
This technique can also be applied to the manufacturing method of the present invention. Further, JP-A-11-235728.
After the film is peeled off, the web at any position in the drying process
The width is A, and the residual solvent ratio is reduced by 10% from that position.
The width B of the selected position, and the shrinkage rate Sa between them, Sa =
When {(A−B) / A} * 100, Sa ≦ 5
The production method of polycarbonate resin to be dried and transported is
Lot variation due to lateral shrinkage of web
It is described that it can be prevented. Japanese Laid-Open Patent Publication No. 1
1-090942 discloses a film from a metal support.
In the drying and transporting process between peeling and winding,
Polycarbonate that suppresses curled parts and conveys them
A method for producing a resin based on the curl at both ends of the web is disclosed.
Bending has been improved. Japanese Patent Laid-Open No. 11-048271
In the gazette, the solvent content of the peeled film is 50-1
At 2% by mass, stretch and dry the film with a width stretcher
When the solvent content is 10% by mass or less,
Pressure of 0.2 to 10 KPa from both sides of the web
And at a time of 50% by mass or more,
Width retention High temperature drying, sudden shrinkage cutting, unevenness and tension
A method for preventing flatness deterioration of a film is disclosed.
The Japanese Patent Application Laid-Open No. 64-055214 discloses a back surface.
Apply drying air to the air and start drying within 15 seconds from the start of casting.
The direction of the drying air is diagonally forward of the metal support traveling direction,
The angle formed by the metal support surface is 40 to 80 degrees, and the dry wind static pressure
Is 5mmHg or more, between dry air outlet and metal support surface
How to produce cellulose triacetate with a gap of 5-50mm
The law is disclosed. These methods are also applicable to the present invention.
Yes. Further, Japanese Patent Laid-Open No. 11-0777718 discloses
When drying the web while holding the width with a tenter,
Dry gas blowing method, blowing angle, wind speed distribution, wind
Speed, air volume, temperature difference, air volume difference, up / down air volume ratio, high ratio
By appropriately controlling the use of heat drying gas,
Increase speed by solution casting method or increase film width
A method to prevent quality degradation such as flatness when spreading is disclosed.
It is. Japanese Patent Application Laid-Open No. 11-255387 discloses drying.
The flatness of the winding process can be corrected with the subsequent winding tension and winding diameter.
Keeps the flatness even during storage after winding.
It is disclosed that it can be done. JP2000-2394
No. 03 discloses a residual solvent ratio X at the time of peeling of 15 ≦ X ≦ 1.
20, the web is peeled from the metal support and then dried.
Of the produced cellulose acylate film
It is a thin film, optically isotropic, and has good flatness.
A drying method for cellulose acylate is disclosed.
ing. JP-A-11-216732 discloses TAC.
When casting the dope from the die onto the metal support of the casting part,
The temperature of the metal support depends on the boiling point of the main solvent used for the dope.
0.5-55 ° C lower and the casting draw ratio is 1.0 or more
Method for producing cellulose acylate film of 3.0 or less
This method occurs in a die-cast dope film
In addition to suppressing vertical and die lines, foaming,
Method intended to improve film formation, adhesion reduction, and peelability
It is. JP-A-10-006351 discloses casting.
After that, until the film is peeled off, the support temperature is 10-30.
It is a manufacturing method of TAC by the solution casting method that passes through the state of ℃
Cellulose with excellent dimensional stability as a liquid crystal display component
Suacylate technology is disclosed. These technologies are also
It can be applied to the present invention. Furthermore, Japanese Patent Application Laid-Open No. 11-123732.
In the gazette, a dope having a solvent content of 300% by mass or more,
Drying on the metal support at the casting part or after drying.
In the region, the solvent content is less than 300% by weight per minute
Disclosed is a method for producing cellulose acylate that decreases with speed.
Flatness, coating properties and mechanical properties during rapid drying during high-speed casting
Is prevented from falling. JP-A-11-138568
The publication uses a casting device having a plurality of cooling rolls.
At the end of the drying process where the web is immediately before the cooling process.
After the temperature has passed, the web does not wind the cooling roll.
For manufacturing cellulose acylate that cools while transporting
Regarding flatness without vertical wrinkles or vertical creases during high temperature drying
It is possible to obtain an excellent polycarbonate resin
Are disclosed. Japanese Patent Laid-Open No. 2000-17695
No. 0 discloses two or more drive rollers and a number of rollers.
Cellulose acyle in the drying process consisting of a roller
The residual solvent is 20% by mass or less, and the surface temperature is 80 ° C. or less.
Top, web draw ratio is 1-1.05, dry starting point
Brawler transport tension is 10kgf / m or more
-Cellulose with a total contact time of 10 seconds or more with the roll
A method for conveying an acylate is disclosed, whereby
Whey, good planar cellulose acylate without wrinkles
Is disclosed. These cellulose acyles
The technology used in the cart is also the policy of the present invention.
-It can be applied to a method for producing a sulfonate resin film. Residual solvent is removed by the drying step.
And a film is obtained. Then the film is taken up
It moves to a process and is wound up in roll shape. Winder
There are no particular restrictions on the winder used.
Use a commonly used winder
Can do. Constant tension method, constant torque method, taper tenn
Method, program tension control with constant internal stress
It can be wound up by a winding method such as a roll method.
Winding tension is 0.01-5kgf / mm²In
More preferably, 0.05-2 kgf / mm²In
The By transporting the film by the transport member
The casting process, drying process, and winding process are continuously performed.
Can be implemented. Transport rollers used for transport
-Surface shape is smooth / satin / grooved or patent registration number
Described in the specification of Nos. 2683122 to 2683124
Can be used. From the casting process to the winding process (or
Until each step described later is added if desired)
It may be carried out under an atmosphere, or an inert gas such as nitrogen gas
You may implement in atmosphere. Far-infrared and Japanese Patent Laid-Open No. 8-13
No. 4336, No. 8-259706, No. 8-3
As described in Japanese Patent No. 25388, a microwave
Can also be dried. Polycarbonate obtained as described above.
The width of the resin film is preferably 0.5 to 3 m, more
Preferably 0.6 to 2.5 m, more preferably 0.8
~ 2.2m. Length is 100 to 10 per roll
It is preferable to wind up at 000 m, more preferably 50
0 to 7000 m, more preferably 1000 to 5 m.
000 m. When winding, at least one end
It is preferable to give a ring with a width of 3 mm to 50 mm,
More preferably, the height is 5 to 30 mm, and the height is 0.5 to 50.
It is 0 μm, more preferably 1 to 200 μm.
This may be a single push or a double push. The present invention
As a preferred embodiment of the present invention, the casting speed in the casting step is 10.
~ 200m / min, wound by the winding process
The wound form of the film taken is less in the longitudinal direction
Both are 100 m or more and 60 cm or more in the width direction,
Before the winding process, both ends of the film (width direction
Slitting both ends), and / or
Or knurling 1 to 200 μm at both ends of the film
The aspect including the process to do is mentioned. Immediately after the drying step, a winding step is performed.
May be implemented, but after the drying step (or the same as the drying step)
Sometimes), following stretching process, post-drying process, low-tensile heat treatment
And / or perform various processing steps,
A winding process can be carried out. Also take up
After the process (or simultaneously with the winding process), the following stretching
Process, post-drying process, low-tension heat treatment process and / or seed
Various processing steps can also be carried out. Below, as desired
Various processes to be added will be described. Poly produced by the production method of the present invention
Carbonate resin film is used for retardation plate
Is particularly preferred. Manufactured through casting process and drying process
Stretched film sequentially or continuously
it can. Stretching after or simultaneously with the drying process
It is preferable to carry out the process. The stretching process can be performed at room temperature or
It can be carried out under heating conditions. The heating temperature is
It is preferably below the glass transition temperature of rum. Phi
Lum stretching may be uniaxial stretching or biaxial stretching. F
The film can also be stretched while being dried, especially solvent
It is effective when is left. For example, transport film
While being transported by a roller, it is dried and a transport roller
Adjust the speed of the film to
By increasing the winding speed of the rumm, fill
The film can also be stretched. The width of the film with a tenter
While holding, convey and gradually widen the tenter.
