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WO2017169306A1 - Procédé de fabrication de film optique - Google Patents

Procédé de fabrication de film optique Download PDF

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Publication number
WO2017169306A1
WO2017169306A1 PCT/JP2017/006409 JP2017006409W WO2017169306A1 WO 2017169306 A1 WO2017169306 A1 WO 2017169306A1 JP 2017006409 W JP2017006409 W JP 2017006409W WO 2017169306 A1 WO2017169306 A1 WO 2017169306A1
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WO
WIPO (PCT)
Prior art keywords
stretching
film
bis
temperature
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/006409
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English (en)
Japanese (ja)
Inventor
直矢 岩上
宏 宮本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of WO2017169306A1 publication Critical patent/WO2017169306A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a method for producing an optical film. More specifically, the present invention relates to a soluble and transparent polyimide resin that can be easily reused as a recycled material and has reduced retardation unevenness due to bowing phenomenon and retardation development during stretching. The present invention relates to a method for producing an optical film containing as a main component.
  • Polyimide resins are used in various applications that require heat resistance, such as IC (Integrated Circuit) substrates, due to their high heat resistance.
  • polyimide resins are often colored, but by using colorless and transparent polyimide resins, application to heat-resistant and transparent applications such as display materials (insulating substrates) can be expected.
  • Patent Document 1 proposes increasing the transparency of a polyimide resin and using it as an insulating substrate for a display.
  • Patent Document 2 proposes a polyimide resin having improved solubility in a solvent.
  • Patent Document 3 proposes a method for adjusting necessary optical characteristics by dissolving a soluble and transparent polyimide resin in a solvent, casting the solution on a resin film (TAC film), and stretching the resin film together.
  • TAC film resin film
  • the stretching conditions are limited to the conditions under which the support can be stretched, and the optical properties and physical properties of the polyimide resin film itself are limited, making it difficult to produce the desired optical film. was there.
  • the inventors of the present invention can easily adjust the necessary optical characteristics used in the production of optical films, and cast a soluble and transparent polyimide resin on a casting support by a solution casting method.
  • the method of manufacturing the optical film (polyimide film) containing a polyimide resin was examined by forming, peeling and extending
  • An object of the present invention is to provide a method for producing an optical film mainly composed of a soluble and transparent polyimide resin.
  • the present inventor formed a casting film by casting a dope containing a specific soluble and transparent polyimide resin in the process of examining the cause of the above-mentioned problem.
  • Mainly polyimide resin which is easy to reuse as a recycled material by stretching the film in a stretching process controlled to specific temperature conditions, and has reduced retardation unevenness due to bowing phenomenon and retardation development during stretching. It discovered that the manufacturing method of the optical film used as a component was obtained.
  • a method for producing an optical film comprising a polyimide resin, having a total light transmittance of 80% or more and a yellow index value (YI value) of 6.0 or less, A step of casting a dope containing a polyimide resin dissolved in 1 g or more in 100 g of dichloromethane or 1,3-dioxolane at 25 ° C.
  • the stretching temperature in the stretching step is in the range of (Tg ⁇ 250 ° C.) to (Tg ⁇ 100 ° C.) when the glass transition temperature of the polyimide resin is Tg (° C.).
  • the change in the stretching temperature from the start of stretching to the end of stretching in the stretching step is within 70 ° C, and
  • the method for producing an optical film, wherein the stretching temperature is 50 ° C. or more higher than the boiling point Tb (° C.) of the main solvent.
  • a method for producing an optical film mainly composed of a polyimide resin which can be easily reused as a recycled material and has reduced retardation unevenness due to the bowing phenomenon and retardation development during stretching. can do.
  • a feature of the method for producing an optical film of the present invention is that a dope containing a specific soluble and transparent polyimide resin is cast to form a cast film, and the cast film is controlled to a specific temperature condition.
  • the said subject is achieved by extending
  • the soluble and transparent polyimide resin according to the present invention is a resin having a glass transition temperature Tg of 250 ° C. or higher.
  • the film is usually stretched in a temperature range of (Tg ⁇ 20 ° C.) to (Tg + 60 ° C.), but in the case of a polyimide resin, the Tg is high. For this reason, when the resin was stretched at a high temperature in the vicinity of Tg, the order of the resin was increased. Therefore, it is desirable to stretch at a temperature lower than Tg.
  • the resin is unevenly oriented, It is assumed that the solubility of the recycled material is improved.
  • the stretching temperature may be stretched at a temperature lower than the boiling point of the solvent for dissolving the resin + 50 ° C., but in the case of the polyimide resin according to the present invention, the stretching temperature is higher than the boiling point of the solvent + 50 ° C.
  • the film was stretched at a low temperature, a phenomenon was observed in which the retardation value was larger than expected, which is considered to be an effect of the residual solvent on the orientation of the resin. Therefore, in the case of the polyimide resin according to the present invention, stretching at a temperature higher than the boiling point of the solvent + 50 ° C. can be easily controlled to obtain a desired retardation value, and can also reduce retardation unevenness. Inferred.
  • Sectional drawing which shows the schematic structure of the manufacturing apparatus used for manufacture of the polyimide film which concerns on embodiment of this invention.
  • Sectional drawing which shows the detailed structure of the 1st extending
  • Sectional drawing which shows the other structure of the said 1st extending
  • Sectional drawing which shows typically the example of arrangement
  • Sectional drawing which shows typically the other example of arrangement
  • Sectional drawing which shows the other structural example of the roller of the upstream of the said 1st extending
  • the method for producing an optical film of the present invention is a method for producing an optical film containing a polyimide resin, having a total light transmittance of 80% or more and a yellow index value (YI value) of 6.0 or less.
  • a step of stretching the peeled cast film (stretching step) is the glass transition temperature of the polyimide resin Tg (° C.).
  • the change in the stretching temperature from the start of stretching to the end of stretching in the stretching step is within 70 ° C., and Stretching temperature, being higher than 50 ° C. than the main solvent having a boiling point Tb (° C.).
  • the amount of residual solvent at the time of stretching in the stretching step is in the range of 3 to 100% by mass, from the viewpoint of controlling optical properties, preferable.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the method for producing an optical film of the present invention is a method for producing an optical film containing a polyimide resin, having a total light transmittance of 80% or more and a yellow index value (YI value) of 6.0 or less.
  • a step of stretching the peeled cast film (stretching step) is the glass transition temperature of the polyimide resin Tg (° C.).
  • the change in the stretching temperature from the start of stretching to the end of stretching in the stretching step is within 70 ° C., and Shin temperature, being higher than 50 ° C. than the main solvent having a boiling point Tb (° C.).
  • the glass transition temperature Tg referred to here is a midpoint glass transition temperature (Tmg) measured at a rate of temperature increase of 20 ° C./min using a commercially available differential scanning calorimeter and determined according to JIS K7121 (1987). It is.
  • a specific method for measuring the glass transition temperature Tg of the polyimide resin can be measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K7121 (1987).
  • the optical film of the present invention contains a polyimide resin as a main component.
  • the “main component” represents that the total amount of polyimide resin in the optical film is 50% by mass or more. Preferably, it means 80% by mass or more.
  • the optical film of the present invention may be referred to as a polyimide film.
  • the optical film manufacturing method of the present invention includes a step of preparing a dope containing the soluble and transparent polyimide resin and a solvent (dope preparation step), and a support for the dope.
  • An apparatus used in the method of manufacturing an optical film of the present invention is a dope preparation unit for preparing a dope containing the soluble and transparent polyimide resin and a solvent, and a support for the dope.
  • a casting part that casts the casting film on top of the casting film; a solvent evaporation part that evaporates the solvent from the casting film on the support; a peeling part that peels the casting film from the support; It may include a stretching section that stretches the film, a drying section that dries the film after stretching, a winding section that winds up the obtained polyimide film, and a heating section that heats and imidizes the film if necessary. preferable.
  • FIG. 1 is a cross-sectional view showing a schematic configuration of a manufacturing apparatus 1 used for manufacturing an optical film of the present embodiment.
  • the manufacturing apparatus 1 is an example, and the present invention is not limited to this, and the first extending section 3 and the second extending section 4 shown in the manufacturing apparatus 1 may serve as one extending section.
  • the production apparatus 1 includes a casting part 2, a first stretching part 3, a second stretching part 4, a drying part 5, and a winding part 6, and a casting film ( Web) 22, while being stretched in the MD (casting) direction or TD (width) direction in the first stretching unit 3, and additionally stretched in the MD direction or TD direction in the second stretching unit 4, and the drying unit 5 is dried (heat treated), and is wound up as an optical film F by the winding unit 6.
  • the cast film 22 is a film formed by casting a resin solution (dope) containing a resin and a solvent on a traveling support and drying it. Note that a drying unit may be disposed between the first stretching unit 3 and the second stretching unit 4 to dry the casting film 22.
  • the casting part 2 includes an endless belt 11 as a support, a die 12, a heating part 13, and a peeling roller 14.
  • the endless belt 11 is a metal belt having a mirror-finished surface.
  • a metal belt having a mirror-finished surface for example, a stainless steel whose surface is mirror finished or a metal endless belt whose surface is plated with a casting is used.
  • the endless belt 11 is wound around a driving roller 11a and a driven roller 11b, and can travel in the direction of an arrow in the figure.
  • the width of the endless belt 11 varies depending on the size of the optical film to be manufactured, but is preferably in the range of 1700 to 2700 mm, for example.
  • the width for casting the dope 21 is preferably, for example, in the range of 80 to 99% of the width of the endless belt 11.
  • a metal cylindrical drum having a mirror-finished surface may be used as the support.
  • the die 12 casts the dope 21 on the endless belt 11.
  • the heating unit 13 is provided to heat the dope 21 (cast film 22) cast on the endless belt 11 and reduce the solvent contained in the dope 21 (cast film 22). Details thereof will be described later.
  • the peeling roller 14 is provided for peeling the casting film 22 formed on the endless belt 11 from the endless belt 11.
  • this casting part 2 a casting process in which a dope 21 containing a resin and a solvent is cast on an endless belt 11 as a traveling support to form a casting film 22, and a state in which the solvent is contained. A peeling step of peeling the casting film 22 from the endless belt 11 is performed.
  • the dope 21 is cast on the endless belt 11 from the die 12 and dried by the heating unit 13. As a result, the dope 21 is dried and gelated on the endless belt 11 to form a cast film 22.
  • the thickness of the casting film 22 on the endless belt 11 can be changed to various values so that the thickness of the optical film wound up by the winding unit 6 becomes a predetermined thickness. Is adjusted according to the casting amount of the belt, the traveling speed of the endless belt 11, and the like.
  • the casting film 22 formed on the endless belt 11 is peeled from the endless belt 11 by the peeling roller 14.
  • the time from casting the dope 21 onto the endless belt 11 to peeling the casting film 22 from the endless belt 11 varies depending on the thickness of the manufactured optical film, the type of solvent, etc. Considering good peelability from the belt 11, for example, a range of 0.5 to 5 minutes is preferable.
  • the above-described peeling tension and conveying tension are preferably in the range of 20 to 400 N / m, for example.
  • the heating unit 13 heats the casting film 22 with heating air to remove the solvent, and includes a drying box 31, a first heating air supply unit 32 and a second heating air supply provided in the drying box 31. A portion 33 and an exhaust port 34 are provided.
