KR20100036931A - Method and apparatus for manufacturing retardation film - Google Patents
Method and apparatus for manufacturing retardation film Download PDFInfo
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- KR20100036931A KR20100036931A KR1020090077287A KR20090077287A KR20100036931A KR 20100036931 A KR20100036931 A KR 20100036931A KR 1020090077287 A KR1020090077287 A KR 1020090077287A KR 20090077287 A KR20090077287 A KR 20090077287A KR 20100036931 A KR20100036931 A KR 20100036931A
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Abstract
The TAC film stored in the supply chamber is sent to the tenter portion. The tenter portion extends the TAC film in the width direction. The TAC film sent out from the tenter portion is sent to the wet gas contact chamber. The wet gas contact chamber is filled with wet gas. In the wet gas contact chamber, the TAC film is in contact with the wet gas. The TAC film sent out from the wet gas contact chamber is sent to a heat treatment chamber filled with dry air. In the heat treatment chamber, the temperature of the TAC film is maintained within a predetermined range.
Retardation film, manufacturing method of retardation film, manufacturing equipment of retardation film
Description
This invention relates to the manufacturing method of retardation film, and its manufacturing equipment.
Polymer films (hereinafter referred to as "films") have been used in various fields as optical functional films because of their excellent light transmittance, flexibility and light weight. Among the films, TAC films formed from cellulose acylate, in particular cellulose triacetate (hereinafter referred to as TAC) having an average degree of oxidation of 57.5% to 62.5%, are protective films for polarizing plates and retardation of liquid crystal displays in which the market is rapidly expanding. It is used as optical functional films, such as a film.
Main methods for producing the film include a melt extrusion method and a solution film forming method. The melt extrusion method is a method of producing a film by heating and dissolving a polymer and then extruding it with an extruder, and has the characteristics of high productivity and relatively low equipment cost. However, this melt extrusion method is not suitable for the manufacturing method for optically functional films because it has difficulty in controlling the precision of the film thickness and also has the drawback that thin streaks (die lines) are easily formed on the film. On the other hand, the solution film-forming method flows out the polymer solution containing a polymer and a solvent (henceforth dope) on a support body, and forms the cast film which consists of dope on a support body. Subsequently, after the flexible film becomes self-supporting, the flexible film is peeled off from the support to obtain a wet film. Then, it is a method of drying a wet film and winding up as a film. This solution film-forming method is suitable for the method for producing an optically functional film because the film thickness is excellent compared to the melt extrusion method and a film with few foreign matters can be obtained.
As a method of expressing self-supportability in the flexible film in the solution film forming method, a method of drying the flexible film on the support to reduce the amount of residual solvent in the flexible film until it reaches a predetermined range (hereinafter referred to as a drying method) and cooling the flexible film To form a flexible membrane (hereinafter referred to as a cooling gelation method) is known (see, for example, Japanese Patent Laid-Open No. 2002-179819).
Moreover, as a method of adjusting the optical characteristic of an optical functional film, the method of immersing a film in water, or exposing a film to water vapor and extending | stretching the film whose water content fell within the predetermined range is known (for example, Unexamined Japanese Patent 2003) -90915, Japanese Patent Laid-Open No. 2003-62899).
By the way, the endurance test which examines whether an optical functional film can ensure a fixed characteristic and quality under predetermined environmental conditions like a liquid crystal display device is performed. By the way, when the endurance test was performed to this optical functional film, it turned out that the optical characteristic of an optical functional film will change. In particular, the retardation (Rth) in the thickness direction is greatly varied before and after the endurance test (hereinafter referred to as a wet heat endurance test) under conditions of high temperature and high humidity (for example, a temperature of 60 ° C or more and a humidity of 90% RH). As a result of throwing away, the phenomenon that the retardation (Rth) of a film largely deviates from the range suitable for a liquid crystal display device frequently occurred.
Japanese Unexamined Patent Application Publication No. 2002-179819 discloses a method in which a film obtained by a solution film forming method is subjected to a humidification process to suppress dimensional change of a film under a high temperature and high humidity environment. This is to remove the strain in the film by using the phenomenon that the glass transition temperature (Tg) is lowered due to the increase in the moisture content of the film. However, this publication does not describe the influence of the humidification treatment on the retardation (Re, Rth), which are important optical properties in the retardation film. It is believed that in the person skilled in the art, this humidification treatment removes the strain in the film, but as a result, the retardation (Re, Rth) is reduced as a result of the orientation being relaxed by the removal of the strain. As mentioned above, it is difficult to apply the humidification process of Unexamined-Japanese-Patent No. 2002-179819 to the manufacturing method of retardation film with high retardation (Re, Rth).
Moreover, the method described in Unexamined-Japanese-Patent No. 2003-90915 and Unexamined-Japanese-Patent No. 2003-62899 relates to the manufacturing method of the film which obtains another Nz factor in Re of (lambda) / 4 vicinity, and each retardation (Re, It is not suitable for the manufacturing method of retardation film with high Rth).
