JP2011042073A - Method for producing phase difference film - Google Patents

Abstract

A method for producing a retardation film capable of controlling in-plane retardation and thickness direction retardation is provided.
A method of producing a retardation film by melt extrusion, wherein a glass transition temperature of resin A is Tg (° C.), a thermal decomposition start temperature is Td (° C.), and a crystallization temperature is Tm (° C.). Sometimes, a melt extrusion process in which the specific energy is 0.02 to 0.24 kWh / kg and the temperature of the resin A is (Tg + 120) ° C. to (Td−5) ° C., and the resin A is melt extruded from the mold 4. And a cooling step of cooling the melt-extruded resin A with a cooling roll whose temperature is adjusted within the range of (Tm-10) ° C. to (Tg-20) ° C., and as resin A to be melt-extruded, A method for producing a retardation film, wherein a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene is used, and a draw ratio is within a range of 5 to 10 in a melt extrusion step and a cooling step.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a retardation film used for improving contrast and enlarging a viewing angle in a liquid crystal display device or the like.

  Liquid crystal display devices are widely used in mobile phones, notebook personal computers, personal computer monitors, and the like. In recent years, liquid crystal display devices are often used for television applications, and the demand is rapidly increasing.

  As one of the liquid crystal display devices, a TN (twisted nematic) liquid crystal display device can be given. The TN liquid crystal display device has a problem that the viewing angle is narrow and the response speed is slow.

  As a liquid crystal display device in which the above problems have been improved, a VA (Vertical Alignment) liquid crystal display device and an IPS (In Plane Switching) liquid crystal display device have been proposed. In these liquid crystal display devices, a retardation film is widely used.

  As a method for producing the retardation film, the following Patent Document 1 includes a step of forming a resin composition containing a polyvinyl acetal resin as a main component into a sheet shape by a melt extrusion method to obtain a polymer film. The manufacturing method of retardation film provided with the process of extending | stretching a polymer film is disclosed.

  Patent Document 2 listed below is a copolymer containing a polymer portion having an alicyclic structure in the main chain skeleton, and has a polymer unit chain having crystallinity as a part of the copolymer. A method for producing a retardation film using a block copolymer or a graft copolymer is disclosed. Here, it is described that a retardation film having a retardation of 20 nm or more can be obtained without stretching.

JP 2006-234878 A JP 2007-226109 A

  In the method for producing a retardation film described in Patent Document 1, the melt-extruded film is stretched. When there exists such a extending process, the manufacturing cost of retardation film will become high. Moreover, in order to perform an extending | stretching process, you have to prepare a big space and equipment.

  When the copolymer described in Patent Document 2 is used, both the in-plane retardation and the thickness direction retardation may not be sufficiently controlled.

  An object of the present invention is to provide a method for producing a retardation film capable of controlling an in-plane retardation and a thickness direction retardation.

  According to a wide specific aspect of the present invention, there is provided a method for producing a retardation film in which a resin is formed into a film by a melt extrusion method, wherein the glass transition temperature of the resin is Tg (° C.) and the thermal decomposition start temperature is Td. (° C.) and the crystallization temperature is Tm (° C.), the specific energy is in the range of 0.02 to 0.24 kWh / kg, and the temperature of the resin is (Tg + 120) ° C. to (Td-5). ) Within the range of ° C., the temperature of the melt-extruding step of melt-extruding the resin from the mold and the temperature of the melt-extruded resin was adjusted within the range of (Tm-10) ° C. to (Tg-20) ° C. In the melt extrusion step and the cooling step, a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene is used as the resin to be melt-extruded. , The ratio of the peripheral speed is the draw ratio of the cooling roll for the flow rate of the resin of Kikin type outlet in the range of 5 to 10, a manufacturing method of a retardation film is provided.

  In a specific aspect of the method for producing a retardation film according to the present invention, the resin is formed into a film using a T-die.

  In another specific aspect of the method for producing a retardation film according to the present invention, the resin is formed into a film using a metal sleeve roll or a metal sleeve belt.

  In another specific aspect of the method for producing a retardation film according to the present invention, as the block copolymer, the vinyl aromatic hydrocarbon is styrene, the conjugated diene is butadiene, and the number of blocks is 5. And a block in which the skeleton derived from the vinyl aromatic hydrocarbon is within a range of 40 to 60 mol% in a total of 100 mol% of the skeleton derived from the vinyl aromatic hydrocarbon and the skeleton derived from the conjugated diene. A copolymer is used.