  • the first heating air supply unit 32 and the second heating air supply unit 33 include heating air supply pipes 32a and 33a and headers 32b and 33b, respectively, and the endless belt 11 is transported in the transport direction of the casting film 22. It is arranged so as to be sandwiched from above and below in the vertical direction.
  • the temperature of the casting film 22 on the endless belt 11 on the first heating air supply unit 32 side and the temperature of the casting film 22 on the endless belt 11 on the second heating air supply unit 33 side are respectively responsible for the evaporation of the solvent.
  • the range of ⁇ 5 to 70 ° C. is preferable in consideration of the degree of dispersion of fine particles, productivity, and the like.
  • a range of 0 to 60 ° C. is more preferable.
  • the wind pressure of the heating air supplied from the first heating air supply unit 32 and the second heating air supply unit 33 is, for example, 50 to 50 in consideration of the uniformity of evaporation of the solvent, the degree of dispersion of the fine particles in the dope 21, and the like. A range of 5000 Pa is preferred.
  • the first heating air supply unit 32 and the second heating air supply unit 33 may supply only the heating air having a constant temperature, or stepwise the heating air having a plurality of temperatures along the traveling direction of the endless belt 11. You may supply.
  • the heating unit 13 is not limited to the one that heats the casting film 22 with heating air as described above.
  • the heating part 13 heats the casting film 22 with an infrared heater, or blows heating air on the back surface of the endless belt 11. What casts the casting film 22 from the back surface etc. may be used.
  • stretching part 3 performs the 1st extending
  • heating air drying air
  • other heating means such as an infrared heater may be used.
  • the drying in the first stretching section 3 may be performed at a constant temperature, or may be performed at several stages of temperatures divided into three to four stages.
  • a conventionally known method typically a heater heating method or an oven heating method, can be used.
  • the temperature is instantaneously increased to the stretching temperature by a heater installed between the low-speed roller group that transports the casting film 22 before stretching and the high-speed roller group that transports the casting film 22 after stretching.
  • stretching is performed with a relatively short stretching span. Since the width shrinkage due to stretching is reduced as the stretching span is shortened, it is preferable that the distance between the low speed roller group and the high speed roller group be as short as possible.
  • the oven heating method is a method in which an oven is installed between the low-speed roller group and the high-speed roller group, and a preheating zone, a stretching zone, and a cooling zone are provided in the oven, and stretching is performed with a relatively long stretching span.
  • the heater heating method is advantageous in that the amount of width shrinkage can be kept small, which is advantageous for forming a wide film and that it can be installed in a relatively small space.
  • the oven heating method has advantages such as high uniformity of the phase difference, less scratches and adhesive failure.
  • the above-described two heating methods may be appropriately selected in consideration of the material to be used, necessary physical properties, etc.
  • an oven heating method is used. At this time, the oven is transported in a non-contact manner while floating the film so that the hot air blown from the nozzles arranged above and below the film (casting film) passage does not come into contact with the nozzle.
  • a floating system that extends while stretching is preferred.
  • adopted the oven heating system is demonstrated.
  • FIG. 2 is a sectional view showing the detailed configuration of the first extending portion 3 along the transport direction.
  • stretching part 3 has the preheating zone Z1, the extending
  • the casting film 22 is heated before stretching.
  • the casting film 22 conveyed from the preheating zone Z1 may be stretched in the MD direction by a roller (not shown).
  • the stretched casting film 22 is cooled.
  • the temperature of the preheating zone Z1 is, for example, 200 ° C.
  • the temperature of the stretching zone Z2 is, for example, 150 ° C.
  • the temperature of the cooling zone Z3 is, for example, 100 ° C.
  • nozzles 41 for blowing heated air are arranged in a zigzag pattern in the up and down direction in the transport direction of the casting film 22, and cast between the upper and lower nozzles 41 and 41.
  • the film 22 is conveyed.
  • the nozzle 41 in the preheating zone Z1 is not shown for convenience.
  • the some nozzle 41 may be opposingly arranged by the up-down direction.
  • the arrangement pitch p of the nozzles 41 in the transport direction above or below the casting film 22 is 100 to 1000 mm, more preferably 250 to 500 mm. Further, the distance d between the upper and lower nozzles 41 and 41 is ⁇ 50 to 50 mm, more preferably 10 to 30 mm. When the nozzles 41 and 41 are arranged to face each other as shown in FIG. 3, the distance d between the nozzles 41 and 41 is set to be larger than 0 mm.
  • the blowing speed (wind speed) when blowing the heating air from the nozzle 41 is 10 to 40 m / sec, more preferably 20 to 30 m / sec.
  • the end of the casting film 22 may flutter, and the surface of the casting film 22 may be scratched due to contact with the nozzle 41 or may break.
  • the arrangement pitch p of the nozzles 41 and the distance d between the upper and lower nozzles 41 and 41 according to the elasticity of the casting film 22 in the above range the fluttering of the casting film 22 is suppressed and surface defects are reduced. High wind speed can be realized while suppressing.
  • the air curtain C1 is generated between the preheating zone Z1 and the stretching zone Z2, and the casting film 22 is preheated while generating the air curtain C2 between the stretching zone Z2 and the cooling zone Z3.
  • the zone Z1, the stretching zone Z2, and the cooling zone Z3 are passed in this order.
  • the air curtains C1 and C2 are a kind of wall generated by blowing air from a nozzle (not shown), and the air (heating air) in adjacent zones mixes to change the temperature, or the casting film. 22 is generated for the purpose of preventing the accompanying air accompanying the conveyance of 22 from flowing into the downstream zone.
  • the adjacent zones of the first extending portion 3 are partitioned by, for example, partition walls, depending on the partition wall gaps (gap through which the casting film 22 passes), if the casting film 22 flutters during transportation, the casting film 22 is separated from the partition walls. Touching the surface may scratch or damage the surface. However, by generating the air curtains C1 and C2 as described above, there is no fear of surface damage due to fluttering of the casting film 22.
  • the peripheral surface is a holding angle capable of stably transporting a film (casting film) such as a suction roller or a guide roller.
  • a film such as a suction roller or a guide roller.
  • a roller that is wound around, held, and conveyed is disposed.
  • FIG. 4 is a cross-sectional view schematically showing an arrangement example of rollers on the upstream side and the downstream side in the transport direction of the first stretching unit 3.
  • At least one tension regulating roller 51 is provided on the upstream side of the first stretching unit 3 in the transport direction.
  • three tension regulating rollers 51 are provided. These tension regulating rollers 51 correspond to the above-described low-speed roller group.
  • the tension regulating roller 51 is provided for regulating (relaxing) the tension in the conveying direction applied to the peeling portion of the casting film 22 from the endless belt 11 by MD stretching of the casting film 22 by the first stretching unit 3. Yes.
  • the tension applied to the peeling portion during MD stretching is relaxed, and the casting film 22 is not forcibly pulled in the transport direction at the peeling portion.
  • variation of the peeling position of the casting film 22 can be suppressed, and the casting film 22 can be peeled and conveyed with a predetermined residual solvent amount (described later).
  • the holding angle ⁇ of the casting film 22 in the tension regulating roller 51 is preferably set to 180 ° or more. In FIG. 4, the holding angle ⁇ is approximately 270 °.
  • the holding angle ⁇ is the upstream contact on the circumferential surface, the central axis of the roller, and the downstream side on the circumferential surface in a state where the casting film 22 is in contact with the circumferential surface of the tension regulating roller 51. Refers to the angle between contact points.
  • auxiliary rollers 52 and 53 are arranged on the upstream side and the downstream side of the tension regulating roller 51, respectively, and pass between the auxiliary roller 52 and the tension regulating roller 51 and between the tension regulating roller 51 and the auxiliary roller 53.
  • the holding angle (270 °) is realized by allowing the casting film 22 to wrap around the circumferential surface of the tension regulating roller 51.
  • the casting film 22 is reliably held on the peripheral surface of the tension regulating roller 51, so that the tension during MD stretching is surely secured by the tension regulating roller 51. It can cut and the fluctuation
  • the apparatus becomes larger, so that 1 to 10 tension regulating rollers 51 are preferably provided, and more preferably 1 to 3 tension regulating rollers 51 are provided.
  • At least one transport roller 54 is provided on the downstream side in the transport direction of the first stretching unit 3, and in the present embodiment, three transport rollers 54 are provided.
  • These transport rollers 54 correspond to the above-described high-speed roller group, and transport the casting film 22 at a speed corresponding to the stretching ratio in the MD direction in the first stretching section 3. For example, if the stretching ratio in the MD direction is twice, the transport roller 54 transports the casting film 22 at twice the speed before stretching.
  • the holding angle ⁇ of the casting film 22 in the transport roller 54 is set to 180 ° or more, similarly to the tension regulating roller 51 on the upstream side.
  • auxiliary rollers 55 and 56 are arranged on the upstream side and the downstream side of the conveyance roller 54, respectively, and are cast between the auxiliary roller 55 and the conveyance roller 54 and between the conveyance roller 54 and the auxiliary roller 56.
  • the holding angle ⁇ is set to 270 °. With such a holding angle ⁇ of 180 ° or more, the cast film 22 after MD stretching can be reliably held and transported by the peripheral surface of the transport roller 54.
  • the apparatus becomes large, and therefore it is preferable to provide 1 to 10 transport rollers 54, and more preferably 1 to 3 transport rollers 54.
  • FIG. 5 is a cross-sectional view schematically showing another arrangement example of the rollers on the upstream side and the downstream side in the transport direction of the first stretching unit 3.
  • the tension regulating rollers 51 are alternately arranged up and down from the upstream side to the downstream side
  • the conveyance rollers 54 are alternately arranged up and down from the upstream side to the downstream side, thereby regulating the tension.
  • the casting film 22 may be transported by setting the holding angle ⁇ of the roller 51 and the transport roller 54 to 180 °. Even in this case, the same effect as described above can be obtained.
  • FIG. 6 is a cross-sectional view along the width direction showing another configuration example of the roller on the upstream side in the transport direction of the first stretching unit 3.
  • one tension regulating roller 51 is disposed on the upstream side in the transport direction of the first stretching unit 3, and both end portions in the width direction of the casting film 22 between the tension regulating roller 51.
  • Auxiliary rollers 57 and 57 for niping may be arranged.
  • the tension in the transport direction of the casting film 22 during MD stretching can also be achieved by niping the end part in the width direction of the casting film 22 with the tension regulating roller 51 and the auxiliary roller 57 (side nip). Therefore, the fluctuation of the peeling position of the casting film 22 can be suppressed.
  • a defect such as a scratch may occur on the surface of the edge part of the casting film 22 due to the nip.
  • roller configuration shown in FIG. 6 can of course be applied to the roller on the downstream side of the first stretching section 3.
  • a tenter When stretching in the TD direction in the first stretching step, it is preferable to use a tenter as disclosed in JP-A-62-46625.
  • the tenter to be used is not particularly limited and is versatile. From the viewpoint of ease of operation, for example, a clip tenter, a pin tenter and the like can be mentioned, and can be selected and used as necessary. Among these, a tenter method using a clip is preferably used.