The objective of this invention is providing the manufacturing method of retardation film which can manufacture retardation film with small amount of fluctuation | variation of the optical characteristic and dimension before and after an endurance test, and its manufacturing equipment.
In order to achieve the said objective and other objective, the manufacturing method of the retardation film of this invention draws a polymer film. The stretching adjusts the optical properties of the polymer film. Water vapor is brought into contact with the polymer film that has undergone the stretching step. The temperature Tf1 of the polymer film while in contact with the water vapor is maintained within a range of 100 ° C or more and 150 ° C or less. Dry gas is brought into contact with the polymer film which has undergone contact step with the water vapor. The temperature of the polymer film during contact with the dry gas is maintained in the range of 120 ° C or more and 130 ° C or less.
The method for producing a retardation film of the present invention further makes a dew point having a dew point lower than the temperature Tf1 in contact with the polymer film between the stretching step and the contact step with the water vapor. The temperature of the polymer film during contact with the low dew point drying gas is maintained within a range of 100 ° C or more and 130 ° C or less.
The contact with the dry gas is performed for 1 minute to 4 minutes. The water vapor is contacted for 5 seconds to 60 minutes. A gas containing the water vapor is brought into contact with the polymer film that has undergone the stretching step, and the relative humidity of the gas is 20% RH or more.
In-plane retardation Re of the retardation film is 30 nm or more and 100 nm or less, and thickness direction retardation Rth of the retardation film is 70 nm or more and 300 nm or less.
The manufacturing method of the retardation film of this invention pulls out the strip | belt-shaped polymer film further from the said roll-shaped polymer film before the extending | stretching step.
The manufacturing method of the retardation film of this invention further forms a casting | flow_spread film in the support body which flows out the dope containing a polymer and a solvent using a die | dye. The flexible membrane is cooled until the flexible membrane becomes self supporting. The cast film is peeled off from the support as a wet film. The solvent is evaporated from the wet film to form the polymer film. Evaporation of the solvent from the wet film is performed continuously with the stretching.
The manufacturing method of the retardation film of this invention further forms a casting | flow_spread film in the support body which flows out the dope containing a polymer and a solvent using a die | dye. The solvent is evaporated from the flexible membrane until the flexible membrane becomes self supporting. The cast film is peeled off from the support as a wet film. The solvent is evaporated from the wet film to form the polymer film. Evaporation of the solvent from the wet film is performed continuously with the stretching.
The residual solvent amount of the polymer film at the start of contact with the water vapor is 5% by weight or less. The polymer film contains cellulose acylate.
In order to achieve the above object and other objects, the production equipment of the retardation film of the present invention comprises a drawing device for drawing a polymer film, a water vapor contacting device for bringing water vapor into contact with the stretched polymer film, and a contact with the water vapor. A dry gas contact device for bringing dry gas into contact with the polymer film. The stretching apparatus adjusts the optical properties of the polymer film by the stretching. The water vapor contacting device maintains the temperature Tf1 of the polymer film while in contact with the water vapor within a range of 100 ° C or more and 150 ° C or less. The dry gas contact device maintains the temperature of the polymer film while in contact with the dry air within a range of 120 ° C or more and 130 ° C or less.
The production equipment for the retardation film of the present invention also includes a low dew point dry gas contact device for bringing a dew point of a dew point lower than the temperature Tf1 into the polymer film after the stretching and before contact with the water vapor. . The low dew point dry gas contact device maintains the temperature of the polymer film in the range of 100 ° C. or higher and 130 ° C. or lower during contact with the low dew point dry gas.
The water vapor contact device has a first casing filled with the water vapor and a first introduction means for introducing the polymer film into the first casing. The low dew point dry gas contact device includes a second casing filled with the low dew point dry gas, and second introduction means for introducing the polymer film into the second casing. The first casing is installed inside the second casing.
The water vapor contact device contains the water vapor so that a relative humidity of 20% RH or more of gas is brought into contact with the polymer film.
According to this invention, it becomes possible to manufacture the film with a small amount of fluctuation | variation of the optical characteristic and dimension before and after an endurance test. Therefore, according to this invention, the retardation film which can exhibit the stable optical characteristic can be provided, regardless of the change of the temperature and humidity of a use environment.
The above objects and advantages will be readily understood by those skilled in the art by referring to the accompanying drawings and reading the detailed description of the preferred embodiments.
As shown in FIG. 1, the
As shown in FIG. 2, the
The film holding position PA is formed in the upstream of the conveyance path of the
The first and
As shown in FIG. 1, the
The winding
The wet
As shown in FIG. 3, the wet
Moreover, the piping which connects the
The
A part of the
Next, the effect | action of this invention in the
The air conditioner which is not shown in figure adjusts the atmospheric temperature, humidity, solvent dew point, etc. in the
As shown in FIG. 1, the wet
The
The present invention performs a water vapor contact treatment for bringing the
Thus, according to the present invention, the variation (ΔRth WET) of a thickness direction retardation (Rth) in the wet heat durability tests before and after this it is possible to manufacture the
It is preferable that it is 100 degreeC or more, and, as for the minimum of the temperature Tf1 of the
In order to increase the inhibitory effect of ΔRth WET , the humidity Hu1 of the
In addition, although the range of the processing time P1 of a steam contact treatment is not specifically limited, If it is in the range in which the effect of this invention is exhibited, it is preferable to be as short as possible from a point of production efficiency. As an upper limit of processing time P1, it is preferable that it is 60 minutes or less, for example, and it is more preferable that it is 10 minutes or less. On the other hand, the lower limit of the processing time P1 is preferably, for example, 5 seconds or more, more preferably 10 seconds or more, and particularly preferably 30 seconds or more.