Also, the film can be stretched. After the drying step
And stretching using a stretching machine (preferably long stretch)
Uniaxial stretching using a stretching machine) is also preferable. The draw ratio is preferably 1.1 to 3 times.
More preferably, 1.2 to 2.5 times is preferable.
1.3 to 2.0 times is preferable. Also, stretching is performed in one stage
Alternatively, it may be performed in multiple stages. When performing in multiple stages,
What is necessary is just to make it the product of each draw ratio become this range. Total
The stretching speed is preferably 5% / min to 1000% / min.
Furthermore, it is preferable that the rate is 10% / min to 500% / min.
That's right. The stretching temperature is preferably 30 to 260 ° C.
Furthermore, it is preferable to carry out at 70 ° C. to 230 ° C.,
100-230 degreeC is especially preferable. Stretching is a heat roll
Or / and radiant heat source (IR heater, etc.), warm air
More preferably. It also increases the temperature uniformity
For this purpose, a thermostatic bath may be provided. Uniaxial stretching by roll stretching
When performing, the distance between rolls (L) and the retardation film
L / W, which is the ratio of width (W), is 2.0 to 5.0
Are preferred. Other various techniques of the stretching process
Are disclosed in, for example, JP-A-62-115035 and JP-A-HEI2-
4-152125, JP-A-4-28411
Information, JP-A-4-298310, JP-A-11-48
Cellulose acyle described in Japanese Patent No. 271
A film film stretching technique can be applied. Before carrying out the stretching process, a preheating process is provided.
You can also. Also, after the stretching process, stretched film
May be heat-treated. Heat treatment temperature is polycarbonate
A temperature 20 ° C. lower than the glass transition temperature Tg of the resin film
Is preferably performed at a temperature higher by 10 ° C., and the heat treatment time
Is preferably 1 second to 3 minutes. Also, how to heat
Even if the method is zone heating, the part using the infrared heater
Minute heating may be used. During or at the end of the process,
Both ends of the rum may be slit. These slit scraps
Is preferably recovered and reused as a raw material. In the present invention, it is possible to reduce the size of the produced film.
Low tension heat treatment process for the purpose of improving qualitative
Is preferably carried out. In this specification,
“Tension” refers to the force applied to the support, the cross-sectional area of the support (width
X means the value divided by (thickness). Such tension adjustment
Winding motor and / or feeding motor torque
This can be easily achieved by adjusting the key. Also a dancer
By installing a roll and adjusting the load applied to it,
Can be easily achieved. In addition, to control low tension,
Measure the amount of heat shrinkage of the support in advance and meet this amount
A method of reducing the winding amount by the amount is also preferable. the above
The tension generated by heat shrinkage stress is also controlled by this method, making it weaker
Processing with high tension becomes possible. The width direction is clip
So that the support can contract freely
Is preferred. To transport the support with such low tension
Use air levitation transport in addition to roll transport if possible
Is preferred. This is due to the reduced roll hold force
This is to prevent the occurrence of scratches. In the present invention, the low tension heat treatment step is performed.
After the drying process, the film is loaded with low tension
You may carry out a heat treatment for carrying out heat treatment.
However, after the drying step, the
It is more preferable to carry out the heat treatment in the form of a shell. mechanism
Details are not clear, but rolled up into a roll
The heat dimensional change rate is smaller when heat-treated
An unexpected synergistic effect can be obtained. Also dry
After the process, it is very long to carry out the transfer heat treatment continuously
This is because a heat treatment zone is required and equipment costs increase.
The First, the transfer heat treatment method will be described. Po
Surface treatment of the carbonate resin film itself and the support
After finishing or undercoating, 0.04kg / cm²~
6kg / cm²It heat-processes, heating and conveying with the tension of.
At this time, the preferable tension is 0.04 kg / cm.²~ 6kg
/ Cm², More preferably 0.2 kg / cm²~ 5.5k
g / cm²More preferably, 1 kg / cm²~ 5kg /
cm²It is. If the tension exceeds this range, the dimensional change will be large.
If it falls below this range, the transfer
Can not be held by the
Become. The temperature at this time is polycarbonate resin resin.
-50 ° C to + 80 ° C of the Tg of the film, more preferably
-40 ° C to + 70 ° C of Tg of film, more preferably
The Tg of the film is −30 ° C. to + 50 ° C. During heat treatment
The interval is preferably 1 to 60 minutes, more preferably 2 to 40 minutes
3 minutes to 30 minutes is more preferable. This heat treatment
Further post-heat treatment may be performed. Post heat treatment is above
Following heat treatment, 15 ° C. to 70 ° C., more preferably 2
Heat at 0 ° C to 60 ° C, more preferably at 25 ° C to 50 ° C
Process. The treatment time is preferably from 1 second to 5 minutes, and from 5 seconds to 3
Minutes are more preferred, and 10 seconds to 1 minute is even more preferred. This
The post-heat treatment is performed while being conveyed following the heat treatment of the present invention.
The preferred tension is 0.04 kg / cm.²
~ 6kg / cm², More preferably 0.2 kg / cm²~
5.5kg / cm²More preferably, 1 kg / cm²~
5kg / cm²It is. Next, the roll heat treatment method will be described.
After the drying step, a surface treatment step or an undercoat as desired.
0.1 kg / cm²More than 20kg /
cm²Or less, more preferably 0.2 kg / cm²18
kg / cm²Or less, more preferably 0.5 kg / cm²
15 kg / cm²Take up the roll with the following tension,
Thereafter, the same heat treatment is performed. Actually polycarbonate
-50 ° C. to + 80 ° C. of Tg of the resin-based resin film, more preferable
Preferably, the Tg of the film is −40 ° C. to + 70 ° C.
Preferably, the Tg of the film is −30 ° C. to + 50 ° C.
The The heat treatment time is preferably from 1 minute to 60 minutes, preferably 2 minutes
More preferably 40 minutes or less, more preferably 3 minutes or more and 30 minutes or less.
Further preferred. Further, a surface treatment for performing a surface treatment on the film.
You may implement a process. In addition, polycarbonate tree
Carry out the process of bonding other functional layers to the grease film
You can also. By performing surface treatment, polycarbonate
Resin film and each functional layer (for example, undercoat layer and bar
Adhesiveness with the back layer) can be improved. concrete
In glow discharge treatment, ultraviolet irradiation treatment, corona treatment,
Flame treatment, acid or alkali treatment can be used
The The glow discharge treatment here is 10^-3~ 20 To
It may be low-temperature plasma that occurs under low pressure gas of rr,
In addition, plasma treatment under atmospheric pressure is also preferable. plasma
Excitable gas means plasma excitation under the above conditions
Gas, argon, helium, neon, chestnut
Puton, xenon, nitrogen, carbon dioxide, tetrafluoro
Chlorofluorocarbons like methane and their mixtures
It is done. Details of these are disclosed in the Technical Report of the Japan Society of Inventions.
(Public number 2001-1745, March 15, 2001
Published in detail on pages 30-32
ing. In addition, plasma at atmospheric pressure has been attracting attention in recent years
The treatment is, for example, 20 to 500 under 10 to 1000 Kev.