  • stretching part 4 shown in FIG. 1 performs the 2nd extending
  • the first stretching portion 3 can be stretched in the MD direction
  • the second stretching portion 4 can be stretched in the TD direction. Therefore, depending on the extending direction, the first extending portion 3 or the second extending portion 4 can be omitted.
  • the second stretching unit 4 stretches in the TD direction while heating the casting film 22 to remove the solvent.
  • the solvent removing means dry air can be used, but there is no particular limitation.
  • a heating means such as an infrared heater can also be used.
  • the drying conditions in the second stretching section 4 vary depending on the amount of residual solvent in the casting film 22 at the start of stretching by the second stretching section 4, but drying time, shrinkage unevenness, stability of the amount of stretching, etc. In addition, it achieves a reasonable stretching, and from the viewpoint of ensuring good dryness, flatness and film thickness uniformity without voids in the manufactured optical film, and ensuring elastic modulus and optical properties. It may be dried at a temperature of 3 or 4 stages, and may be divided into several stages and dried at several stages.
  • the drying unit 5 performs drying of the cast film 22 that has been MD-stretched in the first stretching step and TD-stretched in the second stretching step.
  • the drying unit 5 includes a drying box 5a having a drying air inlet 5b and an outlet 5c, an upper transport roller 5d that transports the casting film 22, and a lower transport roller 5e.
  • the upper transport roller 5d and the lower transport roller 5e are composed of a plurality of sets, one set for the upper and lower sides.
  • the number of transport rollers 5d and 5e disposed in the drying unit 5 varies depending on the drying conditions, the drying method, the length of the optical film to be manufactured, and the like, and may be set as appropriate.
  • the upper conveyance roller 5d and the lower conveyance roller 5e are free rotation rollers that are not rotationally driven by a drive source.
  • a transport roller that freely rotates is not used between the drying unit 5 and the winding unit 6, but usually one to several transport drive rollers (rollers that are driven to rotate by a drive source). Requires installation.
  • the purpose of the driving roller for conveyance is to convey the casting film 22 by its driving, so that the casting film 22 is conveyed and the driving roller is rotated by nip, suction (air suction) or the like. With a mechanism to synchronize with.
  • the drying unit 5 may dry using heated air, infrared rays, or the like alone, or may dry using heated air and infrared rays in combination. It is preferable to use heated air from the viewpoint of simplicity.
  • FIG. 1 shows a case where heated air is used.
  • a suitable drying temperature varies depending on the amount of residual solvent in the casting film 22 when entering the drying process, but in consideration of drying time, shrinkage unevenness, stability of the stretch amount, etc., for example, in the range of 30 to 180 ° C. What is necessary is just to select and decide suitably by the amount of residual solvents. Further, it may be dried at a constant temperature, or may be divided into three to four stages of temperature and may be divided into several stages of temperature.
  • the residual solvent amount of the cast film 22 after the drying process in the drying unit 5 is in the range of 0.01 to 0.5% by mass in consideration of the load of the drying process, the dimensional stability during storage and the expansion / contraction rate. Is preferred.
  • the casting film 22 formed in the casting part 2 is gradually removed in the drying part 5, and the casting film 22 having a total residual solvent amount of, for example, 2% by mass or less is formed into a film. There is a case.
  • the winding unit 6 is a drying unit 5 that winds an optical film having a predetermined residual solvent amount in a roll shape around a core to a required length.
  • the temperature at the time of winding is preferably cooled to room temperature in order to prevent abrasion, loosening, etc. due to shrinkage after winding.
  • the winder to be used can be used without particular limitation, and may be a commonly used one.
  • a winder that winds by a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension controller method with a constant internal stress can be used.
  • the cast film 22 that has been MD-stretched or TD-stretched is dried by the above-described drying section 5 and winding section 6 and wound as an optical film F.
  • the return material may be contained in a mass ratio of 10 to 70% by mass with respect to the optical film. If it is 10% by mass or more, it is advantageous in terms of production cost, and if it is 70% by mass or less, it is preferable from the viewpoint of reducing failures (occurrence of foreign matter and gouge) caused by the recycled material.
  • Recycled material refers to material generated on the web or film that has not been turned into a product due to a loss due to cutting off both ends of the film roll, immediately after the start of the work, condition adjustment, or in the final stage during the drying of the optical film.
  • the film is crushed to a size of 0.5 to 40 mm, preferably 10 to 30 mm, with a crusher to obtain chips.
  • ⁇ Pulverized chips are transferred to a storage container by pneumatic transportation means such as a blower, temporarily stored in a storage container, and then the determined input amount is weighed with a measuring instrument and put into a dissolution tank.
  • the dope is prepared by dissolving with heating and stirring together with new polyimide resin and solvent. After dissolution is complete, the solution is fed with a feed pump, the impurities are filtered with a filter, stored in a stationary storage tank, and defoamed.
  • a low-boiling solvent having a boiling point of 80 ° C. or lower as the main solvent because the film manufacturing process temperature (particularly the drying temperature) can be reduced and the thermal shrinkage rate can be reduced to improve the flatness of the film.
  • “used as a main solvent” means that if it is a mixed solvent, 55% by mass or more is used with respect to the total amount of the solvent, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably Is 90% by mass or more. Of course, if it is used alone, it becomes 100% by mass.
  • the low boiling point solvent only needs to dissolve the polyimide resin and other additives at the same time.
  • chlorinated solvent dichloromethane
  • non-chlorinated solvent methyl acetate, ethyl acetate, amyl acetate, acetone , Methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3 -Difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2 , 2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol,
  • the low boiling point solvent having a boiling point of 80 ° C. or less among the above solvents, dichloromethane (40 ° C.), ethyl acetate (77 ° C.), methyl ethyl ketone (79 ° C.), tetrahydrofuran (66 ° C.), acetone (56.5 ° C.) And at least one selected from 1,3-dioxolane (75 ° C.) as a main solvent (the parentheses each represent a boiling point).
  • solvents such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene may be used to the extent that the polyimide resin and additives according to the present invention do not precipitate. .
  • Alcohol solvents can also be used.
  • the alcohol solvent is preferably selected from methanol, ethanol, and butanol from the viewpoint of improving peelability and enabling high-speed casting. Of these, methanol or ethanol is preferably used. When the ratio of the alcohol in the dope increases, the cast film gels, and peeling from the metal support becomes easy.
  • a method carried out at normal pressure a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544 and JP-A-9
  • Various dissolution methods can be used, such as a method using the cooling dissolution method described in JP-A-95557 or JP-A-9-95538, and a method using high pressure described in JP-A-11-21379.
  • the prepared dope is guided to a filter by a liquid feed pump or the like and filtered.
  • the main solvent of the dope is dichloromethane
  • the gel-like foreign matter in the dope can be removed by filtering the dope at a temperature of boiling point at 1 atm of the dichloromethane + 5 ° C. or more.
  • a preferred temperature range is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably within a range of 45 to 55 ° C.
  • a material obtained by pelletizing a polyimide resin and other compounds in advance can be preferably used.
  • the metal support in casting (casting) is preferably a mirror-finished surface, and the support is preferably a metal support such as a stainless steel belt or a drum whose surface is plated with a casting.
  • the cast width can be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m.
  • the support may not be made of metal, for example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6,6 film, polypropylene film.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • nylon 6 film nylon 6,6 film
  • polypropylene film polypropylene film.
  • a belt made of polytetrafluoroethylene or the like can be used.
  • the polyimide resin may be wound together with the metal
  • the traveling speed of the metal support is not particularly limited, but is usually 5 m / min or more, preferably 10 to 180 m / min, particularly preferably 80 to 150 m / min. As the traveling speed of the metal support increases, entrained gas is more likely to be generated, and the occurrence of film thickness unevenness due to disturbance is more pronounced.
  • the traveling speed of the metal support is the moving speed of the outer surface of the metal support.
  • the surface temperature of the metal support is preferable because the higher the temperature, the faster the casting film can be dried. However, if the surface temperature is too high, the casting film may foam or the flatness may deteriorate. It is preferably carried out within a temperature range of ⁇ 50 to ⁇ 10 ° C. with respect to the boiling point of the solvent to be used.
  • the die has a shape that becomes gradually narrower toward the discharge port in the vertical cross section with respect to the width direction. Specifically, the die has tapered surfaces on the downstream side and the upstream side in the lower traveling direction, and a discharge port is formed in a slit shape between the tapered surfaces.
  • a die made of metal is preferably used, and specific examples include stainless steel and titanium. In the present invention, when manufacturing films having different thicknesses, it is not necessary to change to dies having different slit gaps.
  • ⁇ It is preferable to use a pressure die that can adjust the slit shape of the die base and easily make the film thickness uniform.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used. Even when films with different thicknesses are continuously manufactured, the discharge rate of the dies is maintained at a substantially constant value. Therefore, when a pressure die is used, conditions such as extrusion pressure and shear rate are also substantially reduced. Maintained at a constant value.
  • two or more pressure dies may be provided on the metal support, and the dope amount may be divided and laminated.
  • solvent evaporation process The solvent evaporation step is performed on the metal support, and the cast film is heated on the metal support to evaporate the solvent.
  • a method of appropriately selecting and combining them is also preferable.
  • the surface temperature of the metal support may be the same as a whole or may be different depending on the position.
  • the temperature of the heating air is preferably in the range of 10 to 220 ° C.
  • the temperature of the heating air (drying temperature) is preferably 200 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 120 ° C. or lower.
  • the solvent evaporation step it is preferable to dry the cast film until the residual solvent amount is in the range of 10 to 150% by mass from the viewpoint of the peelability of the cast film and the transportability after peeling.
  • the amount of residual solvent can be expressed by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
  • M is the mass at a predetermined point of the casting membrane (web)
  • N is the mass when M is dried at 200 ° C. for 3 hours.
  • M when calculating the amount of residual solvent achieved in the solvent evaporation step is the mass of the cast film immediately before the peeling step.
  • the peeling tension when peeling the metal support from the casting film is usually in the range of 60 to 400 N / m. However, if wrinkles are likely to occur during peeling, peeling is performed with a tension of 190 N / m or less. It is preferable.
  • the temperature at the peeling position on the metal support is preferably in the range of ⁇ 50 to 60 ° C., more preferably in the range of 10 to 40 ° C., and in the range of 15 to 40 ° C. Is most preferred.
  • the peeled film may be sent directly to the stretching process, or may be sent to the stretching process after being sent to the preliminary drying process so as to achieve a desired residual solvent amount.
  • the film is preferably sequentially sent to the preliminary drying step and the stretching step after the peeling step.
  • the preliminary drying step (not shown) is a drying step in which the film is heated to further evaporate the solvent.
  • the preliminary drying step may be the zone Z1 of the first drying step.
  • the drying means is not particularly limited, and for example, hot air, infrared rays, a heating roller, microwaves and the like can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner.
  • the drying temperature is preferably in the range of 30 to 200 ° C., taking into account the amount of residual solvent and the stretching ratio during conveyance.
  • the drying temperature is preferably 200 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 120 ° C. or lower.
  • a feature of the present invention is that the stretching temperature in the stretching step is in the range of (Tg ⁇ 250 ° C.) to (Tg ⁇ 100 ° C.) when the glass transition temperature of the polyimide resin is Tg (° C.),
  • the stretching temperature is performed at a temperature higher by 50 ° C. or more than the boiling point Tb (° C.) of the main solvent.