As shown in FIG. 3, hard water, pure water, etc. can be used besides the
In addition, the pure egg electrical resistivity in the specification of the present invention is at least 1 MΩ or more, especially the content concentration of metal ions such as sodium, potassium, magnesium, calcium, etc. is less than 1 ppm, and anions such as chlorine and nitric acid contain less than 0.1 ppm. Indicates concentration. Pure water can be easily obtained by a single or combination of reverse osmosis membranes, ion exchange resins, distillation and the like.
Instead of the
In the above embodiment, the
In the above embodiment, the water vapor contact treatment is performed in the wet
In the water vapor contact treatment of the above embodiment, the water vapor was brought into contact with the
It is preferable to use the
It is preferable that the width | variety of the
It is preferable to use the thing manufactured by the solution film forming method for the
As shown in FIG. 5, the
The casting die 84 continuously discharges the casting dope 81 to the circumferential surface 82b. The discharged cast dope 81 is cast on the circumferential surface 82b and forms the
The
Moreover, in the
In the drying
The
The film manufacturing equipment for performing a solution film forming method is not limited to the said
In the said embodiment, although the extending | stretching process was performed to the
In the said embodiment, after winding up the
In the said embodiment, although the
(Heat treatment)
It is preferable to perform the heat processing which makes the temperature of the
It is preferable that it is 110 degreeC or more, and, as for the minimum of the temperature Tf2 of the
Moreover, it is preferable that it is 5 minutes or less, and, as an upper limit of the processing time P2 of heat processing, it is more preferable that it is 4 minutes or less. On the other hand, it is preferable that it is 1 minute or more as a minimum of processing time P2. If the treatment time P2 exceeds 5 minutes or less than 1 minute, the amount of change in each retardation, the amount of change in the dimension in the X direction, and the amount of change in the dimension in the Y direction before and after the wet heat endurance test and the dry heat endurance test cannot be suppressed. Because it is not desirable.
As shown in FIG. 7, heat processing is performed in the
(Condensation prevention processing)
In order to suppress condensation in the
The temperature of the low dew
As shown in FIG. 7, the dew condensation prevention process is performed in the condensation
In addition, as shown in FIG. 8, you may use the wet
According to the present invention, when the dope is flexible, a simultaneous lamination shared lead in which two or more types of dopes are co-leaded and laminated at the same time, or a sequential lamination shared lead in which a plurality of dopes are sequentially laminated and laminated. In addition, you may combine both covalent lead. When performing simultaneous lamination sharing, a flexible die with a feed block may be used, or a multi-pocket flexible die may be used. However, it is preferable that at least any one of the layer thickness of an air surface side, and the layer thickness of a support body side is 0.5-30% of the film total thickness in the film which consists of multilayers by covalent lead. In addition, in the case of performing simultaneous lamination sharing, it is preferable that the high-viscosity dope is wrapped by the low-viscosity dope when the dope is cast from the die slit to the support. It is preferable that the composition ratio of alcohol is larger than internal dope.
In the above embodiment, the water vapor contact treatment is performed using the
In the said embodiment, although TAC film was used, this invention is not limited to a TAC film, The polymer film obtained by the solution film forming method from other polymers, such as a cellulose acylate and a cyclic polyolefin, and the polymer film manufactured by the melt film forming method It is available.
(Cellulose acylate)
As cellulose acylate, triacetyl cellulose (TAC) is particularly preferable. And it is more preferable that the ratio in which the hydroxyl group of a cellulose is esterified with carboxylic acid among a cellulose acylate, ie, the substitution degree of an acyl group, satisfy | fills all following formula (I)-(III). In the following formulas (I) to (III), A and B represent a degree of substitution of an acyl group, A is a degree of substitution of an acetyl group, and B is a degree of substitution of an acyl group having 3 to 22 carbon atoms. to be. Moreover, it is preferable that 90 weight% or more of TAC is 0.1 mm-4 mm of particle | grains.
(I) 2.5≤A + B≤3.0
(II) 0≤A≤3.0
(III) 0≤B≤2.9
Glucose units bound to β-1,4 constituting cellulose have free hydroxyl groups at the 2, 3 and 6 positions. Cellulose acylate is a polymer (polymer) in which some or all of these hydroxyl groups are esterified by acyl groups having 2 or more carbon atoms. Acyl substitution degree means the ratio (100% esterification is substitution degree 1) in which the hydroxyl group of a cellulose is esterified with respect to 2-position, 3-position, and 6-position, respectively.