  In the method for producing a retardation film according to the present invention, it is preferable to obtain a retardation film without stretching the melt-extruded resin.

  In the method for producing a retardation film according to the present invention, it is preferable to obtain a retardation film having an Nz coefficient in the range of 1.4 to 1.6.

  In the present invention, a hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene is used as the resin to be melt extruded, and the specific energy at the time of melt extrusion is 0.02 to 0.24 kWh / kg. The temperature of the resin during melt extrusion is (Tg + 120) ° C. to (Td−5) ° C., the temperature of the cooling roll during cooling is (Tm−10) to (Tg−20) ° C., and the draw ratio is 5 to 5 ° C. Therefore, the in-plane retardation and the thickness direction retardation can be controlled. According to the method for producing a retardation film according to the present invention, a retardation film having an Nz coefficient of 1.4 to 1.6 can be easily obtained.

FIG. 1 is a schematic configuration diagram showing an example of an apparatus used for forming a resin into a film by a melt extrusion molding method.

  Details of the present invention will be described below.

  In the method for producing a retardation film according to the present invention, a resin is formed into a film by a melt extrusion method.

(Hydrogenated block copolymer)
In the present invention, a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene is used as a resin that is melt-extruded by a melt-extrusion method. The block copolymer is obtained by block copolymerization of a vinyl aromatic hydrocarbon and a conjugated diene.

  Examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. Of these, styrene is preferable. As for the said vinyl aromatic hydrocarbon, only 1 type may be used and 2 or more types may be used together.

  Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. Of these, butadiene is preferable, and 1,3-butadiene is more preferable. As for the said conjugated diene, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the block copolymer include a styrene block copolymer having a block copolymer containing a styrene polymer block (A) and a conjugated diene polymer block (B) as a main skeleton. Can be mentioned.

  Examples of the block copolymer include an AB block copolymer in which one block of each of the above (A) and (B) is bonded, and the above (A) bonded to both ends of the above (B). A-B-A block copolymer, and (AB) n block copolymer, (AB) nX block copolymer, and (A) in which (A) and (B) are repeated or coupled. -BA) nX block copolymer etc. are mentioned. X represents a residue of the coupling agent, and n represents an integer of 1 or more.

  Since the spreadability of the film at the time of melt extrusion can be further enhanced, the number of blocks of the block copolymer is preferably in the range of 3-7. The number of blocks is most preferably 5 because the spreadability of the film during melt extrusion can be further enhanced.

  The method for obtaining the block copolymer may be a conventionally known method and is not particularly limited. Examples of the method for obtaining the block copolymer include the methods described in JP-T-2003-502455 and JP-A-2006-313335. All the methods described in the above publications are methods in which a vinyl aromatic hydrocarbon and a conjugated diene are block copolymerized in a hydrocarbon solvent using an anionic initiator such as an organolithium compound.

  Examples of the hydrocarbon solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of the aliphatic hydrocarbon include butane, pentane, hexane and heptane. Examples of the alicyclic hydrocarbon include cyclopentane and cyclohexane. Examples of the aromatic hydrocarbon include benzene, toluene and xylene. As for the said hydrocarbon solvent, only 1 type may be used and 2 or more types may be used together.

  Examples of the organolithium compound include a carbanion initiator. Specific examples of the organic lithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium and the like. As for the said organolithium compound, only 1 type may be used and 2 or more types may be used together.

  For the purpose of adjusting the reaction ratio between the vinyl aromatic hydrocarbon and the conjugated diene, or adjusting the polymerization rate, a polar compound or a randomizing agent can be used when obtaining the block copolymer.

  Examples of the polar compound or randomizing agent include ethers, amines, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, sodium alkoxides, and potassium alkoxides. Examples of the ethers include tetrahydrofuran and diethylene glycol dimethyl ether. Examples of the amines include triethylamine and tetramethylethylenediamine.

  The polymerization temperature for obtaining the block copolymer is generally in the range of −10 to 150 ° C. A more preferable lower limit of the polymerization temperature is 40 ° C, and a more preferable upper limit is 120 ° C. The polymerization time can be appropriately changed. The polymerization time is preferably within 24 hours, and more preferably within 10 hours. The polymerization system for obtaining the block copolymer is preferably under an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas. Under an air atmosphere, the living polymer or catalyst may be inactivated by water or oxygen in the air.