  • stretching temperature refers to the atmospheric temperature in the stretching step.
  • the atmospheric temperature and the temperature of the casting film are almost the same.
  • the measurement can be performed by a thermometer installed in each zone in the stretching process.
  • the “stretching temperature” is defined as the temperature of each stretching zone Z2 when the stretching process includes the first stretching portion 3 and the second stretching portion 4 as described above.
  • the stretching temperatures must be in the range of (Tg ⁇ 250 ° C.) to (Tg ⁇ 100 ° C.). It is.
  • what is necessary is just to adjust the temperature of the extending
  • the stretching temperature is less than (Tg ⁇ 250 ° C.)
  • the tension at the time of stretching of the optical film becomes too large, and the retardation development property for stretching becomes too high, which makes it difficult to control and there is a risk of breakage and the like. It is not preferable because it increases.
  • the “stretching temperature” refers to the temperature when the stretching temperature is constant, and the average temperature during stretching when the stretching temperature is changed within the range of the stretching temperature.
  • the stretching temperature is characterized by being performed at a temperature higher by 50 ° C. or more than the boiling point Tb (° C.) of the main solvent.
  • Tb boiling point
  • a preferable temperature is in the range of + 80 ° C. to + 200 ° C. from the boiling point Tb (° C.) of the main solvent.
  • the change in the stretching temperature from the start of stretching to the end of stretching in the stretching step is characterized by being within 70 ° C.
  • the stretching in the first stretching section 3 may be performed at a constant temperature, or divided into three to four stages of temperature and several stages of temperature.
  • the stretching temperature changes greatly during the process, a bowing phenomenon in which the optical axis is bowed is likely to occur, and in-plane retardation unevenness increases.
  • display unevenness is likely to occur.
  • the temperature change when the temperature change is performed, the temperature change needs to be within 70 ° C, preferably within 50 ° C, more preferably within 30 ° C, Particularly preferred is stretching at a constant temperature.
  • a temperature history may be taken such that the temperature is gradually increased, gradually decreased, or the temperature is increased and then decreased. If the temperature change width does not exceed 70 ° C. Good.
  • the draw ratio in the TD direction is preferably in the range of 0 (width retention) to 100%, and more preferably in the range of 5 to 50%.
  • the stretching operation may be performed in multiple stages.
  • simultaneous biaxial stretching may be performed or may be performed stepwise.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
  • the amount of residual solvent during stretching is preferably controlled within the range of 3 to 100% by mass.
  • “at the time of stretching” means from the start of stretching to the end of stretching.
  • the residual solvent amount refers to the solvent residual amount from the start of stretching to the end of stretching, and the history thereof is not questioned.
  • the amount of residual solvent from the start of stretching to the end of stretching may be adjusted to be constant, or at the start of stretching is 100% by mass or less, and gradually decreases during stretching. If it is 3 mass% or more, it is judged to be within the preferable range of the present invention.
  • the residual solvent amount at the start of stretching may be adjusted in the preliminary drying step described above, or may be performed in the preheating zone Z1.
  • stretching in the width direction stretching in the width direction of the film at a stretching speed in the range of 50 to 1000% / min is preferable from the viewpoint of improving the flatness of the film.
  • the stretching speed is 50% / min or more, the planarity is improved and the film can be processed at high speed, which is preferable from the viewpoint of production aptitude, and if it is within 1000% / min, the film is broken. Can be processed without any problem.
  • More preferable stretching speed is in the range of 100 to 500% / min.
  • the stretching speed is defined by the following formula.
  • Stretching speed (% / min) [(d 1 / d 2 ) ⁇ 1] ⁇ 100 (%) / t
  • d 1 is the width dimension in the stretching direction of the resin film after stretching
  • d 2 is the width dimension in the stretching direction of the resin film before stretching
  • t is the time (min) required for stretching. .
  • the stretching step usually, after stretching, holding and relaxation are performed. That is, in this step, it is preferable to perform a stretching step for stretching the film, a holding step for holding the film in a stretched state, and a relaxation step for relaxing the film in the stretched direction in this order.
  • the drawing at the draw ratio achieved in the drawing step is held at the drawing temperature in the drawing step.
  • the relaxation stage the stretching in the stretching stage is held in the holding stage, and then the stretching is relaxed by releasing the tension for stretching.
  • the relaxation stage may be performed at a temperature lower than the stretching temperature in the stretching stage.
  • the stretched film is heated and dried.
  • a means for preventing the mixing of used hot air by installing a nozzle capable of exhausting used hot air (air containing solvent or wet air) is also preferably used.
  • the hot air temperature is more preferably in the range of 40 to 350 ° C.
  • the drying time is preferably about 5 seconds to 30 minutes, more preferably 10 seconds to 15 minutes.
  • the heating and drying means is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, etc. can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner.
  • the drying temperature is preferably in the range of 40 to 150 ° C. from the viewpoint of easy heating shrinkage. More preferably, it is 40 to 120 ° C.
  • the drying step it is preferable to dry the film until the residual solvent amount is 0.5% by mass or less.
  • Winding process is a process of winding up the obtained optical film and cooling to room temperature.
  • the winding machine may be a commonly used one, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, or the like.
  • the thickness of the optical film is not particularly limited and is preferably in the range of 1 to 200 ⁇ m, particularly 1 to 100 ⁇ m, for example.
  • both ends of the optical film sandwiched between tenter clips when stretched and conveyed may be slit.
  • the slit end portion of the optical film is preferably cut into a width of 1 to 30 mm, then dissolved in a solvent and reused as a recycled material.
  • Each step from the solvent evaporation step to the winding step described above may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. Moreover, each process, especially a drying process and a extending process, are performed in consideration of the explosion limit concentration of the solvent in the atmosphere.
  • a heating step of further heat-treating the polyimide film dried in the drying step may be performed in order to advance imidization in the polymer chain molecule and between the polymer chain molecules to improve mechanical properties.
  • the said drying process may serve as a heating process.
  • the heating means is performed using a known means such as hot air, an electric heater, or a microwave.
  • a known means such as hot air, an electric heater, or a microwave.
  • the electric heater the above-described infrared heater can be used.
  • the heating step when the polyimide film is heated rapidly, problems such as an increase in surface defects occur, and therefore it is preferable to select a heating method as appropriate.
  • the heating step is preferably performed in a low oxygen atmosphere.
  • the heating temperature in the second drying step and the heating step exceeds 450 ° C.
  • the energy required for heating becomes very large, resulting in an increase in manufacturing cost and an increase in environmental load.
  • the following is preferable.
  • the optical film of the present invention is preferably long, specifically, preferably has a length in the range of about 100 to 10,000 m, and is wound up in a roll shape.
  • the width of the optical film of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.
  • polyimide resin according to the present invention is a polyimide resin that is dissolved in 1 g or more in 100 g of dichloromethane or 1,3-dioxolane at 25 ° C.
  • the film which formed the said solution cast film by using the said polyimide resin as a main component forms the film in which the total light transmittance mentioned later is 80% or more, and a yellow index value (YI value) is 6.0 or less.
  • YI value yellow index value
  • the polyimide resin according to the present invention is a resin having an imide structure, and is a resin including an imide bond in a repeating unit.
  • the polyimide resin (hereinafter simply referred to as polyimide) is preferably formed from diamine or a derivative thereof and an acid anhydride or a derivative thereof.
  • Preferred polyimides for the present invention include polyimide, polyamideimide, polyetherimide, and polyesterimide having a structure represented by the following formula (1.1).
  • Polyimide having the structure represented by the formula (1.1) (1) Structure of acid anhydride
  • the polyimide that can be used in the present invention is particularly represented by the following formula (1.1).
  • a polyimide having a repeating unit is preferred.
  • R represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, or a tetravalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 4 to 39 carbon atoms.
  • A represents a group consisting of a divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and as a bonding group, —O—, — At least one selected from the group consisting of SO 2 —, —CO—, —CH 2 —, —C (CH 3 ) 2 —, —OSi (CH 3 ) 2 —, —C 2 H 4 O—, and —S—.
  • One group may be contained.
  • Examples of the aromatic hydrocarbon ring represented by R include fluorene ring, benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o- Terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthre Ring.
  • examples of the aromatic heterocycle represented by R include a silole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and an oxadiene ring.
  • Azole ring triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring ( Any one of the carbon atoms constituting the dicarbosyl ring, dibenzofuran ring, dibenzothiophene ring, benzothiophene ring or dibenzofuran ring.
  • Examples of the tetravalent aliphatic hydrocarbon group having 4 to 39 carbon atoms represented by R include a butane-1,1,4,4-tetrayl group, an octane-1,1,8,8-tetrayl group, Examples include decane-1,1,10,10-tetrayl group.
  • Examples of the tetravalent alicyclic hydrocarbon group having 4 to 39 carbon atoms represented by R include cyclobutane-1,2,3,4-tetrayl group, cyclopentane-1,2,4,5. -Tetrayl group, cyclohexane-1,2,4,5-tetrayl group, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetrayl group, bicyclo [2.2.2] Octane-2,3,5,6-tetrayl group, 3,3 ′, 4,4′-dicyclohexyltetrayl group, 3,6-dimethylcyclohexane-1,2,4,5-tetrayl group, 3,6- And groups such as diphenylcyclohexane-1,2,4,5-tetrayl group.
  • Examples of the divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms which may or may not have the above linking group represented by A include groups represented by the following structural formula.
  • n represents the number of repeating units, preferably 1 to 5, and more preferably 1 to 3.
  • X is an alkanediyl group having 1 to 3 carbon atoms, that is, a methylene group, an ethylene group, a trimethylene group, or a propane-1,2-diyl group, and a methylene group is preferable.
  • Examples of the divalent alicyclic hydrocarbon group having 2 to 39 carbon atoms which may or may not have the above linking group represented by A include groups represented by the following structural formula.
  • Examples of the divalent aromatic hydrocarbon group having 2 to 39 carbon atoms which may or may not have the above linking group represented by A include groups represented by the following structural formula.
  • Examples of the group consisting of a combination of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group represented by A include groups represented by the following structural formulas.
  • the group represented by A is preferably a divalent aromatic hydrocarbon group having 2 to 39 carbon atoms having a linking group, or a combination of the aromatic hydrocarbon group and an aliphatic hydrocarbon group.
  • a group represented by the following structural formula is preferred.
  • the acid anhydride used in the present invention is a carboxylic acid anhydride and is preferably a derivative of an aliphatic or alicyclic tetracarboxylic acid, such as an aliphatic or alicyclic tetracarboxylic acid ester, aliphatic or An alicyclic tetracarboxylic dianhydride etc. are mentioned.
  • an aliphatic or alicyclic tetracarboxylic acids or derivatives thereof alicyclic tetracarboxylic dianhydrides are preferred.
  • the derivative is a compound that can be changed to an aliphatic or alicyclic tetracarboxylic acid.
  • a compound having two carboxy groups instead of the anhydride A compound in which one or both of these two carboxy groups is an esterified product, or an acid chloride in which one or both of these two carboxy groups are chlorinated is preferably used.