As for all acylation substitution degree, ie, DS2 + DS3 + DS6, 2.00-3.00 are preferable, More preferably, it is 2.22-2.90, Especially preferably, it is 2.40-2.88. Moreover, as for DS6 / (DS2 + DS3 + DS6), 0.28 or more are preferable, More preferably, it is 0.30 or more, Especially preferably, it is 0.31-0.34. Here, DS2 is the substitution degree by the acyl group of the hydroxyl group of 2-position of a glucose unit (henceforth "acyl substitution degree of 2-position"), and DS3 is the substitution degree by the acyl group of the hydroxyl group of 3-position (hereinafter, " 3-position acyl substitution degree ", and DS6 is the substitution degree (henceforth" acyl substitution degree of 6-position ") by the acyl group of the 6-position hydroxyl group.
Only one kind of acyl group may be used for the cellulose acylate of the present invention, or two or more kinds of acyl groups may be used. When using two or more types of acyl groups, it is preferable that one of them is an acetyl group. If the sum of substitution degree by hydroxyl group of 2, 3 and 6 position is DSA, and the sum of substitution degree by acyl group other than acetyl group of hydroxyl group of 2, 3 and 6 position is DSB, DSA + DSB The value of is more preferably 2.22 to 2.90, and particularly preferably 2.40 to 2.88. Moreover, DSB is 0.30 or more, Especially preferably, it is 0.7 or more. In addition, DSB is 20% or more of the substituent of the 6-position hydroxyl group, more preferably 25% or more of the substituent of the 6-position hydroxyl group, 30% or more is more preferable, in particular 33% or more is a substituent of the 6-position hydroxyl group It is preferable. Moreover, the substitution degree of the 6-position of a cellulose acylate is 0.75 or more, More preferably, it is 0.80 or more, Especially preferably, the cellulose acylate of 0.85 or more is mentioned. By these cellulose acylates, a solution (dope) in which solubility is preferable can be produced. In particular, preparation of a favorable solution in a non-chlorine organic solvent is attained. In addition, it is possible to produce a solution having a low viscosity and good filterability.
The cellulose which is a raw material of cellulose acylate may be obtained from any one of a linter and a pulp.
The acyl group having 2 or more carbon atoms of the cellulose acylate of the present invention may be an aliphatic group or an aryl group, and is not particularly limited. They are alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc. of cellulose, for example, and may further have a substituted group, respectively. Preferred examples thereof include propionyl, butanoyl, pentanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butayl Noyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleyl, benzoyl, naphthylcarbonyl, cinnamoyl, and the like are more preferable, and particularly preferably propionyl and butanoyl.
(solvent)
As a solvent for preparing the dope, an aromatic hydrocarbon (for example, benzene, toluene, etc.), a halogenated hydrocarbon (for example, dichloromethane, chlorobenzene, etc.), an alcohol (for example, methanol, ethanol, n-propanol, n- Butanol, diethylene glycol, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), esters (e.g. methyl acetate, ethyl acetate, propyl acetate, etc.) and ethers (e.g. tetrahydrofuran, methyl Cellosolve, etc.) etc. are mentioned. In addition, in this invention, dope means the polymer solution obtained by melt | dissolving or disperse | distributing a polymer in a solvent, and a dispersion liquid.
Among these, halogenated hydrocarbons having 1 to 7 carbon atoms are preferably used, and dichloromethane is most preferably used. From the viewpoints of physical properties such as TAC solubility, peelability from the support of the flexible membrane, mechanical strength of the film, and optical properties of the film, it is preferable to mix one or several alcohols having 1 to 5 carbon atoms in addition to dichloromethane. . 2 weight%-25 weight% are preferable with respect to the whole solvent, and, as for content of alcohol, 5 weight%-20 weight% are more preferable. Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol and the like, but methanol, ethanol, n-butanol or a mixture thereof is preferably used.
By the way, the solvent composition in the case of not using dichloromethane for the purpose of minimizing the influence on the environment in recent years is also examined. For this purpose, the ether having 4 to 12 carbon atoms and the 3 to 3 carbon atoms is studied. 12 ketones, esters of 3 to 12 carbon atoms, and alcohols of 1 to 12 carbon atoms are preferably used. These may be mixed and used suitably. For example, the mixed solvent of methyl acetate, acetone, ethanol, n-butanol is mentioned. These ethers, ketones, esters and alcohols may have a cyclic structure. Moreover, the compound which has two or more of functional groups of ether, ketone, ester, and alcohol (namely, -O-, -CO-, -COO-, and -OH) can also be used as a solvent.
In addition, the detail of cellulose acylate is described in the paragraphs [0140]-[0195] of Unexamined-Japanese-Patent No. 2005-104148. These descriptions can also be applied to the present invention. In addition, additives such as solvents and plasticizers, anti-degradants, ultraviolet absorbers (UV agents), optically anisotropic control agents, retardation control agents, dyes, matting agents, release agents, and release accelerators are similarly described in Japanese Patent Application Laid-Open No. 2005-104148. ] To the paragraph [0516].