Kgy irradiation energy is used, more preferably 3
Irradiation energy of 20-300Kgy under 0-500Kev
Ghee is used. Alkali treatment is performed on the film surface with alkali.
In this process, a coating solution is applied and saponified. As a coating method
Dip coating method, curtain coating
Method, extrusion coating method, bar coating
And the E-type coating method. Arca
The solvent for reprocessing coating solution is easy to apply to the film.
In addition, it has good wettability and maintains a good surface condition of the film.
It is preferable to select such a solvent. Specifically
Is preferably an alcohol solvent, isopropyl alcohol
Is particularly preferred. Also, an aqueous solution of surfactant
It can also be used as Alkaline treatment coating solution
Lucari is preferably an alkali that dissolves in the above solvent.
More preferred are OH and NaOH. Alkaline treatment coating solution
The pH of is preferably 10 or more, more preferably 12 or more
Yes. Saponification proceeds by alkali treatment.
The condition is preferably from 1 second to 5 minutes at room temperature, and from 2 seconds to 1
Minutes or less are more preferable, and 3 seconds or more and 30 seconds or less are particularly preferable.
Good. After alkali saponification reaction, the coated surface is washed with water or acid
It is preferable to wash with water after washing. Arca
Re-processing and alignment film de-coating described later can be performed continuously.
In such a case, the number of steps can be reduced. After performing the surface treatment step,
Application of functional layer forming coating solution on Bonate resin film
Thus, a functional layer can be formed. Or surface
Do not perform the surface treatment process after performing the treatment process.
An undercoat layer (adhesive layer) is provided, and a functional layer coating solution is provided thereon.
Can be applied to form a functional layer. The primer
For details about the layer, please refer to the Japan Society for Invention Information (Public Technical Number 20
01-1745, March 15, 2001
Cellulose acylate described on page 32
The technology about the film can be applied as it is. Also book
The functional layer of the polycarbonate resin film of the invention
However, various functional layers are disclosed by the Japan Society of Inventions (Technical Number 20)
01-1745, March 15, 2001
Cellulos described in detail on pages 32 to 45
The technology of the cellulose acylate film is applied to the polycarbonate of the present invention.
It can be applied to a salt type resin film. An example of the production method of the present invention is specifically described below.
Show. First, polycarbonate resin in the melting machine (kettle)
The solution is temporarily stored in a storage kettle and contained in the solution
Defoam the foam to make the final preparation. The solution from the spout,
For example, a pressurizing mold that can deliver a fixed amount of liquid with high accuracy by the number of rotations.
To the pressure die through the volume gear pump and add the solution.
Running endlessly from the die (slit) of the pressure die
Cast evenly on the metal support of the cast part (casting work)
About). At the peeling point where the metal support almost goes around,
Remove web (also called doped film) from metal support
(Stripping process). Clip the ends of the resulting web
While sandwiched and held in width, transported with a tenter and dried, then
Then, it is transported by the rolls of the drying device and finished drying (drying process
), Wind up to a predetermined length with a winder (winder)
About). The present invention is conventionally used in a solution casting method.
Various equipment, eg casting equipment, drying equipment, winding
Take-off device, transport device that transports film, etc. between devices
Can be used. For the drying device,
-Various combinations of rolls and rolls can be selected depending on the purpose.
Can be selected. Silver halide photographic materials and electronic
When manufacturing functional protective films for displays,
Films such as antistatic layer, antihalation layer, protective layer
A coating device for surface processing may be used. Polycarbonate obtained by the production method of the present invention
The thickness of the Bonate resin film is 10 to 1000 μm
Is preferred. If the thickness is less than 10 μm, the substrate production process
There is a problem that handling becomes difficult
The If it is thicker than 1000μm, it is lightweight
Not only the characteristics of the fat base material are lost, but also the parallax increases.
As a result, the display quality is lowered. Better
It is preferably 30-500 μm, and 40-300 μm
More preferably it is. Film thickness adjustment is
The polycarbonate resin solution is used to achieve the desired thickness.
Concentration of solids contained in the liquid, between the slits of the die base
Adjust gap, extrusion pressure from die, metal support speed, etc.
do it. Further, the polycarbonate film (hereinafter
The haze value of the base material is preferably 1% or less, and
Is less than 0.8%, especially 0.5% or less
Yes. Next, obtained by the production method of the present invention.
Convert polycarbonate resin film to retardation film
Describe the preferred characteristic values when applied. Main departure
Polycarbonate resin film obtained by Ming's manufacturing method
When the film is a retardation film, the thickness unevenness is ±
Preferably it is 5% or less, more preferably ± 3%
Or less, and further ± 1.5% or less. Typically
In-plane retardation varies for substrates with little thickness variation
The thickness is also reduced from the uniformity of the retardation film.
Smaller unevenness is more preferable. The thickness of the film
Mimura uses a rectangular sample of 5cm x 10cm.
In the middle of the film, at three points on both ends, the machine direction (MD),
10 samples each in the transverse direction (TD)
Measure 10 samples each with a contact-type thickness meter,
Divide the difference between the maximum and minimum values of each average thickness by the total average thickness.
Can be obtained. Polycarbonate obtained by the production method of the present invention
When using a sulfonate resin film as a retardation film
The rate of thermal dimensional change at a temperature of 100 ° C. is 0.001
% To 0.04% is preferable. Dimensional change rate is
If it is within the range, it is optical even when used in a high-temperature atmosphere.
This is preferable because the characteristics do not vary. The thermal dimensional change rate
The measuring method will be described in detail in Examples. Polycarbonate obtained by the production method of the present invention
When using a sulfonate resin film as a retardation film
Has a residual solvent amount of 1% by mass or less and a water content of 4
It is preferable that it is below mass%. The residual solvent amount and
The measurement method of water content is described in detail in the examples below.
explain. Polycars obtained by the production method of the present invention
When using a sulfonate resin film as a retardation film
Are two pieces of the film arranged in a crossed Nicol state
Between the two polarizing plates, shining light from one polarizing plate side
When observed from the other polarizing plate side, the diameter is 0.01 mm.
The number of bright spots is 100 / cm²Is less than
50 / cm²Less preferred
10 / cm²More preferably, it is less than. Na
For the measurement of the number of bright spot foreign materials, see the examples below.
This will be described in detail. Polycar used as retardation film
The in-plane retardation value of the sulfonate resin has a wavelength of 55
It is in the range of 40-350nm when measured at 0nm.
Is preferred. Wavelength 5 when used as a λ / 4 plate
In-plane retardation value measured at 50 nm (Re55
0) was measured at 110 to 160 nm and a wavelength of 450 nm.
In-plane retardation value (Re450) is 100 to 12
In-plane letter measured at 5 nm and at a wavelength of 590 nm
When the retardation value (Re590) is 120 to 175 nm
Yes, and Re590-Re450 ≧ 2 nm
It is preferable to satisfy Re590-Re450 ≧ 5
More preferably, it is Re590-Re4.
Most preferably, 50 ≧ 10 nm. Wavelength 450
In-plane retardation value measured in nm (Re450)
Is 108-120 nm, measured at a wavelength of 550 nm
In-plane retardation value (Re550) of 125-1
In-plane letter measured at 42nm and wavelength 590nm
The foundation value (Re590) is 130 to 152 nm.
And Re590-Re550 ≧ 2 nm
It is more preferable to satisfy. Re590-Re550
More preferably, ≧ 5 nm, Re590-R
Most preferably, e550 ≧ 10 nm. Also,
It is also preferable that Re550-Re450 ≧ 10 nm.
Yes. When used as a λ / 2 plate, the wavelength is 550.
In-plane retardation value measured in nm (Re550)
Is 220-320 nm, measured at a wavelength of 450 nm
In-plane retardation value (Re450) of 200-2
In-plane measurement measured at 50 nm and at a wavelength of 590 nm.