  • Examples of the aliphatic tetracarboxylic acid include 1,2,3,4-butanetetracarboxylic acid.
  • Examples of the alicyclic tetracarboxylic acid include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid.
  • Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, etc. Can be mentioned.
  • Examples of the aliphatic tetracarboxylic acid esters include monoalkyl esters, dialkyl esters, trialkyl esters, and tetraalkyl esters of the above aliphatic tetracarboxylic acids.
  • Examples of the alicyclic tetracarboxylic acid esters include monoalkyl esters, dialkyl esters, trialkyl esters, and tetraalkyl esters of the above alicyclic tetracarboxylic acids.
  • the alkyl group site is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.
  • Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, , 4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] And octane-2,3,5,6-tetracarboxylic dianhydride.
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride is particularly preferred.
  • a polyimide having an aliphatic diamine as a constituent component forms a strong salt between the polyamic acid, which is an intermediate product, and a diamine. Therefore, in order to increase the molecular weight, a solvent having a relatively high salt solubility (for example, cresol).
  • a solvent having a relatively high salt solubility for example, cresol.
  • N, N-dimethylacetamide, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc. are preferably used.
  • an acid anhydride having a fluorene skeleton or a derivative thereof may be used. It has the effect of improving the coloring unique to polyimide.
  • the acid anhydride having a fluorene skeleton include 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride and 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl.
  • Fluoronic acid dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-phenylphenyl] fluoric acid dianhydride, and the like can be used.
  • Aromatic, aliphatic or alicyclic tetracarboxylic acids or derivatives thereof may be used alone or in combination of two or more. Further, other tetracarboxylic acids or derivatives thereof (particularly dianhydrides) may be used in combination as long as the solvent solubility of polyimide, the flexibility of the polyimide film, thermocompression bonding, and transparency are not impaired.
  • Examples of such other tetracarboxylic acids or derivatives thereof include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2, 2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,4-dicarboxy) Phenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, bis (2,3-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2
  • 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or biphenyltetracarboxylic dianhydride is excellent in transparency and heat due to heat shrinkage. This is preferable from the viewpoint of easy correction.
  • the repeating unit represented by the formula (1.1) is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably all the repeating units. Is 90 to 100 mol%.
  • the number of repeating units of formula (1.1) in one molecule of polyimide (A) is 10 to 2000, preferably 20 to 200, and further within this range, the glass transition temperature is 230 to 350 ° C. The temperature is preferably 250 to 330 ° C.
  • diamine or derivative thereof for example, aromatic diamine or isocyanate ester is preferable, and aromatic diamine is preferable.
  • the diamine or derivative thereof used in the present invention may be an aromatic diamine, an aliphatic diamine or a mixture thereof, and is preferably an aromatic diamine from the viewpoint of suppressing whitening of the polyimide film.
  • aromatic diamine refers to a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or any other part of its structure. It may contain a substituent (for example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.).
  • aliphatic diamine refers to a diamine in which an amino group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group or other substituent (for example, it may contain a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.).
  • aromatic diamines include, for example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolidine, m-tolidine, bis (trifluoromethyl) Benzidine, octafluorobenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl 3,3'-difluoro-4,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 ' -Diaminodiphenyl
  • aliphatic diamine examples include ethylene diamine, hexamethylene diamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, 1,3-bis (aminomethyl) cyclohexane, 1,4 -Bis (aminomethyl) cyclohexane, m-xylylenediamine, p-xylylenediamine, 1,4-bis (2-amino-isopropyl) benzene, 1,3-bis (2-amino-isopropyl) benzene, isophorone Diamine, norbornanediamine, siloxane diamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylme
  • a diamine having a fluorene skeleton or a derivative thereof may be used for the purpose of improving the coloring unique to polyimide.
  • a diamine compound having a triazine mother nucleus represented by the following formula can be preferably used.
  • R 1 represents a hydrogen atom or an alkyl group or an aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
  • R 2 represents an alkyl group or an aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
  • R 1 and R 2 may be different or the same. May be.
  • alkyl group or aryl group having 1 to 12 carbon atoms of R 1 and R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl, benzyl, naphthyl, methylphenyl, and biphenyl.
  • aminoanilino group connected to the two NH groups of triazine is 4-aminoanilino or 3-aminoanilino, which may be the same or different, but 4-aminoanilino is preferred.
  • diamine compound represented by the above formula having a triazine mother nucleus examples include 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine, 2,4-bis ( 3-aminoanilino) -6-anilino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-benzylamino-1,3,5-triazine, 2,4-bis (3-aminoanilino ) -6-Benzylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-naphthylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino)- 6-biphenylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-diphenylamino-1,3,5-triazine, 2,4-bis
  • examples of other diamine derivatives include diaminodisilanes, such as trimethylsilylated aromatic or aliphatic diamines obtained by reacting the above aromatic or aliphatic diamines with chlorotrimethylsilane.
  • the diamine is preferably 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl from the viewpoint of excellent transparency and easy thermal correction by heat shrinkage.
  • the above diamines and derivatives thereof may be used in an arbitrary mixture, but the amount of diamine in them is preferably 50 to 100 mol%, more preferably 80 to 100 mol%.
  • polyamic acid is a polymerization reaction of at least one of the tetracarboxylic acids and at least one of the diamines. Is obtained.
  • the polyamic acid ester is diesterified by ring-opening the tetracarboxylic dianhydride with an alcohol such as methanol, ethanol, isopropanol, or n-propanol, and the obtained diester is converted into the above-mentioned diester in an appropriate solvent. It can be obtained by reacting with a diamine compound. Furthermore, the polyamic acid ester can also be obtained by esterification by reacting the carboxylic acid group of the polyamic acid obtained as described above with an alcohol as described above.
  • the reaction between the tetracarboxylic dianhydride and the diamine compound can be carried out under conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound.
  • a polycarboxylic acid can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.
  • the amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more with respect to 1 mol of tetracarboxylic dianhydride. On the other hand, it is 1.2 mol or less normally, Preferably it is 1.1 mol or less.
  • the yield of the polyamic acid obtained can be improved by making the quantity of a diamine compound into such a range.
  • the concentration of tetracarboxylic dianhydride and diamine compound in the solvent is appropriately set according to the reaction conditions and the viscosity of the polyamic acid solution.
  • the total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more with respect to the total amount of the solution, while usually 70%. It is not more than mass%, preferably not more than 30 mass%.
  • the reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 100 ° C. or lower, preferably 80 ° C. or lower.
  • the reaction time is not particularly limited but is usually 1 hour or longer, preferably 2 hours or longer, and is usually 100 hours or shorter, preferably 24 hours or shorter.
  • Examples of the polymerization solvent used in this reaction include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene.
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene
  • carbon tetrachloride dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene.
  • halogenated hydrocarbon solvents such as fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N, N— Amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide and ⁇ -butyrolactone; pyridine, picoline, lutidine, quinoline and isoquinoline Ring-based solvents; phenols and phenolic solvents such as cresol, but and the like, but is not particularly limited.
  • a polymerization solvent only 1 type can also be used and 2 or more types of solvents can also be mixed and used.
  • an acid anhydride group or an amino group can be arbitrarily selected by using either one of a tetracarboxylic dianhydride and a diamine compound in excess during the polymerization reaction.
  • the acid anhydride terminal may be left without performing the subsequent treatment, or may be hydrolyzed to obtain a dicarboxylic acid. Moreover, it is good also as ester using C4 or less alcohol. Furthermore, you may seal a terminal
  • the amine compound or isocyanate compound used here is not particularly limited as long as it is a monofunctional primary amine compound or isocyanate compound.
  • aniline methylaniline, dimethylaniline, trimethylaniline, ethylaniline, diethylaniline, triethylaniline, aminophenol, methoxyaniline, aminobenzoic acid, biphenylamine, naphthylamine, cyclohexylamine, phenyl isocyanate, xylylene isocyanate, cyclohexyl isocyanate , Methylphenyl isocyanate, trifluoromethylphenyl isocyanate, and the like.
  • the terminal group is an amine terminal, it is possible to prevent the amino group from remaining at the terminal by sealing the terminal amino group with a monofunctional acid anhydride.
  • a monofunctional acid anhydride if it is a monofunctional acid anhydride which becomes dicarboxylic acid or tricarboxylic acid when hydrolyzed, it can be used without particular limitation.
  • maleic anhydride methylmaleic anhydride, dimethylmaleic anhydride, succinic anhydride, norbornene dicarboxylic acid anhydride, 4- (phenylethynyl) phthalic anhydride, 4-ethynylphthalic anhydride, phthalate Acid anhydride, methylphthalic anhydride, dimethylphthalic anhydride, trimellitic anhydride, naphthalenedicarboxylic anhydride, 7-oxabicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] Heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 4-oxatricyclo [5.2 .2.0 2,6] undecane-3,5-dione, octahydro-1,3-dioxo-isobenzofuran-5-car
  • the polyimide is prepared by heating a polyamic acid solution to imidize the polyamic acid (thermal imidization method), or adding a ring-closing catalyst (imidation catalyst) to the polyamic acid solution. It can be obtained by a method of imidizing polyamic acid (chemical imidization method).
  • thermo imidization method a method of imidizing polyamic acid by heating the polyamic acid solution
  • a reaction vessel for polymerizing polyamic acid from an acid anhydride and a diamine may be continued as it is and imidized in the reaction vessel.
  • the polyamic acid in the polymerization solvent is heated for, for example, 80 to 300 ° C. for 0.1 to 200 hours to advance imidization.
  • the temperature range is preferably 150 to 200 ° C., and by setting the temperature range to 150 ° C. or higher, imidization can be reliably progressed and completed. It is possible to prevent the resin concentration from increasing due to oxidation of unreacted raw materials and volatilization of the solvent.
  • an azeotropic solvent can be added to the polymerization solvent in order to efficiently remove water generated by the imidization reaction.
  • the azeotropic solvent for example, aromatic hydrocarbons such as toluene, xylene and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane can be used.
  • the amount added is about 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of organic solvent.
  • a known ring closure catalyst is added to the polyamic acid in the polymerization solvent to advance imidization.
  • the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and picoline. Examples thereof include substituted nitrogen-containing heterocyclic compounds, N-oxide compounds of nitrogen-containing heterocyclic compounds, substituted or unsubstituted amino acid compounds, aromatic hydrocarbon compounds having an hydroxy group, or aromatic heterocyclic compounds.
  • alkyl imidazole such as dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl-2-methyl Imidazole derivatives such as imidazole, isoquinoline, 3
  • a substituted pyridine such as 5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, p-toluenesulfonic acid, etc. can be preferably used. it can.
  • the addition amount of the ring closure catalyst is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
  • a dehydrating agent may be added to the polyamic acid solution.
  • a dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, phthalates, and the like. Examples thereof include aromatic acid anhydrides such as acid anhydrides, and these can be used alone or in combination.
  • it is preferable to use a dehydrating agent because the reaction can proceed at a low temperature.
  • it is possible to imidize polyamic acid only by adding a dehydrating agent to the polyamic acid solution it is preferable to imidize by heating or addition of a ring-closing catalyst as described above because the reaction rate is slow. .