(Usage)
The polymer film of this invention is useful as a polarizing plate protective film or retardation film. An optically anisotropic layer, an antireflection layer, an antiglare functional layer, etc. may be provided to this polymer film, and it may be set as a high function film.
When used as a retardation film, it is preferable that in-plane retardation Re of a polymer film is 30 nm or more and 100 nm or less, and it is preferable that thickness direction retardation Rth of a retardation film is 70 nm or more and 300 nm or less.
(Melt film production facility)
Next, the melt
In the lateral stretched
After the post-heat treatment is performed after lateral stretching, the lateral stretched film Fb is shrunk in the A direction in the
The lateral stretched film Fb is shrink-treated in the
You may extend in A direction before or after extending | stretching to B direction. Stretching in the A direction can be achieved by conveying the film using a plurality of nip roll pairs arranged in the A direction, and making the peripheral speed of the nip roll pair on the downstream side faster than the peripheral speed of the upstream nip roll pair. The stretching method differs depending on the size of the distance (L) between the nip rolls in the A direction and the ratio (L / W) of the film width (W) in the upstream nip roll pair. A stretching method in the A direction can be employed, such as those described in -330411 and Japanese Unexamined Patent Application, First Publication No. 2006-348114. This approach tends to increase Rth but makes the device compact. On the other hand, when the L / W is large, the stretching method in the A direction as described in JP 2005-301225 A can be used. This method can make Rth small, but the apparatus is likely to be large.
The polymer which can be used for a melt film forming method will not be specifically limited if it is a thermoplastic resin, For example, a cellulose acylate, a lactone ring containing polymer, a cyclic polyolefin, a polycarbonate, etc. are mentioned. Among them, preferred are cellulose acylates and cyclic polyolefins. Among these, preferred are cellulose acylates containing acetate groups and propionate groups and cyclic polyolefins obtained by addition polymerization, and more preferably cyclic polyolefins obtained by addition polymerization. .
(Cyclic polyolefin)
The cyclic polyolefin is preferably polymerized from the norbornene-based compound. This polymerization can be carried out by any of ring-opening polymerization and addition polymerization. Examples of the addition polymerization include those described in Japanese Patent No. 3517471, Japanese Patent No. 3559360, Japanese Patent No. 3867178, Japanese Patent No. 3871721, Japanese Patent No. 3907908, Japanese Patent No. 3945598 and Japanese Patent Publication 2005- The thing of 527696, Unexamined-Japanese-Patent No. 2006-28993, and international publication 2006/004376 pamphlet can be mentioned. Especially preferred are those described in Japanese Patent No. 3517471.
Examples of the ring-opening polymerization include International Publication No. 98/14499, Japanese Patent 3060532, Japanese Patent 3220478, Japanese Patent 3273046, Japanese Patent 3404027, Japanese Patent 3428176, Japanese Patent 3687231, and Japanese Patent. 3873934 and the thing of Unexamined-Japanese-Patent No. 3912159 are mentioned. Especially, the thing of international publication 98/14499 pamphlet and Unexamined-Japanese-Patent No. 3060532 is described.
Among these cyclic polyolefins, addition polymerization is more preferable.
(Lactone ring-containing polymer)
The thing which has a lactone ring structure represented by following General formula (1) is pointed out.
In general formula (1), R <1> , R <2> , R <3> represents a hydrogen atom or an organic residue of C1-C20 each independently. In addition, the organic residue may contain the oxygen atom.
The content rate of the lactone ring structure of General formula (1) becomes like this. Preferably it is 5-90 weight%, More preferably, it is 10-70 weight%, More preferably, it is 10-50 weight%.
Polymer structure formed by superposing | polymerizing at least 1 sort (s) chosen from a (meth) acrylic acid ester, a hydroxyl group containing monomer, an unsaturated carboxylic acid, and the monomer represented by following General formula (2) other than the lactone ring structure represented by General formula (1) Units (repeated structural units) are preferred.
Formula (2) of the R 4 represents a hydrogen atom or a methyl group, X is a hydrogen atom, an alkyl group of carbon number 1-20, an aryl group, an -OAc group, a -CN group, a -CO-R 5 group, or a -COR 6 group is represented, Ac group represents an acetyl group, R <5> and R <6> represents a hydrogen atom or C1-C20 organic residue.
For example, international publication 2006/025445 pamphlet, Unexamined-Japanese-Patent No. 2007-70607, Unexamined-Japanese-Patent No. 2007-63541, Unexamined-Japanese-Patent No. 2006-171464, and Unexamined-Japanese-Patent No. 2005-162835 are described. Can be used.
Example 1
Next, Example 1 of the present invention will be described with reference to some experimental results.
(Manufacture of Film)
First, the manufacturing method of each polymer film (sample No. A1-A4, B-D) used for experiment is demonstrated.