The retardation value (Re590) is 240 to 350 nm.
And the relationship of Re590-Re450 ≧ 4 nm.
It is preferable to satisfy the relationship. Re590-Re450
More preferably, ≧ 10 nm, Re590−
Most preferably, Re450 ≧ 20 nm. wavelength
In-plane retardation value measured at 450 nm (Re4
50) is 216 to 240 nm, and the wavelength is 550 nm.
The measured in-plane retardation value (Re550) is 25.
In-plane measured from 0 to 284 nm at a wavelength of 590 nm
Retardation value (Re590) is 260 to 304n
m and Re590-Re550 ≧ 4 nm
It is more preferable to satisfy the relationship. Re590-
More preferably, Re550 ≧ 10 nm, R
e590-Re550 ≧ 20 nm is most preferred
That's right. In addition, Re550−Re450 ≧ 20 nm.
It is also preferable. In-plane retardation value (Re) is
Calculate according to the following formula. In-plane retardation value (Re) = (nx−ny) × d In the equation, nx is the in-plane slow axis direction refraction in the retardation plate.
Ny is the in-plane of the retardation plate
And the refractive index in the direction perpendicular to the slow axis of
It is the thickness (nm) of the phase difference plate. Furthermore, it is manufactured by the manufacturing method of the present invention.
The manufactured polycarbonate resin film is suitable for manufacturing conditions.
It is possible to satisfy the formula
it can. 1 ≦ (nx−nz) / (nx−ny) ≦ 2 In the equation, nx is the in-plane slow axis direction refraction in the retardation plate.
Ny is the direction perpendicular to the slow axis in the plane of the retardation plate
And nz is the refractive index in the thickness direction.
The The polycarbonate resin film is
Refractive index (refractive index n in in-plane slow axis direction) by stretching treatment
x, refractive index ny and thickness in the direction perpendicular to the in-plane slow axis
Direction refractive index nz) can be adjusted to a preferred range.
Yes. If the intrinsic birefringence is positive, the polymer chains are oriented.
The refractive index increases in the direction of the difference. Such intrinsic birefringence is
When a positive polymer is stretched, the refractive index is usually nx> n
y ≧ nz. This is a polymer oriented in the in-plane direction.
The chain has more x component due to stretching, and z component is the most
This is because it becomes smaller. Thus, 1 ≦ (nx−n
z) / (nx-ny) can be satisfied.
Furthermore, the relationship of (nx−nz) / (nx−ny) ≦ 2 is established.
In order to be satisfied, control the draw ratio of uniaxial stretching,
Alternatively, the refractive index is adjusted by unbalanced biaxial stretching.
Just adjust. Specifically, the maximum draw ratio SA and its
The stretching ratio SB in the direction perpendicular to the stretching direction is 1 <SA
/ SB ≦ 3 so as to satisfy the relationship
Balance biaxial stretching may be performed. The draw ratio is
It is a relative value when the length before stretching is 1. S
When B is less than 1 (in other words, shrinks)
There is also. If the above equation is satisfied, SB is less than 1.
It may be. Furthermore, the draw ratio is the front letter day.
Adjustment to be λ / 4 or λ / 2. Total
The stretching process can be simultaneous or sequential.
Yes. Polycars obtained by the production method of the present invention
The bonate resin film can be used as it is.
Can be used as difference film, especially λ / 4 plate
However, even if a linear polarizing film is sequentially laminated on one side of the film,
Good. Although it does not specifically limit as said polarizing film, PVA
A film in which water is dissolved in water or an organic solvent is cast to form a film.
After stretching VA film, iodine or dichroic dye
Use a dyed or stretched dye
Can do. The polarizing film and the polycarbonate thus prepared
Λ / 4 plate made of nate resin film, λ / 4 plate
Laminating by changing the angle between the in-plane slow axis and the polarization axis of the polarizing film
By doing so, an elliptically polarizing plate can be obtained. Also,
When laminated so that it is substantially 45 °, a circularly polarizing plate is obtained.
It is. Substantially 45 ° means that it is 40-50 °.
means. The slow axis in the plane of the λ / 4 plate and the polarization axis of the polarizing film
Is preferably 41 to 49 °, 42 to
48 ° is more preferable, and it is 43 to 47 °.
More preferably, it is most preferably 44 to 46 °
preferable. Polycarbonate obtained by the production method of the present invention
-Retardation film made of bonate resin
Can be applied to film for plate and liquid crystal display panel
The embodiment is not particularly limited. Sometimes
Gas barrier layer, hard coat layer, transparent conductive layer,
Agent layer, color filter layer, antireflection layer, light scattering layer, etc.
Can be provided. The retardation film is assembled in a liquid crystal display device.
The display mode is not particularly limited, but TN
(Twisted nematic) type, VA (Ver
tical alignment) type, HAN (Hyb)
rid-aligned Nematic) type, STN
(Super Twisted Nematic)
Type or GH (Guest Host) type
Are preferred. The twist angle of TN type liquid crystal cell is 40 ~
100 ° is preferable, and it is 50 to 90 °.
And more preferably 60 to 80 °.
Good. Refractive index anisotropy (Δn) of liquid crystal layer and thickness of liquid crystal layer
The value of product (Δnd) with (d) is 0.1 to 0.5 μm.
Preferably, it should be 0.2 to 0.4 μm
Further preferred. A TN liquid crystal cell is a single unit without a drive circuit.
Pure matrix system and active with drive circuit
Can be used in a matrix manner. Acte with drive circuit
The active matrix method is more preferable. STN type liquid
The twist angle of the crystal cell should be 180-360 °
Preferably, the angle is 220 to 270 °.
Yes. Refractive index anisotropy (Δn) of liquid crystal layer and thickness of liquid crystal layer
The value of product (Δnd) with (d) is 0.3 to 1.2 μm.
Preferably, it should be 0.5 to 1.0 μm
Further preferred. STN type liquid crystal cell has no drive circuit
Acti with simple matrix method and drive circuit
Can be used in the submatrix method The HAN type liquid crystal cell has a liquid on one substrate.
The crystals are oriented substantially vertically, and the crystal on the other substrate
The tilt angle is preferably 0 to 45 °. Of the liquid crystal layer
The product of the refractive index anisotropy (Δn) and the thickness (d) of the liquid crystal layer (Δ
The value of nd) is preferably 0.1 to 1.0 μm.
More preferably 0.3 to 0.8 μm.
The substrate on the side that vertically aligns the liquid crystal is the substrate on the reflector side.
It may be a substrate on the transparent electrode side. GH
Type liquid crystal cell, the liquid crystal layer is a mixture of liquid crystal and dichroic dye
It becomes. When both liquid crystal and dichroic dye are rod-like compounds,
The long axis direction of the director of the liquid crystal and the dichroic dye are parallel.
The When the alignment state of the liquid crystal changes due to voltage application,
The dichroic dye also changes the major axis direction like the liquid crystal. GH type
Liquid crystal cells include Heilmeier type and cholesteric
White-Taylor type, two-layer type using liquid crystal, λ
A method using a / 4 plate is known.
Therefore, it is preferable to use a system using a λ / 4 plate.
For guest-host reflective liquid crystal display devices with λ / 4 plates
JP-A-6-222350 and JP-A-8-36174.
No., No. 10-268300, No. 10-292175
No. 10-293301 No. 10-311976
No., No. 10-319442, No. 10-325953
No. 10-333138, 11-38410
There are descriptions in each publication. The λ / 4 plate is composed of a liquid crystal layer and a reflector.
Between. The liquid crystal layer is either horizontal or vertical
May be used, but it is preferable to use vertical alignment.