  The block copolymer has a skeleton derived from the vinyl aromatic hydrocarbon in a total amount of 100 mol% of the skeleton derived from the vinyl aromatic hydrocarbon and the skeleton derived from the conjugated diene. It is preferable to be within the range. In this case, the rigidity and transparency of the retardation film can be further enhanced.

  The molar amount of the skeleton derived from the vinyl aromatic hydrocarbon and the skeleton derived from the conjugated diene can be measured as follows.

  For example, proton nuclear magnetic resonance spectrum measurement is performed using “ECA” manufactured by JEOL Datum. The peaks of the skeleton derived from the vinyl aromatic hydrocarbon and the skeleton derived from the conjugated diene are assigned. Chloroform-d is used as a measurement heavy solvent.

  The hydrogenated product of the block copolymer can be obtained by partially or completely hydrogenating the aromatic ring derived from the vinyl aromatic hydrocarbon and the unsaturated double bond derived from the conjugated diene. .

  The preferable lower limit of the hydrogenation rate of the block copolymer is 90%, the more preferable lower limit is 95%, and the preferable upper limit is 100%. Even if the hydrogenation is attempted completely, a portion that has not been slightly hydrogenated remains, and the hydrogenation rate may not reach 100%. By adding hydrogen to the aromatic ring derived from the vinyl aromatic hydrocarbon and the unsaturated double bond derived from the conjugated diene, the effect of reducing the photoelastic coefficient is obtained. By adding hydrogen to the aromatic ring derived from the vinyl aromatic hydrocarbon, an effect of suppressing the wavelength dependency of retardation can be obtained. The unsaturated double bond derived from the conjugated diene causes the film to turn yellow by light or heat, or the transmittance of the film to decrease.

  The hydrogenation reaction of the block copolymer is performed, for example, in a dilution system using a solvent. As the solvent, a solvent that sufficiently dissolves the block copolymer and is not hydrogenated is used. The temperature of the hydrogenation reaction is preferably in the range of 40 to 170 ° C. When the temperature of the hydrogenation reaction is within the above range, the catalyst is hardly deteriorated and a sufficient reaction rate can be obtained. The hydrogenation pressure of the hydrogenation reaction can be appropriately selected depending on the type of catalyst. The hydrogen pressurization is preferably within a range of 0.7 to 10.3 MPa.

  The kind and amount of the catalyst used in the hydrogenation reaction are not particularly limited. The type and amount of the catalyst used in the hydrogenation reaction are preferably selected so as to satisfy the range of the hydrogenation rate. Homogeneous hydrogenation containing at least one metal selected from the group consisting of titanium, zirconium, hafnium, molybdenum, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum as the catalyst for the hydrogenation reaction, for example A catalyst, a heterogeneous hydrogenation catalyst, or the like can be used. Specific examples of the homogeneous catalyst include nickel chloride, nickel carbonyl and cobalt chloride. Examples of the heterogeneous catalyst include those in which the metal oxide is supported on alumina, silica, titania or the like.

  The hydrogenation rate of the aromatic ring derived from the vinyl aromatic hydrocarbon and the unsaturated double bond derived from the conjugated diene can be measured as follows.

  For example, proton nuclear magnetic resonance spectrum measurement is performed using “ECA” manufactured by JEOL Datum. The peaks of the skeleton derived from the vinyl aromatic hydrocarbon and the skeleton derived from the conjugated diene are assigned. As a measurement heavy solvent, o-dichlorobenzene-d4 is used.

(Method for producing retardation film)
In the method for producing a retardation film according to the present invention, the resin is formed into a film by a melt extrusion method. The method for producing a retardation film according to the present invention includes a melt extrusion step of melt-extruding a resin from a mold and a cooling step of cooling the melt-extruded resin by a cooling roll.

  The retardation film according to the present invention can be produced using, for example, the apparatus shown in FIG.

  FIG. 1 is a schematic configuration diagram illustrating an example of an apparatus used for forming a resin into a film by a melt extrusion molding method.

  As shown in FIG. 1, when the resin is formed into a film, the resin is first extruded from the extruder 1 and supplied to the mold 4. A gear pump 2 is disposed between the extruder 1 and the mold 4. A filter 3 is disposed between the extruder 1 and the mold 4. The filter 3 is disposed between the gear pump 2 and the mold 4. However, the gear pump 2 and the filter 3 are not necessarily used.