  • the polyimide solution imidized in the reaction kettle is advantageous because it is less likely to cause a decrease in molecular weight due to hydrolysis over time as compared with the polyimide solution.
  • the imidization reaction has progressed in advance, for example, in the case of a polyimide having an imidization rate of 100%, imidization on the cast film is unnecessary, and the drying temperature can be lowered.
  • the ring-closed polyimide may be reprecipitated using a poor solvent or the like, purified to a solid, dissolved in a solvent, cast and dried, and then formed into a film.
  • the polymerization solvent and the solvent to be cast can be made different types, and the performance of the polyimide film can be further extracted by selecting the optimum solvent for each.
  • polyamic acid in order to increase the molecular weight of polyamic acid, it is polymerized and cyclized with dimethylacetamide, solidified with methanol, dried, then made into a solution containing an additive with dichloromethane, then cast and dried.
  • dimethylacetamide solidified with methanol
  • dichloromethane a solution containing an additive with dichloromethane
  • dichloromethane when used as a solvent, it can be used in combination with other solvents.
  • a co-solvent such as tetrahydrofuran (THF), 1,3-dioxolane, cyclohexanone, cyclopentanone, ⁇ -butyrolactone, ethanol, methanol, butanol, and isopropyl alcohol can be used as appropriate.
  • polyimides containing atoms such as phosphorus, silicon, and sulfur can also be used.
  • the polyimide containing phosphorus for example, as the polyimide containing phosphorus, the polyimides described in paragraphs [0010]-[0021] of JP2011-74209A and paragraphs [0011]-[0025] of JP2011-074177A are used. Can do.
  • polyimide containing silicon a polyimide obtained by imidizing a polyimide precursor described in paragraphs [0030] to [0045] of JP2013-028796A can be used.
  • Examples of the polyimide containing sulfur include paragraphs [0009]-[0025] of JP 2010-189322 A, paragraphs [0012]-[0025] of JP 2008-274234 A, and paragraphs of JP 2008-274229 A.
  • Polyimides obtained by imidizing polyimide precursors described in [0012]-[0023] can be used.
  • alicyclic polyimides described in paragraphs [0008]-[0012] of JP-A-2009-256590 and paragraphs [0008]-[0012] of JP-A-2009-256589 are preferably used. it can.
  • polyamideimide used in the present invention is a polyamideimide containing tricarboxylic acid or tetracarboxylic acid, dicarboxylic acid as an acid component, and diamine as a structural unit as an amine component.
  • the polyamideimide used is an acid component a) Tricarboxylic acid; diphenyl ether-3,3 ', 4'-tricarboxylic acid, diphenylsulfone-3,3', 4'-tricarboxylic acid, benzophenone-3,3 ', 4'-tricarboxylic acid, naphthalene-1,2 , 4-tricarboxylic acid, butan-1,2,4-tricarboxylic acid and other tricarboxylic acid monoanhydrides, esterified products and the like, or a mixture of two or more.
  • Tetracarboxylic acid diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid , Naphthalene-1,4,5,8-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid monoanhydride, dianhydride , Esterified compounds alone, or a mixture of two or more.
  • amine component d) Amine component 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, p-phenylenediamine, m -Phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminobiphenyl, 3,3 ' -Diamin
  • trimellitic anhydride TMA
  • BTDA 3,3,4', 4'-biphenyltetracarboxylic acid
  • BPDA raw material containing dianhydride
  • NDI 1,5-naphthalene diisocyanate
  • the molar ratio between the imide bond and the amide bond of the polyamideimide is preferably 99/1 to 60/40, more preferably 99/1 to 75/25, and even more preferably 90/10 to 80/20. is there.
  • the molar ratio of the imide bond to the amide bond is 60/40 or more, the heat resistance, moisture resistance reliability, and heat resistance reliability are improved.
  • it is 99/1 or less, the elastic modulus tends to be low, and the folding resistance and bending characteristics tend to be improved.
  • Polyamideimide having a structure represented by the formula (2) as an essential component One preferred embodiment has a structure represented by the formula (2) as an essential component, and further includes formulas (3) and (4). ) And at least one structure selected from the group represented by formula (5) is a polyamide-imide resin containing in the molecular chain as a repeating unit.
  • Y represents an oxygen atom, CO, or OOC—R—COO.
  • N represents 0 or 1
  • R represents a divalent organic group.
  • Y is preferably a benzophenone type (CO) or a bond type (biphenyl bond).
  • Y is preferably a benzophenone type (CO) or a bond type (biphenyl bond).
  • formula (2) is a repeating unit from trimellitic anhydride and 1,5-naphthalene diisocyanate
  • formula (3) is a repeating unit from terephthalic acid and 1,5-naphthalene diisocyanate
  • the polyamideimide resin can be synthesized by a usual method. For example, an isocyanate method, an amine method (acid chloride method, low temperature solution polymerization method, room temperature solution polymerization method, etc.), etc., but the polyamideimide resin used in the present invention is preferably soluble in an organic solvent, as described above. For reasons such as ensuring the reliability of peel strength (adhesive strength), production by the isocyanate method is preferred. Also, industrially, it is preferable because the solution at the time of polymerization can be applied as it is.
  • Polyamideimide having a structure represented by formula (6) or formula (7) As a preferred polyamideimide resin, a compound containing the following formula (6) as a structural unit can be preferably used. Hereinafter, the compound having a structure represented by the formula (6) will be described.
  • R 1 is an aryl group or a cycloalkane group, and may contain nitrogen, oxygen, sulfur, or halogen.
  • the diamine component includes p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone.
  • 3,3′-dimethyl-4,4′-diaminobiphenyl, dicyclohexylmethane-4,4′-diamine (trans isomer, cis isomer, trans / cis mixture), 4,4′-diaminodiphenyl ether, p- Use of phenylenediamine, 4-methyl-1,3-phenylenediamine, or the like alone, or a mixture of two or more thereof, or a diisocyanate corresponding to these alone, or a mixture of two or more, as the diamine component. it can.
  • 3,3′-dimethyl-4,4′-diaminobiphenyl, dicyclohexylmethane-4,4′-diamine (trans isomer, cis isomer, trans / cis mixture), 4,4′-diaminodiphenyl ether, 4 -Methyl-1,3-phenylenediamine or the like alone, or a mixture of two or more kinds, or the corresponding diisocyanate or the like alone or a mixture of two or more kinds can be used as the diamine component.
  • 3,3′-dimethyl-4,4′-diaminobiphenyl, dicyclohexylmethane-4,4′-diamine (trans isomer, cis isomer, trans / cis mixture), 4-methyl-1,3-phenylene A diamine or the like alone, or a mixture of two or more kinds, or a diisocyanate corresponding to these alone or a mixture of two or more kinds can be used as the diamine component.
  • the following components are obtained from the heat resistance, solvent resistance, and durability in the process of forming a film, and the heat resistance, surface smoothness, and transparency of the produced polyamideimide film. Is preferably used.
  • cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride can be used as the acid component.
  • Polyamideimide resin containing cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride as an acid component can be used.
  • the diamine component at least one or two compounds selected from the group consisting of 3,3′-dimethyl-4,4′-diaminobiphenyl and 4-methyl-1,3-phenylenediamine, or 3,3 At least one or two compounds selected from the group consisting of '-dimethyl-4,4'-diisocyanate biphenyl (o-tolidine diisocyanate) and 4-methyl-1,3-phenylene diisocyanate (tolylene diisocyanate); Can be used.
  • a compound containing a structure represented by the following formula (7) as a structural unit can be used as a preferred polyamideimide resin.
  • R 2 and R 3 each represent hydrogen, an alkyl group having 1 to 3 carbon atoms, or an aryl group, and may contain nitrogen, oxygen, sulfur, or halogen.
  • the exemplified acid component is preferably contained in an amount of 50 mol% to 100%, more preferably 70 mol% to 100%.
  • the exemplified diamine component may be contained in an amount of 50 mol% to 100%, more preferably 70 mol% to 100%.
  • the molecular weight of the polyamideimide resin used is a molecular weight corresponding to 0.3 to 2.5 cm 3 / g in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / cm 3 ) in terms of logarithmic viscosity at 30 ° C. And more preferably those having a molecular weight corresponding to 0.5 to 2.0 cm 3 / g.
  • the logarithmic viscosity is 0.3 cm 3 / g or more, mechanical properties are sufficient when formed into a molded product such as a film.
  • it is 2.0 cm 3 / g or less, the solution viscosity does not become too high and the molding process becomes easy.
  • polyetherimide used is a thermoplastic resin containing an aromatic nucleus bond and an imide bond in its structural unit, and is not particularly limited. Specifically, the following formula (8 Or a polyetherimide having a repeating unit having a structure represented by the following formula (9).
  • Polyetherimides having a repeating unit having the structure represented by the above formula (8) are trade names “Ultem 1000” (glass transition temperature: 216 ° C.) and “Ultem 1010” (glass transition temperature: 216) manufactured by General Electric. ° C), polyetherimide having a repeating unit having the structure represented by the above formula (9) includes “Ultem CRS5001” (glass transition temperature Tg 226 ° C.), and other specific examples are manufactured by Mitsui Chemicals, Inc. Trade name “Aurum PL500AM” (glass transition temperature 258 ° C.).
  • the method for producing the polyetherimide is not particularly limited.
  • the amorphous polyetherimide having the structure represented by the above formula (8) is 4,4 ′-[isopropylidenebis (p -Phenyleneoxy)] diphthalic acid dianhydride and m-phenylenediamine as a polycondensate
  • polyetherimide having the structure represented by the above structural formula (9) is 4,4 ′-[isopropylidenebis (P-phenyleneoxy)] diphthalic dianhydride and p-phenylenediamine are synthesized by a known method.
  • polyetherimide may contain other copolymerizable monomer units such as an amide group, an ester group, and a sulfonyl group within the range not exceeding the gist of the present invention.
  • polyetherimide can be used individually by 1 type or in combination of 2 or more types.
  • Polyesterimide The resin having an imide structure used in the present invention preferably contains a polyesterimide structure represented by the formula (10) in the structural unit.
  • R 1 represents a divalent group having a specific structure.
  • R 2 represents a divalent chain aliphatic group, a divalent cycloaliphatic group or a divalent aromatic group.
  • R 1 represents a divalent group having a structure represented by Formula (11), Formula (12), or Formula (13), respectively.
  • R represents a divalent chain aliphatic group, cycloaliphatic group or aromatic group, and a plurality of R may be the same or different from each other. .
  • These chain aliphatic groups, cycloaliphatic groups or aromatic groups can be used alone or in combination of two or more.
  • M is a positive integer of 1 or more, preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
  • the upper limit of m is not specifically limited, Preferably it is 25 or less, More preferably, it is 20 or less, More preferably, it is 10 or less. When it exceeds 25, the heat resistance tends to decrease.
  • the chain aliphatic group, cycloaliphatic group or aromatic group is “chain aliphatic compound having a divalent hydroxy group”, “cycloaliphatic compound having a divalent hydroxy group” or “2
  • a residue derived from a diol such as an “aromatic compound having a valent hydroxy group” is desirable. Further, it may be a residue derived from “polycarbonate diol” which can be polymerized from the diol and carbonates or phosgene.
  • chain aliphatic compound having a divalent hydroxy group a branched or linear diol having two hydroxy groups can be used.