Yes. The dielectric anisotropy of the liquid crystal is preferably negative. The VA liquid crystal cell has two sheets when no voltage is applied.
The liquid crystal is vertically aligned between the substrates. Generally dielectric constant
Liquid crystal with negative anisotropy is used, and the voltage between the upper and lower electrodes
The liquid crystal is horizontally aligned by applying. In general
-Used in Marie Black mode, very expensive
A contrast ratio is obtained. To improve viewing angle dependency
Negative uniaxial or negative biaxial retardation film
Is done. In addition, protrusions and depressions on the electrode and slip
The viewing angle dependency can be improved by using the G-shaped electrode.
Is disclosed in JP-A-11-258605.
The Refractive index anisotropy (Δn) of liquid crystal layer and thickness of liquid crystal layer
The value of product (Δnd) with (d) is 0.1 to 1.0 μm.
Preferably, it should be 0.3 to 0.6 μm
Further preferred. Horizontal direction of substrate on liquid crystal with positive dielectric anisotropy
VA can be applied by applying an electric field in the horizontal direction to align the liquid crystal horizontally.
It can be considered as one of the type liquid crystal cells. The reflection type liquid crystal display device has a low applied voltage.
Normally white
Even if the applied voltage is low, the display is dark when the applied voltage is low and bright when the applied voltage is high
Can also be used in normally black mode
The The liquid crystal display device has one or two λ / 4 plates.
As the λ / 4 plate, the polycarbonate
To resin film can be used. Liquid crystal display
The device is basically of a reflective or transflective type.
The driving method of the transflective liquid crystal display device is a simple matrix.
The active matrix method is preferred over the
TFT (Thin Film Transist
or), TFD (Thin Film Diode)
Or MIM (Metal Insulator Meta
It is more preferable to use l). Low temperature for TFT
It is better to use polysilicon or continuous grain boundary silicon
preferable. For details, see “LCD Device Handbook”.
"The Japan Society for the Promotion of Science 142nd Committee, Nikkan Kogyo Shimbun"
Company, "Liquid Crystal Application", Mitsuji Okano et al., Baifukan, "Color Liquid
Crystal Display "Shunsuke Kobayashi et al., Industrial Books," Next Generation Liquid Crystal
"Display Technology" Tatsuo Uchida, Industrial Research Committee, "LCD
The latest in spray ", Young Liquid Crystal Research Group, Sigma Publishing,
"Liquid Crystal: Fundamentals and New Applications of LCD" Liquid Crystal Young Research Group
Ed., Sigma Publishing, etc. [0123] The present invention will be more specifically described with reference to the following examples.
Explained. The materials, reagents, proportions and operations shown in the following examples
The work and the like are appropriately changed without departing from the spirit of the present invention.
be able to. Therefore, the scope of the present invention is shown below.
It is not limited to a specific example. Special features in each example
The sex value was measured according to the following method. <Intrinsic viscosity> The intrinsic viscosity [η] is Ubello.
Use a viscometer with a methylene chloride solvent at 20 ° C.
Obtained by extrapolation. <Thermal dimensional change> Sampling: Sample film in raw film
At the three points at the center and both ends, the vertical direction (MD) and the horizontal direction (T
Three samples were sampled each in D). Sample is 5c
Dimensional change in the MD direction is measured using a mx25cm rectangle.
When doing a 25cm piece parallel to MD direction, TD direction
When measuring the dimensional change of a 25cm piece in the TD direction
Sampled in parallel. Measurement of dimensional change rate: 20 cm interval in the center of the sample
Two holes were drilled. This temperature is 25 ° C. and relative humidity is 60%.
After measuring the humidity for 12 hours or longer, measure the length using a pin gauge.
(This length is L1). After this, the temperature is 100 ° C.
Lay conditions (without changing the absolute humidity of 25% relative humidity 60%
12 hours under conditions where only the temperature is raised to 100 ° C)
After this, 12 hours or more at 25 ° C. and 60% relative humidity
After humidity control, the length was measured again using a pin gauge (this length was
L2). The thermal dimensional change rate was determined based on the following formula. Thermal dimensional change rate (%) = | 100 × (L1-L2) / L1
｜ This is measured at each measurement point (the center of the original film, 3 points at both ends)
D and TD in two directions (6 points in total)
The largest value among these 6 points is shown as the thermal dimensional change rate.
did. <Thermo-optical property change> <Thermal dimensional change>
Samples before and after the experiment were run by JASCO Corporation M-15
450 nm, 550 nm using a type 0 ellipsometer,
Measured at 590 nm and determined from the difference. <Residual solvent amount> Gas chromatograph of sample 7 mm x 35 mm
Measure Raffy (GC-18A, Shimadzu Corporation)
Then, the amount of residual solvent in the sample was measured. 200 samples
It heated for 12 hours and calculated | required from the mass change before and behind a heating. <Slow axis angle distribution, in-plane retardation
> The sample film is the center of the original film, 3 at both ends.
10 points each in the longitudinal direction (MD)
I was The sample was a 5 cm × 15 cm rectangle.
These samples were added to the ellipsometer (KOBRA-31
PR, 450 nm, 550 by Oji Scientific Instruments)
Retardation at nm and 590 nm, from MD direction
Measure the deviation of 10 points each, and the retardation is all points
From the average, the slow axis angular distribution is the maximum of the deviation of each angle
And from the minimum. <Haze> Haze meter (1001DP type, sun
This was measured using Denden Kogyo Co., Ltd. <Moisture content> Sample 7mm x 35mm was measured with moisture meter and sample dry
Dryer (CA-03, VA-05, both Mitsubishi Chemical
) Measured by the Karl Fischer method. amount of water
It was calculated by dividing (g) by the sample weight (g). <Measurement of Bright Spot Foreign Body> Orthogonal State (Cross Nico
2), two polarizing plates are arranged to block the transmitted light,
Place each sample between the polarizing plates. The polarizing plate is made of a glass protective plate
I used something. Irradiate light from one side and optical from the other side
1cm with a microscope (50x)²Per diameter 0.01mm
The number of bright spots above was counted. [Example 1] (1-1) Preparation of polycarbonate resin Bisphenol A and biscresol fluorene 1: 2
Sodium hydroxide aqueous solution and ion exchange at a molar ratio of
Dissolve in water and add a small amount of hydrosulfite. Next
To the mixture, add methylene chloride and phosgene for 65 minutes at 20 ° C.
It was blown over. Furthermore, p-tert-butylfe
After adding the emulsified emulsion, add triethylamine.
The reaction was terminated by stirring at 30 ° C. for about 3 hours. End of reaction
After completion, the organic phase is separated and the methylene chloride is evaporated to remove poly
A carbonate resin was obtained. The resulting resin was 120 ° C
For 6 hours, and after pulverization with a pulverizer, the average particle
Classify with a sieve so that the size is 1-4mm,
Bonate resin (PC-A) was obtained. Tg is about 220 ° C
The intrinsic viscosity was 0.61 dl / g. (1-2) Polycarbonate resin solution
Preparation 400L stainless steel dissolution tank with stirring blades
While stirring and dispersing well in the following solvent mixed solution,
The polycarbonate resin (PC-) prepared in (1-1)
Gradually add the powder from A) and the whole will be 200kg
It was charged. The solvent dichloromethane and meta
Use a diol with a moisture content of 0.2% by mass or less
did. First, the polycarbonate resin powder
The tank is depressurized to 1000 Pa after being put into the tank.
And mixed with stirring. Stirring is initially 15 m / sec.