  The resin supplied to the mold 4 is extruded from the opening of the mold 4 and discharged, and the resin is formed into a film. The discharged film-like resin A is brought into contact with the cooling roll 12 and cooled. A touch roll 11 is provided to press the resin A against the cooling roll 12. Instead of the touch roll 11, an air knife or electrostatic pinning may be used.

  The resin A cooled by the cooling roll 12 is further cooled by the cooling rolls 13 and 14 and wound up. In order to adjust the cooling temperatures of the cooling rolls 12 to 14, respectively, temperature adjusting devices 15 to 17 are provided.

  From the viewpoint of improving moldability, the mold 4 is preferably a T-die. From the viewpoint of improving formability, the touch roll 11 is preferably a metal sleeve roll or a metal sleeve belt.

  The specific energy E represented by the following formula (1) of the extruder 1 is in the range of 0.02 to 0.24 kWh / kg. The preferable lower limit of the specific energy is 0.05 kWh / kg, and the preferable upper limit is 0.20 kWh / kg. If the specific energy is too small, the dischargeability of the resin from the mold 4 may become unstable. If the specific energy is too large, the Nz coefficient of the resulting film may be small.

E = 0.85 [(Vr × Ar) − (V0 × A0)] / 1000Q (1)
Vr: Voltage consumed by the extruder motor during resin discharge (V)
Ar: Current consumption of the extruder motor during resin discharge (A)
V0: Voltage consumed by the extruder motor during idle operation (V)
A0: Current consumption of extruder motor during idling (A)
Q: Discharge rate per unit time of the extruder (kg / h)

  When the glass transition temperature of the resin is Tg (° C.) and the thermal decomposition start temperature is Td (° C.), the temperature of the resin during melt extrusion is in the range of (Tg + 120) ° C. to (Td-5) ° C. It is. The preferred lower limit of the temperature of the resin during melt extrusion is (Tg + 130) ° C., and the preferred upper limit is (Td-15) ° C. If the temperature of the resin during melt extrusion is too low, the haze of the resulting film may increase. If the temperature of the resin during melt extrusion is too high, the resin may be thermally deteriorated.

  The draw ratio V represented by the following formula (2) is in the range of 5-10. In the melt extrusion step and the cooling step, the draw ratio, which is the ratio of the cooling roll 12 to the peripheral speed with respect to the flow rate of the resin A at the outlet of the mold 4, is in the range of 5 to 10. The preferable lower limit of the draw ratio is 6, and the preferable upper limit is 9. If the draw ratio is too small, unevenness in the thickness of the resulting film tends to occur. When the said draw ratio is too large, the Nz coefficient of the film obtained may become large.

V = V1 / V2 Formula (2)
V1: Peripheral speed of cooling roll V2: Resin flow rate at mold outlet

  When the glass transition temperature of the resin is Tg (° C) and the crystallization temperature is Tm (° C), the temperature of the cooling roll 12 is in the range of (Tm-10) ° C to (Tg-20) ° C. . The melt-extruded resin A is cooled by a cooling roll 12 whose temperature is adjusted within the range of (Tm-10) ° C. to (Tg-20) ° C. The preferable lower limit of the temperature of the cooling roll 12 is (Tm-5) ° C., and the preferable upper limit is (Tg-30) ° C. If the temperature of the cooling roll 12 is too low, unevenness in the thickness of the resulting film tends to occur. If the temperature of the cooling roll 12 is too high, the peelability when the film is taken from the cooling roll may be lowered.

  The temperature of the cooling rolls 13 and 14 is not particularly limited, but is preferably lower than the temperature of the cooling roll 12.

  In the method for producing a retardation film according to the present invention, it is preferable to obtain a retardation film without stretching the melt-extruded resin A. Moreover, in the manufacturing method of the retardation film which concerns on this invention, it is preferable to obtain the retardation film whose Nz coefficient is in the range of 1.4-1.6. In the method for producing a retardation film according to the present invention, a retardation film having an Nz coefficient in the range of 1.4 to 1.6 can be easily obtained without stretching. Since it does not need to extend | stretch, the manufacturing cost of retardation film can be made low. Furthermore, it is not necessary to prepare a large space and equipment to perform the stretching process.