  • alkylene diol, polyoxyalkylene diol, polyester diol, polycaprolactone diol and the like can be mentioned.
  • Examples of branched or linear diols having two hydroxy groups that can be used as the “chain aliphatic compound having a divalent hydroxy group” are listed below.
  • alkylene diol examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4- And cyclohexanedimethanol.
  • polyoxyalkylene diol examples include dimethylolpropionic acid (2,2-bis (hydroxymethyl) propionic acid), dimethylolbutanoic acid (2,2-bis (hydroxymethyl) butanoic acid), polyethylene glycol, polypropylene glycol, Examples include polytetramethylene glycol, polyoxytetramethylene glycol, and a random copolymer of tetramethylene glycol and neopentyl glycol. Polyoxytetramethylene glycol is preferable.
  • polyester diol examples include polyester diols obtained by reacting polyhydric alcohols and polybasic acids exemplified below.
  • any “polyhydric alcohol” can be used as the “polyhydric alcohol component” used in the polyester diol.
  • any of various polybasic acids can be used.
  • terephthalic acid isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid Acids, adipic acid, sebacic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, etc.
  • Aliphatic and alicyclic dibasic acids can be used.
  • polyester diol examples include ODX-688 (aliphatic polyester diol manufactured by DIC Corporation: adipic acid / neopentyl glycol / 1,6-hexanediol, number average molecular weight of about 2000), Vylon (registered). (Trademark) 220 (polyester diol manufactured by Toyobo Co., Ltd., number average molecular weight of about 2000).
  • polycaprolactone diol examples include polycaprolactone diol obtained by ring-opening addition reaction of lactones such as ⁇ -butyllactone, ⁇ -caprolactone, and ⁇ -valerolactone.
  • chain aliphatic compound having a divalent hydroxy group can be used alone or in combination of two or more.
  • Cycloaliphatic compound having a divalent hydroxy group” or “aromatic compound having a divalent hydroxy group” includes “a compound having two hydroxy groups in an aromatic ring or cyclohexane ring”, “two "Compounds in which phenol or alicyclic alcohol is bonded with a divalent functional group”, “Compounds having one hydroxy group in both nuclei of the biphenyl structure”, “Compounds having two hydroxy groups in the naphthalene skeleton”, etc. Is used.
  • Examples of the “compound having two hydroxy groups in the aromatic ring or cyclohexane ring” include hydroquinone, 2-methylhydroquinone, resorcinol, catechol, 2-phenylhydroquinone, cyclohexanedimethanol, tricyclodecanemethanol, 1,4-dihydroxycyclohexane, , 3-dihydroxycyclohexane, 1,2-dihydroxycyclohexane, 1,3-adamantanediol, dicyclopentadiene dihydrate, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxy Carboxy group-containing diols such as benzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid can be used.
  • two phenols or “a compound in which an alicyclic alcohol is bonded with a divalent functional group”
  • examples of “two phenols” or “a compound in which an alicyclic alcohol is bonded with a divalent functional group” include 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4, 4 '-(9-fluorenylidene) diphenol, 4,4'-dihydroxydicyclohexyl ether, 4,4'-dihydroxydicyclohexyl sulfone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like can be used.
  • Examples of “compound having one hydroxy group in both nuclei of biphenyl structure” include 4,4′-biphenol, 3,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5. 5,5'-tetramethyl-4,4'-biphenol and the like can be used.
  • the number average molecular weight of the diol is preferably 100 or more and 30000 or less, more preferably 150 or more and 20000 or less, and further preferably 200 or more and 10,000 or less. When the number average molecular weight is less than 100, low hygroscopicity and flexibility cannot be sufficiently exhibited.
  • phase separation may occur and the mechanical properties and colorless transparency may not be fully exhibited. .
  • the polycarbonate diol may be a polycarbonate diol having a plurality of types of alkylene groups as described above in the skeleton (copolymerized polycarbonate diol). For example, a combination of 2-methyl-1,8-octanediol and 1,9-nonanediol, a combination of 3-methyl-1,5-pentanediol and 1,6-hexanediol, 1,5-pentanediol and 1 , 6-hexanediol, and the like can be synthesized as a copolymerized polycarbonate diol.
  • a copolymer polycarbonate diol that can be synthesized from a combination of 2-methyl-1,8-octanediol and 1,9-nonanediol is preferable. Two or more of these polycarbonate diols can be used in combination.
  • Kuraray Kuraray Polyol C Series Asahi Kasei Chemicals Duranol Series, etc.
  • Kuraray polyol C-1015N Kuraray polyol C-1065N (Kuraray Co., Ltd. carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 1000)
  • Kuraray polyol C -2015N Kuraray polyol C2065N (Kuraray Co., Ltd.
  • polycarbonate diol 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 1000
  • Duranol T5652 Asahi Kasei Chemicals Co., Ltd. polycarbonate diol
  • polycarbonate diol 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 2000
  • Kuraray polyol C-1015N is used.
  • Examples of the method for producing the polycarbonate diol include transesterification between the raw diol and carbonates, and dehydrochlorination reaction between the raw diol and phosgene.
  • Examples of the carbonic acid ester as a raw material include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate and propylene carbonate.
  • R 3 is a direct bond, an alkylene group (—C n H 2n —), a perfluoroalkylene group (—C n F 2n —), an ether bond (—O—), an ester bond (—COO—). ), Carbonyl group (—CO—), sulfonyl group (—S ( ⁇ O) 2 —), sulfinyl group (—SO—), sulfenyl group (—S—), carbonate group (—OCOO—), or fluorenylidene Represents a group.
  • n is a positive integer of 1 or more.
  • n is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
  • X 1 to X 8 may be the same or different and each represents a hydrogen, halogen or alkyl group.
  • divalent group having a structure represented by the formula (12) are not particularly limited, but include diphenyl ether skeleton, diphenyl sulfone skeleton, 9-fluorenylidene diphenol skeleton, bisphenol A skeleton, bisphenol F skeleton, Examples thereof include an ethylene oxide adduct skeleton of bisphenol A, a propylene oxide adduct skeleton of bisphenol A, a biphenyl skeleton, and a naphthalene skeleton.
  • the skeleton is preferably a residue derived from a compound having one hydroxy group on each of the benzene rings in the formula (12).
  • the raw material for the divalent group having the structure represented by the formula (12) include 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4,4 ′-(9-fluorenylidene) diphenol, Bisphenol A, bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 4,4'-biphenol, 3,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 5'-tetramethyl-4,4'-biphenol, 2,6-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,8-naphthalenediol, and the like can be used.
  • 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4,4 ′-(9-fluorenylidene) diphenol or bisphenol A ethylene oxide adduct is preferred. More preferably, 4,4′-dihydroxydiphenyl ether or ethylene oxide adduct of bisphenol A is used.
  • diphenyl ether skeleton or the like can be introduced into the R 1 position of the formula (10).
  • R 4 represents a direct bond, an alkylene group (—C n H 2n —), a perfluoroalkylene group (—C n F 2n —), an ether bond (—O—), an ester bond (—COO—). ), Carbonyl group (—CO—), sulfonyl group (—S ( ⁇ O) 2 —), sulfinyl group (—SO—), sulfenyl group (—S—), carbonate group (—OCOO—), or fluorenylidene Represents a group.
  • n is a positive integer of 1 or more.
  • n is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
  • X 1 ′ to X 8 ′ may be the same or different and each represents a hydrogen, halogen or alkyl group.
  • divalent group having the structure represented by the formula (13) are not particularly limited, but include a dicyclohexyl ether skeleton, a dicyclohexyl sulfone skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, and a hydrogenated bisphenol A. And the propylene oxide adduct skeleton of hydrogenated bisphenol A.
  • the skeleton is preferably a residue derived from a compound having one hydroxy group on each of the cyclohexane rings of the formula (13).
  • the raw material for the divalent group having the structure represented by the formula (13) include 4,4′-dihydroxydicyclohexyl ether, 4,4′-dihydroxydicyclohexylsulfone, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated An ethylene oxide adduct of bisphenol A or a propylene oxide adduct of hydrogenated bisphenol A can be used.
  • 4,4′-dihydroxydicyclohexyl ether or 4,4′-dihydroxydicyclohexyl sulfone is used.
  • dicyclohexyl ether skeleton or the like can be introduced at the R 1 position of the formula (10).
  • a halide of cyclohexanetricarboxylic anhydride and a diol are reacted to obtain an ester group-containing tetracarboxylic dianhydride, and then the ester group-containing tetracarboxylic acid. It can be obtained by condensation reaction (polyimidation) of dianhydride and diamine or diisocyanate.
  • the polyesterimide resin may further contain a structure represented by the formula (14) in the structural unit.
  • R 2 in the formula (10) and R 2 ′ in the formula (14) will be described.
  • R 2 and R 2 ′ are not particularly limited as long as they are each independently a divalent chain aliphatic group, a divalent cycloaliphatic group, or a divalent aromatic group.
  • These “divalent chain aliphatic group”, “divalent cycloaliphatic group”, and “divalent aromatic group” can be used alone or in combination of two or more.
  • R 2 is a divalent group having a structure represented by the following formula (15), and R 2 ′ is a divalent group having a structure represented by the following formula (16).
  • R 2 in the formula (10) is preferably a divalent group having a structure represented by the formula (15) from the balance of heat resistance, flexibility, low hygroscopicity, and the like.
  • R 5 represents a direct bond, an alkylene group (—C n H 2n —), a perfluoroalkylene group (—C n F 2n —), an ether bond (—O—), an ester bond (—COO—). ), A carbonyl group (—CO—), a sulfonyl group (—S ( ⁇ O) 2 —), a sulfinyl group (—SO—) or a sulfenyl group (—S—).
  • n is preferably a positive integer of 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • X 9 to X 16 may be the same or different and each represents a hydrogen, halogen or alkyl group.
  • R 2 ′ in the formula (14) is preferably a divalent group having a structure represented by the formula (16) from the viewpoint of heat resistance, flexibility, low hygroscopic balance, and the like.
  • R 5 ′ is a direct bond, an alkylene group (—C n H 2n —), a perfluoroalkylene group (—C n F 2n —), an ether bond (—O—), an ester bond (—COO -), A carbonyl group (—CO—), a sulfonyl group (—S ( ⁇ O) 2 —), a sulfinyl group (—SO—) or a sulfenyl group (—S—).
  • n is preferably a positive integer of 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • X 9 ′ to X 16 ′ may be the same or different and each represents a hydrogen, halogen or alkyl group.
  • a divalent chain aliphatic group is represented by R in the formula (10)
  • R is represented by R in the formula (10)
  • a corresponding diamine component or diisocyanate component respectively. That is, “aromatic diamine or the corresponding aromatic diisocyanate”, “cycloaliphatic diamine or the corresponding cycloaliphatic diisocyanate”, “chain aliphatic diamine or the corresponding chain aliphatic diisocyanate” are appropriately used.
  • a polyesterimide resin excellent in heat resistance, flexibility and low hygroscopicity can be obtained.
  • the diamine component of R 2 of formula (10) and R 2 ′ of formula (14) or the corresponding diisocyanate component may be the same or different. If based on the preferable manufacturing method mentioned later, it is preferable that it is the same.