Breaking stress 5 × 10^Fourkgf / m / sec²)
Dissolver type eccentric stirring shaft and central shaft are
With ringer blades, peripheral speed 1 m / sec (shear stress 1 × 10
^Fourkgf / m / sec²) For 60 minutes. T
By cooling the tank with a refrigerant, the start temperature of dispersion is -20.
The final temperature reached 25 ° C. 0 ° C or less here
The cooling was held to hold for 30 minutes. Distributed end
After that, high-speed agitation was stopped, and the peripheral speed of the anchor blade was 0.5 m /
Stir for another 100 minutes as a second, and polycarbonate
Swelled resin flakes. Nitrogen gas until the end of swelling
The tank was pressurized to 0.12 MPa.
At this time, keep the oxygen concentration in the tank below 2% by volume.
It was. The water content in the solution is 0.2% by mass or less.
I confirmed that there was. [0131]   Polycarbonate resin (water content 0.2% by mass) 20 parts by mass   Dichloromethane 58 parts by mass   5 parts by mass of methanol   Plasticizer B (Triphenyl phosphate) 0.4 parts by mass   UV agent a: 0.2 part by mass   (2,4-Bis- (n-octylthio) -6- (4-hydroxy-     3,5-di-tert-butylanilino) -1,3,5-triazine   UV agent b: 0.2 part by mass   2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)-     5-chlorobenzotriazole   UV agent c: 0.2 part by mass   (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl)-     5-chlorobenzotriazole   Citric acid diethyl ester (release agent) 0.02 parts by mass   0.05 parts by mass of fine particles   (Silicon dioxide (particle size 20 nm), Mohs hardness about 7) The polycarbonate resin used here is Fe
It was confirmed that the atoms were 1 ppm or less. (1-3) Dissolution / filtration process Screw the swollen solution from the tank using a gear pump.
-Liquid was sent to the extruder. Screw primary pressure at this time
Was 0.55 MPa. Screw circulating refrigerant
With jacket to make, refrigerant is 3M Fluorinert
The solution was fed at −80 ° C. using FC-77. Refrigerant is directly expanded
Cooled by freezer. Average velocity in the jacket is 2m
/ Sec and the average solution residence time inside the screw is
It was 180 seconds. Dope coming out of screw is stationary
Up to 35 ° C by jacketed piping with mixer
And then heated to 110 ° C under a pressure of 1 MPa.
It was. The heating time was 15 minutes. Further warm to 120 ° C
Sintered metal fiber filter with a nominal pore diameter of 10 μm
Was passed. At this time, the primary filtration pressure is 1.5 MPa,
The next pressure was 1.2 MPa. Filters exposed to high temperatures
-Has a lot of corrosion resistance for housing and piping
Use the one made of telloy alloy, and flow the heat medium for heat insulation and heating.
A thing with the jacket for letting it pass was used. Na
A comparative example (sample 14) in which no filtration was performed was also produced. (1-4) Concentration and filtration The dope thus obtained is heated at 120 ° C. under normal pressure.
Flash in the tank and remove the evaporated solvent with a condenser.
Separated. The solid concentration of the dope after flashing is 2
It became 4 mass%. The condensed solvent is charged
Was sent to the recovery process to be reused as a solvent for
It is implemented by distillation process and dehydration process.
) The flash tank has an anchor wing on the central axis.
Then, deaeration was performed by stirring at a peripheral speed of 0.5 m / sec. Tan
The temperature of the dope in the tank is 35 ° C, and the average stagnation in the tank
The residence time was 50 minutes. Collect this dope at 40 ℃
The viscosity measured at 25 was 25 (Pa · s). at that time
The dynamic storage viscoelasticity at −5 ° C. was 55000. Next
In addition, this dope is effective in removing bubbles by applying weak ultrasonic waves.
gave. Defoamed dope is pressurized to 1.5 MPa
First, a sintered metal filter with a nominal pore diameter of 10 μm
Passed, then 2.5μm sintered metal filter
-Passed through. Each primary pressure is 1.5, 1.2
The secondary pressure is 1.0 and 0.8 MPa, respectively.
Met. Adjust the dope temperature after filtration to 35 ° C,
Stored in a 00 liter stainless steel stock tank
did. The stock tank has an anchor wing on the central axis.
The mixture was constantly stirred at a peripheral speed of 0.3 m / SEC. (1
-3) Here is a comparative example (sample 14) in which no filtration is performed
No filtration was performed. (1-5) Casting process Next, concentrate the dope with a gear pump for primary pressure increase.
The primary pressure of the high precision gear pump is 0.8MPa
In addition, feedback control is possible with an inverter motor
It was cast by a functional device. High precision gear pump is volumetric efficiency
The performance was 99.2% and the discharge rate fluctuation rate was 0.5% or less.
It was. The discharge pressure was 1.5 MPa. Casting die
Is 1.4m wide and adjusted for co-casting
Equipped with locks and laminated on both sides in addition to the mainstream
Using a device that can form a three-layer film
It was. And the finished polycarbonate resin film
The film thickness will be 5μm, 90μm and 5μm, respectively.
Uni, polycarbonate resin at each die protrusion
The dope flow rate was adjusted. The total thickness of this sample is 100 μm
It was set as film sample-111. Form the outer layer
The dope supplied for the purpose is taken out from the stock tank.
Then, the additive (fine particles (silica dioxide)
Elemental (particle size 20 nm) 0.1 parts by mass and methyl acetate 1
A mixture of parts by mass)
Using a primary pressure booster gear pump and a high-precision gear pump,
Supplied to the feed block. Further, the UV agent c (2 (2'-
Hydroxy-3 ', 5'-di-tert-amylpheny
) About 0.1 parts by mass of 5-chlorobenzotriazole)
For UV absorption in pipes by UV absorption analyzer
The concentration of the agent is measured, and based on the result, the UV agent c additive solution
The predetermined UV absorption performance was realized by adjusting the flow rate. In addition,
Film thickness of polycarbonate resin completed by adjusting flow rate
Are 3 μm, 34 μm and 3 μm, respectively, for a total thickness of 40
The sample of μm was used as the film sample 112, and the finished
The film thickness of the carbonate-based resin is 10 μm and 14 respectively.
Samples with a total thickness of 160 μm were set to 0 μm and 10 μm.
Film sample 113 was obtained. Here, the die, feed block and arrangement
All tubes were kept at 35 ° C. Die is coat hanger
Type die, thickness adjustment bolts are 20mm pitch
Automatic thickness adjuster with heat bolt
The one with the structure was used. This heat bolt
High precision gear pump liquid feeding by preset program
You can also set a profile according to the amount,
Based on the profile of the infrared thickness gauge installed in the process
Possible feedback control by adjustment program
It has the ability. Excluding the casting edge 20mm
The difference in thickness between any two points 50 mm apart on the film is 1 μm
The difference between the maximum and minimum values of the thickness in the width direction is 1 μm / m
It adjusted so that it might become the following. In addition, the average thickness of each layer
The degree is controlled within ± 2% for both outer layers and ± 1% for mainstream.
The overall thickness was adjusted to ± 1.5% or less. Die primary
A chamber for decompressing was installed on the side. This decompression
The degree of decompression of the chaber is 1 to 1000 m before and after the casting bead.
It is designed to apply a pressure difference of Pa.
It can be adjusted according to the speed. At that time,
Set pressure difference so that bead length is 5-40mm
did. The temperature of the chamber is the condensation of the gas around the casting
It has a mechanism that can be set higher than the temperature.
It was. (1-6) Casting die The die material used is made of precipitation hardening stainless steel.
Coefficient of thermal expansion is 2 × 10 ^-Five(℃^-1) The following materials, electric
It is almost the same as SUS316 in the forced corrosion test with a denatured aqueous solution.