(Retardation film)
The retardation film obtained by the method for producing a retardation film according to the present invention can be used for a liquid crystal display device. Examples of the liquid crystal display device include a TN (Twisted Nematic) type liquid crystal display device, a VA (Vertical Alignment) type liquid crystal display device, and an IPS (In Plane Switching) type liquid crystal display device.

  The Nz coefficient represented by the following formula (3) of the retardation film according to the present invention is preferably in the range of 1.4 to 1.6.

Nz coefficient = (nx−nz) / (nx−ny) (3)
nx: refractive index in the x direction in the film plane ny: refractive index in the y direction in the film plane orthogonal to the x direction nz: refractive index in the film thickness direction

  Using the specific resin, the specific energy at the time of melt extrusion is 0.02 to 0.24 kWh / kg, the temperature of the resin at the time of melt extrusion is (Tg + 120) ° C. to (Td−5) ° C. The temperature of the cooling roll is set to (Tm-10) to (Tg-20) ° C., and the draw ratio is set to 5 to 10 to produce a retardation film, whereby the Nz coefficient is 1.4 to 1.6. A retardation film can be easily obtained.

  In the retardation film used for the IPS liquid crystal display device, the Nz coefficient is preferably in the range of 0.4 to 0.7. In a retardation film used for a medium-sized VA liquid crystal display device having a size of 4 inches or more and less than 10 inches, the Nz coefficient is preferably in the range of 1.4 to 1.6. In a retardation film used in a large VA liquid crystal display device having a size of 10 inches or more, the Nz coefficient is preferably 2.5 or more.

  The retardation film obtained by the method for producing a retardation film according to the present invention and having an Nz coefficient in the range of 1.4 to 1.6 is suitably used for a medium-sized VA liquid crystal display device.

  From the viewpoint of enhancing optical properties, the haze of the retardation film is preferably 5% or less, more preferably 1% or less, and further preferably 0.5% or less.

  Since it can use suitably for the said liquid crystal display device, it is preferable that the thickness of the said retardation film exists in the range of 30-300 micrometers.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

  First, hydrogenated products B-1, B-2, and B-3 of the following block copolymers were synthesized. For example, hydrogenated products B-1, B-2, and B-3 of block copolymers were synthesized with reference to the methods described in JP-T-2003-502455 and JP-A-2006-313335.

(Synthesis Example 1)
(1) Preparation of block copolymer A-1 A pentablock copolymer A-1 was prepared using styrene as the vinyl aromatic hydrocarbon monomer and 1,3-butadiene as the conjugated diene monomer. In this pentablock copolymer A-1, the repeating constitution of the polystyrene block (S) and the polybutadiene block (B) was SBS-BSS.

  Further, the molar amount Ms of the skeleton derived from styrene of the pentablock copolymer A-1 and the molar amount Mb of the skeleton derived from 1,3-butadiene were measured by proton nuclear magnetic resonance spectrum. As a result, Ms / Mb = 40/60.

The number average molecular weight Mn in terms of polystyrene and the polydispersity Mw / Mn of the pentablock copolymer A-1 were measured by GPC (gel permeation chromatography). As a result, Mn = 5.8 × 10 ⁴ and Mw / Mn = 1.2.

(2) Preparation of hydrogenated product B-1 of block copolymer A-1 The pentablock copolymer A-1 was dissolved in cyclohexane / isopentane (85/15 by weight), and the pentablock copolymer A- A solution containing 15% by weight of 1 was obtained. Prior to hydrogenation, the solution was degassed and passed through an activated alumina column to remove stabilizers and impurities. The hydrogenation reaction of the pentablock copolymer A-1 was performed in a high-pressure reactor equipped with a gas dispersion stirrer. The above solution was placed in the reactor and 5 wt% Pt / silica catalyst was further added. The reactor was sealed, purged with nitrogen, and finally hydrogen was injected to bring the pressure in the reactor to 8 MPa. Next, the reactor was heated at 170 ° C. for 1 hour, and then the pressure was gradually reduced. Thereafter, a solution containing the hydrogenated product B-1 was taken out from the reactor. 1000 ppm of a sterically hindered phenol heat stabilizer (Irganox 1010, manufactured by Ciba Specialty Chemicals) was added to the solution containing the hydrogenated product B-1. The solvent was volatilized from the solution containing the hydrogenated product B-1 by using heat and vacuum to obtain the hydrogenated product B-1.