(Sample No. A1)
Sample No. Flexible dope used for manufacture of the polymer film of A1 was prepared. The raw material dope, the mat agent liquid, and the ultraviolet absorber solution were used for preparation of casting dope. Hereinafter, the detail of the preparation method of a raw material dope, a mat liquid, and a ultraviolet absorber solution is demonstrated.
[Preparation of raw material dope]
The raw material dope was prepared from the following prescription.
Cellulose triacetate (degree of substitution 2.86) 89.3% by weight
Plasticizer A (triphenyl phosphate) 7.1% by weight
Plasticizer B (biphenyl diphenyl phosphate) 3.6% by weight
Solid content (solute) which consists of composition ratio of
Methanol 13.5 wt%
6.5% by weight of n-butanol
It added to the mixed solvent which consists of these suitably, stirred and melt | dissolved, and prepared raw material dope. In addition, the TAC density | concentration of raw material dope was prepared so that it might become about 23 weight%. After filtering raw material dope with filter paper (# 63LB made by Toyo Roshi Corporation), and further filtration by a sintered metal filter (06N by Nippon Seishen Co., Ltd., 10 micrometers of nominal pore diameter), and also filtering by a mesh filter Put in stock tank.
[Cellulose triacetate]
In addition, the cellulose triacetate used here was 0.1 weight% or less of residual acetic acid, was 57 ppm of Ca, 41 ppm of Mg, 0.4 ppm of Fe, 38 ppm of free acetic acid, and 13 ppm of sulfate ions. In addition, the substitution degree of the acetyl group with respect to hydrogen of the 6-position hydroxyl group was 0.91. In addition, 32.5% of all the acetyl groups were the acetyl group which the hydrogen of the 6-position hydroxyl group substituted. In addition, the acetone extract fraction which extracted this TAC with acetone was 8 weight%, and the weight average molecular weight / number average molecular weight ratio was 2.5. Moreover, the yellow index of obtained TAC was 1.7, haze was 0.08, and transparency was 93.5%. This TAC is synthesize | combined using the cellulose collected from cotton as a raw material. In the following description, this is called cotton raw material TAC.
[Preparation of Matte Liquid]
The mat liquid was prepared from the following prescription.
Silica (Aerosil R972 made by Nippon Aerosol Co., Ltd.) 0.67 wt%
2.93% by weight of cellulose triacetate
0.23% by weight of triphenylphosphate
0.12% by weight of biphenyldiphenylphosphate
Dichloromethane 88.37 wt%
7.68% by weight methanol
The matte liquid was prepared from the said prescription, and it disperse | distributed so that it might become a volume average particle diameter of 0.7 micrometer with the attritor, and it filtered with the astrofilm filter made by Fujifilm. And it put in the tank for liquids of mats.
[Preparation of Ultraviolet Absorber Solution]
The ultraviolet absorber solution was prepared from the following prescription.
2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole 5.83 wt%
11.66% by weight of 2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole
Cellulose triacetate 1.48 wt%
0.12% by weight of triphenylphosphate
Biphenyl diphenyl phosphate 0.06% by weight
Dichloromethane 74.38 wt%
6.47% by weight methanol
The ultraviolet absorber solution was prepared from the said prescription, and it filtered in the astrofilm filter made by Fujifilm Co., Ltd., and put into the tank for ultraviolet absorption solution methods.
As shown in FIG. 5, the
(Sample No. A2-A4)
Except as shown in Table 1, the sample No. Similar to the TAC film of A1, the sample No. The TAC film (3) of A2-A4 was obtained.
(Sample No. B)
The film No. described in Example 1 of Unexamined-Japanese-Patent No. 2001-188128 using the solution film-forming method. 1 (cellulose acetate propionate:
(Sample No. C)
The melt film forming method was performed in accordance with Example 1 of the international publication 2006/025445 pamphlet, and the polymer film (100 micrometers in thickness) which consists of a lactone ring containing polymer resin was obtained. This is sample No. It is called the film of C.
(Sample No. D)
The melt film forming method was performed, and the polymer film (100 micrometers in thickness) which consists of cycloolefin resin (A) was obtained. This is sample No. The film of D is called.
Cycloolefin resin (A) (addition polymerization system): TOPAS6013 (Tg = 130 degreeC) made by Polyplastics
Sample No. The detail of the molten film forming method which produced the film of D is as follows. After drying cycloolefin resin (A) with a 110 degreeC vacuum dryer to make water content 0.1% or less, it melt | dissolved at 260 degreeC using a single screw kneading extruder, and sent out from a gear pump, and the leaf disc of filtration precision of 5 micrometers Molten resin was filtered on a filter and three cast rolls set at (Tg-5) 占 폚, Tg 占 폚 and (Tg-10) 占 폚 from a hanger coat die having a slit interval of 0.8 mm and 270 占 폚 via a static mixer. Extruded. At this time, the touch roll was made to contact the cast roll of the uppermost side by surface pressure of 0.1 Mpa, and the unstretched film of thickness 100micrometer was formed into a film. The touch roll was temperature-controlled at (Tg-5) degreeC using what was described in Example 1 (it is described as a double suppression roll) of Unexamined-Japanese-Patent No. 11-235747 (However, a thin metal outer cylinder thickness is 2 mm).