Corrosion resistant material was used. Methylene chloride,
Even if it is immersed in a mixture of methanol and water for 3 months, it will remain at the gas-liquid interface.
Uses corrosion-resistant material that does not cause pitting
did. Furthermore, grinding that has been aged for more than one month after casting
The surface of the polycarbonate resin film
The shape was kept constant. Casting die and feed block
The finishing accuracy of the wetted surface is 1 μm or less in surface roughness, straightness
Is 1 μm / m or less in any direction,
Clearance is automatically adjusted to 0.5-3.5mm
It was adjustable. At the corner of the wetted part at the tip of the die lip
R is less than 50μm across the entire width of the slit.
Processed. Shear rate inside the die is 1 to 5000
The range was (1 / sec). Furthermore, the die slit
The dope flowing out at the end is locally dried and solidified.
In order to prevent this, acetic acid
The chill is 0.5 on one side to the gas-liquid interface between the bead end and the slit.
Feeded at ml / min. Pulsation rate of the pump supplying this liquid
Was less than 5%. (1-7) Metal support A dope for co-casting with 3 layers is 2.1m wide and 15m long
Cast on a stainless steel endless band. band
Has a thickness of 1.5 mm and a surface roughness of 0.05 μm or less.
What was grind | polished so that it might become down was used. The material is SUS
Made of 316, with sufficient corrosion resistance and strength
used. The thickness unevenness of the entire band is 0.5% or less
It was. The band was driven by two drums. With band
Drive relative to the drum with a relative speed difference of 0.01 m / min or less.
The band tension at the time was adjusted to 15 tons / m. Ma
The band drive speed fluctuation was 0.5% or less. Ba
Detect and control the position of both ends of the
The meandering was 1.5 mm or less. Also, directly under the casting die
Up and down with drum rotation on the surface of the band (metal support)
The positional variation in the direction was 200 μm or less. Band width
The ratio of casting width to 89% was 89%. Casting drum
Is equipped with a facility to circulate refrigerant inside, belt (metal
The support was allowed to cool. The other drum has heat
The medium was passed through to supply heat to the belt. Each refrigerant
And the temperature of the heating medium are 10 ° C and 50 ° C, respectively.
It was. At that time, the surface temperature of the central portion of the support immediately before casting is 20
° C. The temperature difference between both ends was 6 ° C. or less. drum
The overall heat transfer coefficient from band to band is 500 kcal / m²・
The flow rate of the heat medium was adjusted to be hr · ° C. Note that
The ram can also be a direct casting support,
In this case, the rotation unevenness was rotated with an accuracy of 0.2 mm or less.
The average surface roughness of the drum is 0.01 μm or less.
Yes, with sufficient hardness and durability by chrome plating
Is. Both drums and bands
There are no pinholes of 50 μm or more on the surface.
0μm pinhole is 1 piece / m²Below 10 μm or less
2 pinholes / m²The following support without surface defects:
Met. (1-8) Casting drying The dope cast on the band is first dried in parallel flow.
And dried. From drying wind to dope when drying
Overall heat transfer coefficient is 24 kcal / m²・ Hr ・ ℃
It was. The temperature of the drying air is 140 ° C at the top of the band and 10 at the bottom.
The temperature was 0 ° C. The saturation temperature of each gas is -10 ° C and
And -6 ° C. Acid in a dry atmosphere on the support
The elementary concentration was kept at 5% by volume. Wind shield for 5 seconds after casting
So that the dry wind does not directly hit the dope.
Static pressure fluctuations immediately near the casting die were suppressed to 1 mPa or less. Do
When the solvent ratio in the loop reaches 150% by mass on a dry basis
It peeled from the casting support body at the point. Release tension at this time
Is 10 kgf / m, stripped against the support speed
The speed was set to 1.15 times. Also, the stripped web
The surface temperature of was 30 ° C. The drying speed on the support is
The average was 60% by mass dry solvent based solvent / minute. Dry out
The generated solvent gas is led to a condenser and liquefied at -10 ° C.
Then, it was recovered and reused as a charging solvent. Solvent
The removed drying air is heated again and reused as drying air.
It was. At that time, the amount of water contained in the solvent should be 0.15% or more.
Adjusted below and reused. (1-9) Tenter Transport / Drying Process Conditions Remove the peeled web with both tenters with clips.
Transported into the drying zone while fixing the edges,
Dried. The tenter is driven by a chain and its sp
The rocket speed fluctuation was less than 0.5%. Also dry
The drying air temperature is 140 ° C, and the overall heat transfer coefficient from the drying air
Is 70 kcal / m²· Hr · ° C. Dry-style moth
The gas composition was a saturated gas concentration of −30 ° C. In the tenter
The average drying rate was 120% by weight dry solvent based on solvent / minute.
It was. At the tenter outlet, the amount of residual solvent in the film is
It was 15 mass% or less. While transporting in the tenter,
Stretching was also performed in the width direction. From the tenter entrance to the exit
The draw ratio was 5%. The stretch ratio in the tenter
Substantially extended at a part more than 10mm away from the biting part
The difference in elongation is 10% or less, and 20 mm away
The difference in the stretching ratio at two points was 5% or less. At the base end
The ratio of the length fixed with the tenter is 70%.
It was. Also, the temperature of the tenter clip does not exceed 50 ° C
It was conveyed while cooling. Solvent evaporated in the tenter
The agent was condensed and liquefied at a temperature of −30 ° C. and recovered. solvent
Adjust the amount of water contained in the water to 0.15 mass% or less and reuse
I used it. Cut the ears at both ends within 30 seconds from the tenter exit
went. 50mm ears on both sides with rotary cutter
Cut the cut ears with a cutter blower.
80mm on average, blown to the shear²Degree of powder into chips
Crushed. This chip is used again as a raw material for polycarbonate.
As a raw material in the preparation process together with nate resin flakes
Secured to use. Acid in the dry atmosphere of the tenter
The elementary concentration was kept at 5% by volume. (1-10) Post-drying process conditions Polycarbonate system after ear cutting obtained by the method described above
The resin film was dried at high temperature in the roller conveyance zone.
At this time, the film surface temperature is set to 140 ° C at maximum and the roller
-Conveyance tension is 2kgf / mm²As finally
About 10 minutes until the residual solvent amount becomes 0.3 mass% or less
While it was dry. The wrap angle of the roller is 90 degrees and
And 180 degrees. The roller is made of aluminum.
The surface was hard chrome plated. Roll surface
The shape is flat and matted by blasting
Used. All the vibrations due to the rotation of the roller are 5
It was 0 μm or less. Also, tension 1.0kgf /
mm²So that the roller deflection at 0.5mm is 0.5mm or less
Selected. The film voltage during transportation is always 1.5 kV.
Forced static eliminator (static neutralization bar) during the process so that
installed. Solvent gas contained in the drying air is adsorbed.
Adsorption recovery was removed. Adsorbent is silica gel and activated carbon
Yes, desorption was performed using dry nitrogen. The recovered solvent
Adjust the water content to 0.15% by weight or less as a charged solvent
Reused. In addition to solvent gas, the drying air contains plasticizer and UV absorption.
Collect and collect high-boiling substances and remove them by cooling.
Remove these with a cooler and pre-adsorber and remanufacture
Used cyclically. Finally, VO in the outdoor exhaust gas
Adsorption / desorption conditions are set so that C is 10 ppm or less.