  The hydrogenation rate Hs of the aromatic ring derived from styrene of the hydrogenated product B-1 and the hydrogenation rate Hb of the unsaturated double bond derived from 1,3-butadiene were measured by proton nuclear magnetic resonance spectrum. As a result, Hs = 99.9% and Hb = 99.9%.

The number average molecular weight Mn and polydispersity Mw / Mn of the hydrogenated product B-1 were measured by GPC. As a result, Mn = 6.0 × 10 ⁴ and Mw / Mn = 1.2.

(Synthesis Example 2)
(1) Preparation of block copolymer A-2 A pentablock copolymer A-2 was prepared using styrene as the vinyl aromatic hydrocarbon monomer and 1,3-butadiene as the conjugated diene monomer. In this pentablock copolymer A-2, the repeating configuration of the polystyrene block (S) and the polybutadiene block (B) was SBS-BSS.

As a result of evaluating in the same manner as the pentablock copolymer A-1, the pentablock copolymer A-2 was Ms / Mb = 50/50, Mn = 5.7 × 10 ⁴ , and Mw / Mn = 1.2. there were.

(2) Preparation of hydrogenated product B-2 of block copolymer A-2 Except that pentablock copolymer A-1 was changed to pentablock copolymer A-2, the same as in Synthesis Example 1, Hydrogenated product B-2 was obtained.

As a result of evaluation in the same manner as the hydrogenated product B-1, in the hydrogenated product B-2, Hs = 99.9%, Hb = 99.9%, Mn = 6.0 × 10 ⁴ , Mw / Mn = 1. 2.

(Synthesis Example 3)
(1) Preparation of block copolymer A-3 A pentablock copolymer A-3 was prepared using styrene as the vinyl aromatic hydrocarbon monomer and 1,3-butadiene as the conjugated diene monomer. In this pentablock copolymer A-3, the repeating structure of the polystyrene block (S) and the polybutadiene block (B) was SBS-BSS.

As a result of evaluating in the same manner as the pentablock copolymer A-1, in the pentablock copolymer A-3, Ms / Mb = 60/40, Mn = 5.7 × 10 ⁴ , and Mw / Mn = 1.2. there were.

(2) Preparation of hydrogenated product B-3 of block copolymer A-3 Except that the pentablock copolymer A-1 was changed to the pentablock copolymer A-3, the same as in Synthesis Example 1, Hydrogenated product B-3 was obtained.

As a result of evaluation in the same manner as the hydrogenated product B-1, in the hydrogenated product B-3, Hs = 99.9%, Hb = 99.9%, Mn = 6.0 × 10 ⁴ , Mw / Mn = 1. 2.

Example 1
A retardation film was obtained by a melt extrusion method using the apparatus schematically shown in FIG. The specification of the apparatus shown in FIG. 1 is as follows.

Extruder 1: Single screw extruder Die 4: T die Cooling rolls 12-14: Metallic mirror roll Touch roll 11: Metal sleeve roll

  Using the above apparatus, the hydrogenated product B-2 was supplied from the extruder 1 to the mold 4, and the hydrogenated product B-2 was extruded from the mold 4 into a film shape. The specific energy E during melt extrusion was 0.08 kWh / kg, and the temperature of the resin during melt extrusion was 290 ° C. The temperature of the resin during extrusion was adjusted by controlling the temperature from the tip of the extruder 1 to the mold 4.

  After the melt-extruded resin film was cooled by the cooling rolls 12 to 14, the resin film was wound up to obtain a retardation film having an average thickness of 100 μm. The draw ratio V was 7.4, the temperature of the cooling roll 12 was 100 ° C., the temperature of the cooling roll 13 was 50 ° C., and the temperature of the cooling roll 14 was 40 ° C. The draw ratio V was adjusted by the opening width (die lip opening) of the mold 4 corresponding to the thickness direction of the film. The temperature of the cooling rolls 12-14 was adjusted by circulating the temperature-controlled oil inside the cooling rolls 12-14 using the temperature control devices 15-17.

(Examples 2-11 and Comparative Examples 1-9)
A retardation film was obtained in the same manner as in Example 1 except that the type of resin used and the melt extrusion conditions were changed as shown in Table 1 below.