Then, after trimming both ends (each 3% of the whole width) just before winding, thickness forming process (knurling) of width 10mm and height 20micrometer was performed at both ends. Each level was 1.5m wide and wound 3000m for 30m / min.
In addition, CAP shown in Table 1 represents a cellulose acetate propionate, a lactone shows a lactone ring containing polymer resin, and a cycloolefin shows a cycloolefin resin (A), respectively. Substitution degree A is a substitution degree by an acetyl group, and substitution degree B is a substitution degree by a propionyl group. The addition amount shown in Table 1 is an addition amount of the retardation additive shown to the following general formula. In addition, the film | membrane shown in Table 1 is the thickness of the obtained polymer film.
As shown in FIG. 1, each polymer film (sample No. A1-A4, B-D) obtained by the said method was accommodated in the supply part 4 of the
(Experiment 1-35)
The TAC film 3 (Sample No. A1) subjected to the stretching treatment in the
In addition, TH0, Re0, Rth0, Ha1, and Ha2 in Table 3 are TAC films (3) after the dew condensation prevention treatment, the water vapor contact treatment, and the heat treatment under the conditions shown in Table 2, and before the wet heat endurance test and the dry heat endurance test. ) Film thickness, in-plane retardation, thickness direction retardation, haze and internal haze. In addition, "-" shown in Table 3 shows that the value of the corresponding parameter is unmeasured.
(Measurement method of in-plane retardation (Re))
The sample film was humidified for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, and the following formula was obtained from the extrapolation value of the retardation value measured from the vertical direction at 589.3 nm with an automatic birefringence meter (KOBRA21DH Oji Keisoku Co., Ltd.). Calculated according to.
Re = | nX-nY | × d
nX represents a refractive index in the X direction, nY represents a refractive index in the Y direction, and d represents the thickness of the sample film.
(Measurement method of thickness direction retardation (Rth))
The sample film is humidified for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, and the value measured from the vertical direction at 589.3 nm with an automatic birefringence meter (KOBRA21DH Oji Keisoku Co., Ltd.) and the film plane are inclined similarly. It was computed according to the following formula from the extrapolation value of the measured retardation value.
Rth = {(nX + nY) / 2-nTH} × d
nTH represents the refractive index of the thickness direction.
(Measuring method of haze)
The haze is a sample film that is cut out of each polymer film into a size of 40 mm x 80 mm, and a haze meter (type: HGM-2DP, Suga Shikenki) is used for this sample film under an environment of 25 ° C 60% RH. Was measured according to JIS K-6714.
(Measurement method of internal haze)
Internal haze was measured as follows. After humidifying a sample film at 25 degreeC 60% RH for 2 hours or more, it inserted into two slide glass plates through the liquid paraffin, and measured the haze of the sample film with the haze meter (HGM-2DP, Suga Shikenki). Moreover, the blank sample of the state which only sandwiched the flow paraffin without the sample film was created in two slide glass plates, and the haze of this blank sample was measured. And the internal haze was made by subtracting the haze measurement of the blank sample from the haze measurement of the sample film.
The following test was done about the
(Hot Heat Endurance Test)
The sample film whose length in the X direction is X0 and the length in the Y direction is Y0 was cut out from the
(Dry heat endurance test)
From the
ΔX WET , ΔY WET , ΔRe WET , and ΔRth WET shown in Table 4 are the ratios (X1 WET -X0) / X0 in the X direction and the ratio of the dimensional variation in the X direction in the sample film before and after the wet heat endurance test. The variation amount ratio (Y1 WET -Y0) / Y0, the variation amount (Re1 WET -Re0) of in-plane retardation, and the variation amount (Rth1 WET -Rth0) of thickness direction retardation are shown. Also, DRY ΔX, ΔY DRY, DRY ΔRe shown in Table 5, and the dry heat ΔRth DRY sample before and after the running test film X percentage of dimensional change amount of the direction of the in the (X1 -X0 DRY) / X0, Y direction The ratio (Y1 DRY -Y0) / Y0 of the dimensional variation of the surface, the variation amount (Re1 DRY -Re0) of in-plane retardation, and the variation amount (Rth1 DRY -Rth0) of thickness direction retardation are shown.
ΔRe WET mouth and ΔRth WET were measured at 1 day, 5 days, and 10 days after the start of the wet heat endurance test. In Table 4, # 1d, # 5d, # 10d, and # 21d represent the measured values of ΔRe WET and ΔRth WET at 1 day, 5 days, 10 days, and 21 days, respectively. Similarly, ΔRe DRY and ΔRth DRY were measured at 1 day, 5 days, and 10 days after the start of the dry heat endurance test. In Table 5, # 1d, # 5d, # 10d, and # 21d represent the measured values of ΔRe DRY and ΔRth DRY at 1 day, 5 days, 10 days, and 21 days, respectively. In addition, "-" shown in Table 4, 5 shows that the corresponding item was not measured.