It was. The amount of solvent recovered by the condensation method of all evaporated solvents is 9
0% by mass, most of the rest is recovered by adsorption recovery
It was. (1-11) Post-processing and winding conditions The polycarbonate resin film after drying
Cool down and cut off 30mm on both ends and fill
Knurling was performed at both ends of the system. Knurling from one side
The width to be imparted and knurled by embossing is
10 mm, maximum height is 5 μm on average than average thickness
The pressing pressure was set to be higher. Just before knurling
The film temperature is 150 ° C, the temperature immediately after knurling
Was adjusted to 80 ° C. or lower. Obtained in this way
Polycarbonate resin film (sample 111 (thickness
The final width of 80 μm) was 1400 mm. roll
The core diameter is 180mm and the tension is 2.0kg.
f / mm²The end of winding is 0.8 kgf / mm²In
Gradually increase the tension in the longitudinal direction so that
Pattern. The total winding length is 500m
It was. Also, the press roll is pressed against the take-up roll and the pressure is 10
kgf / m was set. The film temperature during winding is 2
5 ° C, water content 0.6% by mass, residual solvent content 0.15
The amount was%. The average drying speed is 20 quality throughout the entire process.
% By dry weight basis solvent / min. Also loose winding, wrinkles
And no winding slip occurred. Also, the roll appearance is good
It was good. The residual solvent was 0.1% by mass. Also,
Slow axis angle distribution and retardation distribution are 0.5% or less
It was in. The film thus prepared was used as Sample 11.
It was set to 1. In the manufacture of sample 111, polycarbonate
PC-A used for the preparation of the resin resin solution
Except for replacing with carbonate resin (PC)
Sample 12 (Comparative Example) was manufactured. Sodium hydroxide water
A solution is charged with 53.2 g of bisphenol A and a small amount.
Of hydrosulfite followed by methylene chloride
In addition, phosgene was blown in for about 60 minutes at 20 ° C.
Then add triethylamine and stir at 30 ° C for about 3 hours.
Stir to obtain polycarbonate resin (PC)
([Η] = 0.75). In the manufacture of sample 111,
The concentration of the resin is reduced by preparing a carbonate resin solution.
The viscosity at the casting temperature (35 ° C.) is 2 Pa · s.
Sample 13 (Comparative Example) was produced in the same manner except that.
In the manufacture of sample 111, the polycarbonate resin solution
Sample 14 (Comparative), except that the liquid was not filtered
Example) was produced. In the manufacture of sample 111, the drying process
In the same manner except that the drying air temperature at 50 ° C.
Sample 15 (Comparative Example) was manufactured. For the manufacture of sample 111
And a polycarbonate resin solution having an average pore size of 30 μm
And filter using a 5 μm filter and dry
The drying air temperature in the process was set to 70 ° C. and 150 ° C.
Sample 16 (the present invention) was produced in the same manner except for the above. each
Table 1 shows various conditions for manufacturing the sample. In addition, the viscosity in Table 1
Is a static non-ni, which has the same temperature as the solution just before casting each sample.
Newton viscosity n^*(Pa · s)
This is as described above. (1-12) Evaluation result Table 1 shows samples 11 and 16 of the present invention and comparative samples 12-1
The evaluation result about 5 is shown. In Table 1, surface unevenness
And A to D in the column of “V” and A to D in the column of film strength are
It means below. <Surface unevenness> Visual observation under a fluorescent lamp
Ejectivity was evaluated. A: Reflection unevenness was not recognized. B: Some reflection unevenness was recognized. C: Reflection unevenness is clearly recognized and is not satisfied as a product
Minutes. D: Reflection unevenness is recognized on the entire surface, and as a product
It was insufficient. 《Surfaced irregularities》 Visual observation under incandescent lamp
Tsu was evaluated. A: No irregularities were found. B: Some irregularities were observed. C: The product is clearly recognized and not enough as a product
there were. D: Goods are recognized on the entire surface, which is insufficient as a product
It was. << Membrane Strength >> The film is heated to 150 ° C. and 500 g / c
The deformation was examined by pulling with a force of m. A: Deformation was not recognized. B: An elongation of less than 1% was observed. C: Elongation of 5% or more is recognized, and it is a problem as a product
there were. D: Elongation of 10% or more is recognized, and it is a problem as a product
Met. Comparative sample 12 has insufficient film strength,
In addition, the comparative sample 13 having a low resin solution concentration has unevenness,
The haze was remarkably large and the haze was large. More
In addition, the comparative sample 14 that has not been filtered has noticeable roughness.
There are many comparative samples 15 with low drying air in the drying process.
The surface condition was inferior. In contrast, the sample 11 of the present invention.
1 (thickness 100 μm) and 116 are excellent in all respects
Met. Further, the samples 112 and 1 of the present invention having different thicknesses are used.
13 also has excellent surface shape, haze and film strength.
It was. Furthermore, the sample 111 of the present invention has zero bright spot foreign matter.
In contrast, the comparative sample 14 has 100 bright spot foreign materials.
It was the above and it was extremely bad. Also the thickness is different
Samples 12 and 13 are both planar, haze, and bright spot foreign matter.
I confirmed that it was. [0145] [Table 1][Example 2] In Example 1, the present invention was
In sample 111, (2-1) its thickness after the stretching step
Except that the thickness is increased so that becomes 100 μm.
Sample 21A was produced in exactly the same manner as Example 111. (2-1) Stretching Longitudinal uniaxial extension of about 1.71 times actual temperature at 216 ° C
Stretched to obtain a λ / 4 plate (21B). (2-2) Heat treatment The above λ / 4 plate (21B) is subjected to the following heat treatment conditions:
Samples 21 to 27 were obtained by carrying out low tension conveyance processing. However, ratio
Some were not processed for comparison. (1) Transfer heat treatment Set the temperature and tension described in Table 2 respectively.
In addition, a heat treatment zone with a total length of 200 m is transported at a speed of 20 m / min.
And was subjected to low-tension transfer heat treatment. (2) Roll heat treatment Through the heat treatment zone set to the temperature described in Table 2, respectively.
After that, it is straightened with the tension shown in Table 2 under the temperature atmosphere.
It wound up on the core of diameter 30cm. After this, 0.2 rotation / hour
Cooling to room temperature at -1 ° C / hour while rotating between
A low tension roll was heat treated. Dimensional changes and optics for each sample
The characteristic change was evaluated, and the results are shown in Table 3. (Result) In the present invention, as shown in Samples 21 to 24, the hypotonicity
The thermal dimensional change at 100 ° C is extreme by performing the heat treatment.
Is small, and the change in optical properties is small, which is preferable.
Met. [0148] [Table 2] [0149] [Table 3] [0150] According to the present invention, with respect to temperature and humidity,
Excellent dimensional stability and excellent surface properties
Providing a method for producing polycarbonate resin films
can do. Especially used as retardation film
In this case, a polycarbonate resin with excellent optical properties is made.
A method of building can be provided.

──────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme code (reference) C08L 69:00 C08L 69:00 F-term (reference) 2H049 BA04 BA06 BA07 BB44 BC22 4F071 AA50 AA86 AA88 AF10 AF30 AH16 BB02 BC01 4F205 AA28 AC05 AG01 AH73 AR06 AR17 GA07 GB02 GC07 GF03 GF24

Claims (1)

What is claimed is: 1. A glass transition point (Tg) obtained by copolymerizing at least one bisphenol derivative comprising a fluorene skeleton and a bisphenol derivative comprising at least one non-fluorene skeleton at 150 ° C. A filtration step of filtering the polycarbonate resin solution containing 10 to 40% by mass of the above polycarbonate resin and having a viscosity at the time of casting of 10 to 200 Pa · s at least once with a filter having an average pore diameter of 1 to 50 μm; A casting step of casting the solution on a metal support to form a web; a step of peeling the web from the metal support; and drying the peeled web at 60 to 250 ° C. Polycarbonate-based resin fill including a drying process for drying at wind temperature to obtain a film and a winding process for winding the dried film Manufacturing method.