(Evaluation)
(1) Glass transition temperature Tg
The resin used in Examples and Comparative Examples was hot press molded at 290 ° C. to obtain a film-like resin sample having a thickness of 0.8 mm. Using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Measurement Control Co., Ltd.) 0.04% tensile deformation was repeatedly applied to the sample. The dielectric loss tangent (loss elastic modulus E ″ / storage elastic modulus E ′) of the resin sample at that time was measured. The peak top temperature of the dielectric loss tangent was defined as the glass transition temperature Tg (° C.).

(2) Thermal decomposition start temperature Td
Using a differential thermothermal gravimetric simultaneous measurement device (“TG / DTA320” manufactured by Seiko Instruments Inc.), the temperature was raised from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min under the condition of an air flow rate of 50 mL / min. The weight loss of the resin during the temperature rise was measured. The temperature at which the weight loss of the resin at the time of temperature increase became 1% was defined as the thermal decomposition start temperature Td (° C.).

(3) Crystallization temperature Tm
Using a differential scanning calorimeter (“DSC 6220” manufactured by SII Nanotechnology Co., Ltd.), the temperature was raised from 25 ° C. to 300 ° C. at a temperature rising rate of 10 ° C./min under the condition of a nitrogen flow rate of 50 mL / min. The temperature was decreased from 300 ° C. to 25 ° C. at a rate of 10 ° C./min, and then the temperature was increased from 25 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min. The endothermic peak temperature of the resin during the second temperature increase was defined as the crystallization temperature Tm (° C.).

(4) Nz coefficient The refractive index of the three-dimensional direction of the obtained retardation film was measured using the automatic birefringence measuring apparatus ("KOBRA-21ADH" by Oji Scientific Instruments). Nz coefficient was calculated | required by the said Formula (3).

(5) In-plane retardation value Ro
Automatic birefringence measuring device (using Oji Scientific Instruments' “KOBRA-21ADH”), measuring the wavelength of the measuring light at 550 nm, measuring the retardation film at 50 mm intervals in the width direction, calculating the average value, The retardation value Ro was measured.

(6) Haze The haze of the obtained retardation film was measured using a haze meter (“TC-HIIIDKP” manufactured by Tokyo Denshoku Co., Ltd.) according to JIS K7105.

(7) Appearance The appearance of the obtained retardation film was visually observed. In Table 1 below, “unstable discharge” indicates that the amount of resin discharged from the extruder varies greatly and the film thickness is not stable. “Peeling failure” indicates that when the film is taken from the cooling roll, the peeling position from the cooling roll is not stable, and a pattern called a peeling mark is generated on the film.

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Extruder 2 ... Gear pump 3 ... Filter 4 ... Mold 11 ... Touch roll 12-14 ... Cooling roll 15-17 ... Temperature control apparatus A ... Resin

Claims (6)

A method for producing a retardation film in which a resin is formed into a film by a melt extrusion method,
When the glass transition temperature of the resin is Tg (° C.), the thermal decomposition start temperature is Td (° C.), and the crystallization temperature is Tm (° C.),
Melting by melting and extruding the resin from a mold with a specific energy in the range of 0.02 to 0.24 kWh / kg and a temperature of the resin in the range of (Tg + 120) ° C. to (Td−5) ° C. An extrusion process;
A cooling step of cooling the melt-extruded resin with a cooling roll whose temperature is adjusted within the range of (Tm-10) ° C to (Tg-20) ° C.
As the resin to be melt extruded, a hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene is used.
In the melt extrusion step and the cooling step, a method for producing a retardation film, wherein a draw ratio that is a ratio of a peripheral speed of the cooling roll to a flow rate of the resin at the mold outlet is in a range of 5 to 10.   The method for producing a retardation film according to claim 1, wherein the resin is formed into a film using a T die.   The method for producing a retardation film according to claim 1, wherein the resin is formed into a film using a metal sleeve roll or a metal sleeve belt.   As the block copolymer, the vinyl aromatic hydrocarbon is styrene, the conjugated diene is butadiene, the number of blocks is 5, and the skeleton derived from the vinyl aromatic hydrocarbon and the conjugated diene are derived. The block copolymer in which the skeleton derived from the vinyl aromatic hydrocarbon is in the range of 40 to 60 mol% in a total of 100 mol% with the skeleton to be used is described in any one of claims 1 to 3. The method for producing a retardation film.   The method for producing a retardation film according to claim 1, wherein a retardation film is obtained without stretching the melt-extruded resin.   The method for producing a retardation film according to claim 1, wherein a retardation film having an Nz coefficient in the range of 1.4 to 1.6 is obtained.

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