(Grid shape staining evaluation)
The surface of the TAC film obtained by experiment 31-35 was visually observed, and the presence or absence of lattice irregularity was investigated. In
(Experiment 101)
As shown in FIG. 5, the TAC film 3 (sample No. A1) was manufactured by the solution-forming method of the cooling gelation system using the dope containing a polymer and a solvent. The elongation (Wb / Wa) of the extending | stretching process in the
(Experiments 102-135)
It carried out similarly to experiment 101 except having performed each condition in each process similarly to experiment 2-35.
The evaluation similar to Experiment 1-35 was performed about the TAC film obtained by Experiment 101-135, and the result of the tendency similar to Experiment 1-35 was obtained.
Sample No. shown in Table 1 The film of A2-A4, B-D was performed similarly to experiment 1-135, and each process was performed, and the obtained TAC film was evaluated similarly to experiment 1-135, and the result of the tendency similar to experiment 1-135 was shown. Could get
It was found that variation in retardation before and after the wet heat endurance test can be suppressed by subjecting the polymer film subjected to the stretching treatment to steam contact treatment. In addition, it was found that after performing a water vapor contact treatment on the polymer film, heat treatment was performed to suppress variation in retardation and variation in dimensions before and after each endurance test. Moreover, it turned out that the dew condensation prevention process in a polymer film can be prevented between the extending | stretching process and the water vapor contact process in the polymer film, and the dew condensation in the water vapor contact process can be prevented.
1 is an explanatory diagram showing an outline of a first offline stretching equipment;
2 is a plan view showing an outline of a tenter portion;
3 is an explanatory diagram showing an outline of a wet gas supply facility;
4 is a perspective view showing an outline of a fixing member for fixing a TAC film in a water vapor contact treatment;
5 is an explanatory diagram showing an outline of a first film production facility that performs a solution film forming method of a cooling gelation method;
FIG. 6 is an explanatory diagram showing an outline of a second film production facility that performs a solution film forming method of a cooling gelation method; FIG.
7 is an explanatory diagram showing an outline of a main part of a second off-line drawing facility;
8 is an explanatory diagram showing an outline of a main part of a third off-line drawing equipment;
9 is an explanatory diagram showing an outline of a melt film production facility;
10 is a perspective view showing an arrangement state of a plurality of rolls in a shrinkage treatment zone;
It is explanatory drawing which shows the roll wrap length D of the some roll in the shrinkage processing zone, and the length G between rolls.
Claims (15)
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| JP5715773B2 (en) * | 2010-06-23 | 2015-05-13 | 株式会社日本触媒 | Method for producing retardation film |
| JP2013018895A (en) * | 2010-07-20 | 2013-01-31 | Fujifilm Corp | Optical film, retardation film, polarizing plate, and liquid crystal display device |
| JP5652211B2 (en) * | 2011-01-11 | 2015-01-14 | コニカミノルタ株式会社 | Manufacturing method of λ / 4 plate with hard coat, manufacturing method of polarizing plate using λ / 4 plate with hard coat, and manufacturing method of liquid crystal display device |
| JP5696015B2 (en) * | 2011-09-16 | 2015-04-08 | 富士フイルム株式会社 | Method for producing polymer film |
| JP7073058B2 (en) * | 2017-07-31 | 2022-05-23 | 住友化学株式会社 | Optical film manufacturing equipment and manufacturing method |
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| JP2000313757A (en) * | 1999-04-28 | 2000-11-14 | Matsushita Electric Ind Co Ltd | Production of film phase plate |
| JP2005344010A (en) * | 2004-06-03 | 2005-12-15 | Konica Minolta Opto Inc | Retardation film, method for producing retardation film, polarizing plate and display device |
| KR20070103422A (en) * | 2005-01-05 | 2007-10-23 | 후지필름 가부시키가이샤 | Cellulose acylate film and method for saponification thereof |
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| JP3418447B2 (en) * | 1994-02-08 | 2003-06-23 | 日本化薬株式会社 | Method for producing retardation film with improved viewing angle |
| JP2005306924A (en) * | 2004-04-19 | 2005-11-04 | Konica Minolta Holdings Inc | Cellulose ester film, film for display substrate and methods for producing them, and liquid crystal display, organic el display and touch panel |
| JP4416687B2 (en) * | 2005-04-01 | 2010-02-17 | 信越ポリマー株式会社 | Method and apparatus for processing resin molded product |
| JP2008191217A (en) * | 2007-02-01 | 2008-08-21 | Konica Minolta Opto Inc | Manufacturing method of retardation film, retardation film, polarizing plate and liquid crystal display |
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| JP2000313757A (en) * | 1999-04-28 | 2000-11-14 | Matsushita Electric Ind Co Ltd | Production of film phase plate |
| JP2005344010A (en) * | 2004-06-03 | 2005-12-15 | Konica Minolta Opto Inc | Retardation film, method for producing retardation film, polarizing plate and display device |
| KR20070103422A (en) * | 2005-01-05 | 2007-10-23 | 후지필름 가부시키가이샤 | Cellulose acylate film and method for saponification thereof |
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