  • a diamine component having R 2 and R 2 ′ as a basic skeleton or a corresponding diisocyanate component will be described.
  • aromatic diamine or the corresponding aromatic diisocyanate examples include 2,2′-bis (trifluoromethyl) benzidine, p-phenylenediamine, m-phenylenediamine, , 4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis (2-methylaniline), 4, 4'-methylenebis (2-ethylaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4 -Diaminodiphenyl ether, 4,4'-
  • cycloaliphatic diamine or the corresponding cycloaliphatic diisocyanate examples include trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-diamino, as diamine compounds.
  • Cyclohexane (trans / cis mixture), 1,3-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) (trans isomer, cis isomer, trans / cis mixture), isophoronediamine, 1,4-cyclohexanebis (methylamine) ), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 4,4′-me Renbis (2-methylcyclohexylamine), 4,4'-methylenebis (2-ethylcyclohexylamine), 4,4'-methylenebis (2,6-dimethylcyclohexylamine), 4,4'-methylenebis (2,6- Diethyl cyclohexy
  • chain aliphatic diamine or the corresponding chain aliphatic diisocyanate examples include 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1, Examples include 6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, and 1,9-nonamethylene diamine. These can be used in combination of two or more.
  • R 2 in formula (10) and R 2 ′ in formula (14) or a preferred diisocyanate component corresponding thereto are exemplified as diamine compounds.
  • 4,4′-diaminodiphenylmethane 4,4′-diaminodiphenyl ether, 1,5-naphthalenediamine, o-tolidine
  • 4,4′-diaminodiphenylmethane 4,4 ′.
  • -Diaminodiphenyl ether o-tolidine
  • Most preferred is a residue derived from 4,4'-diaminodiphenylmethane, o-tolidine.
  • the polyimide according to the present invention preferably contains a fluorinated polyimide from the viewpoint of excellent transparency of the polyimide film and easy thermal correction by thermal shrinkage.
  • the fluorine content is more preferably in the range of 1 to 40% by mass in the film because the effect of the present invention is great.
  • the optical film of the present invention is a transparent polyimide film, and as a measure of transparency, the total light transmittance when a sample having a thickness of 100 ⁇ m is prepared is 80% or more.
  • the total light transmittance is more preferably 85% or more, and still more preferably 90% or more. A higher total light transmittance is preferable because transparency increases.
  • the description of the numerical value that the total light transmittance is 80% or more shows the preferable range.
  • the total light transmittance of the optical film can be measured according to JIS K 7375-2008 for one optical film sample conditioned for 24 hours in an air-conditioned room at 23 ° C. and 55% RH.
  • the transmittance in the visible light region (range of 400 to 700 nm) can be measured using a spectrophotometer U-3300 manufactured by Hitachi High-Technologies Corporation.
  • the total light transmittance 80% or more it can be adjusted by selecting the type of polyimide.
  • the optical film according to the present invention is a colorless polyimide film.
  • the yellow index value (YI value) when a sample having a thickness of 100 ⁇ m is produced is 6.0 or less. More preferably, it is in the range of 0.3 to 4.0, and particularly preferably in the range of 0.3 to 2.0. A smaller yellow index value (YI value) is preferable because coloring is less.
  • the description of the numerical value that the yellow index value (YI value) is 6.0 or less indicates the preferable range.
  • the YI value can be adjusted by selecting the type of polyimide.
  • the yellow index value can be obtained according to the YI (yellow index: yellowness index) of the film defined in JIS K 7103.
  • the yellow index value is measured by preparing a film sample and using a spectrophotometer U-3300 manufactured by Hitachi High-Technologies Corporation and the attached saturation calculation program, etc., as a light source specified in JIS Z 8701.
  • the tristimulus values X, Y and Z of the color are obtained, and the yellow index value is obtained according to the definition of the following formula.
  • the polyimide resin according to the present invention is a polyimide resin that dissolves 1 g or more in 100 g of dichloromethane or 1,3-dioxolane at 25 ° C. If the solubility is 1 g or more, it can be easily produced by the solution casting method. Higher solubility is preferred because it facilitates production by the solution casting method.
  • the description of the numerical value that the solubility is 1 g or more shows an indication of a preferable range as the soluble polyimide resin.
  • a polyimide resin having a solubility of 1 g or more that dissolves in 100 g of dichloromethane at 25 ° C. tends to be a transparent film having a total light transmittance of 80% or more. Further, the film tends to be a colorless film having a yellow index value (YI value) of 6.0 or less.
  • the solubility of the polyimide according to the present invention can be adjusted by selecting the type of polyimide resin used in the present invention.
  • the polyimide resin In order to make the polyimide resin soluble, it is effective to reduce the ratio of the structure of imide groups and aromatic hydrocarbons that work in the direction of increasing the planarity of the molecular skeleton of the polyimide. It is also effective to introduce structural isomers, bending groups, aliphatic groups or alicyclic groups instead of aromatic groups, and bulky skeletons such as fluorine atoms and fluorenes.
  • Examples of compounds include alicyclic, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4, 5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, (bicyclo [4.2.0] octane -3,4,7,8-tetracarboxylic dianhydride) bicyclo [2.2.1] heptanedimethanamine, the structure having a bending group is 2,3 ', 3,4'-biphenyltetracarboxylic Acid dianhydride, 3,4'-oxydiphthalic anhydride, 4,4 'oxydiphthalic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3
  • Examples of the compound containing a fluorine atom include 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 2,2'-bis (trifluoromethyl) benzidine 2,2-bis (3-amino-4 -Hydroxyphenyl) hexafluoropropane, compounds containing a fluorene group include 9,9-bis (4-amino-3-fluorophenyl) fluorene, 9,9-bis [4- (3,4-dicarboxyphenoxy) ) -Phenyl] fluorene anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -phenyl] fluorene anhydride, 9,9-Bis (3,4-dicboxyphenyl) fluorene Pilot fluorene Dianhydride It is done.
  • a haze value is 4% or less from a viewpoint that the transparency of a polyimide film is high.
  • the haze can be measured according to JIS K 7136 using a haze meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Measured under conditions of 23 ° C. and 55% RH, the light source of the haze meter is a halogen bulb of 5 V and 9 W, and the light receiving part is a silicon photocell (with a relative luminous sensitivity filter).
  • additives of optical film The following additives can be further added to the optical film of the present invention.
  • the optical film of the present invention is preferably mixed with inorganic fine particles.
  • the slip ratio is improved when the mixing ratio of the inorganic fine particles into the optical film is 0.01% by mass or more. Accordingly, the flatness of the long-winding optical film is hardly deteriorated. Moreover, there exists an effect which prevents the haze increase of an optical film by setting it as 2.0 mass% or less.
  • the inorganic fine particles the following inorganic compound fine particles are preferably used.
  • fine particles of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.
  • Etc. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • the average primary particle size of the fine particles is preferably in the range of 5 to 400 nm, and more preferably in the range of 10 to 300 nm. These may be mainly contained as secondary aggregates having a particle size in the range of 0.05 to 0.3 ⁇ m. If the particles have an average particle size in the range of 80 to 400 nm, the primary particles are not aggregated. It is also preferable that it is contained.
  • the average particle size of the primary particles of the inorganic fine particles is small from the viewpoint of less variation in the haze value in the surface direction, which is an effect of the present invention.
  • the average particle size of the primary particles is preferably 30 nm or less, and more preferably 10 nm or less.
  • the inorganic fine particles are surface-modified and that the surface is more hydrophobic from the viewpoint of improving the degree of dispersion in the film and reducing variation in haze value.
  • the hydrophobic treatment is preferably surface-modified with at least one compound selected from alkylsilanes having an alkyl group having 5 to 21 carbon atoms, dimethylsiloxane, dimethylsiloxane cyclic, methacryloxysilane, and aminosilane. .
  • silica particles whose surface is modified with a compound having such a long-chain functional group or cyclic functional group improves the entanglement and interaction with the polyimide resin and facilitates the formation of secondary aggregates.
  • the matte effect of the optical film itself can be enhanced.
  • the content of these fine particles in the optical film is more preferably in the range of 0.01 to 1% by mass, and particularly preferably in the range of 0.05 to 0.5% by mass.
  • the surface contains this amount of fine particles.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • resin fine particles examples include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (above, Momentive Performance Materials Japan) It is commercially available under the trade name (made by a limited liability company) and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the haze of the optical film low.
  • the optical film of the present invention preferably contains an ultraviolet absorber from the viewpoint of improving light resistance.
  • the ultraviolet absorber is intended to improve light resistance by absorbing ultraviolet rays of 400 nm or less, and the transmittance at a wavelength of 370 nm is preferably in the range of 0.1 to 30%, more preferably. Is in the range of 1-20%, more preferably in the range of 2-10%.
  • the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, and particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers.
  • a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.
  • the optical film of the present invention preferably contains two or more ultraviolet absorbers.
  • a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used. Moreover, it is preferable that the ultraviolet absorber does not have a halogen group.
  • UV absorber to dope after dissolving UV absorber in alcohol such as methanol, ethanol, butanol, organic solvent such as dichloromethane, methyl acetate, acetone, 1,3-dioxolane or mixed solvent. Or may be added directly into the dope composition.
  • alcohol such as methanol, ethanol, butanol
  • organic solvent such as dichloromethane, methyl acetate, acetone, 1,3-dioxolane or mixed solvent.
  • organic solvent such as dichloromethane, methyl acetate, acetone, 1,3-dioxolane or mixed solvent.
  • organic solvent such as dichloromethane, methyl acetate, acetone, 1,3-dioxolane or mixed solvent.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber and the operating conditions, but when the dry film thickness of the optical film is 15 to 50 ⁇ m, it is 0.5 to 10% by mass relative to the optical film.
  • the range is preferably 0.6 to 4% by mass.
  • Antioxidant are also referred to as deterioration inhibitors. When an electronic device or the like is placed in a high humidity and high temperature state, the optical film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the polyimide film from being decomposed by, for example, halogen remaining in the optical film or phosphoric acid of a phosphoric acid plasticizer, and therefore, in the optical film of the present invention. It is preferable to contain.
  • the compounds described in paragraph numbers 0108 to 0119 of JP 2010-271619 A can be preferably used.
  • the amount of these compounds added is preferably in the range of 1 ppm to 1.0% by mass relative to the optical film, and more preferably in the range of 10 to 1000 ppm.
  • Phase difference control agent In order to improve the display quality of an image display device such as a liquid crystal display device, a retardation control agent is added to the optical film or an alignment film is formed to provide a liquid crystal layer. By combining the phase difference, the optical compensation ability can be imparted to the optical film.
  • Examples of the retardation control agent include aromatic compounds having two or more aromatic rings as described in European Patent No. 91656A2, and rod-shaped compounds described in JP-A-2006-2025. Two or more aromatic compounds may be used in combination.
  • the aromatic ring of the aromatic compound is preferably an aromatic heterocyclic ring including an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.
  • the aromatic heterocycle is generally an unsaturated heterocycle. Of these, the 1,3,5-triazine ring described in JP-A-2006-2026 is preferable.
  • the addition amount of these retardation control agents is preferably in the range of 0.5 to 20% by mass and preferably in the range of 1 to 10% by mass with respect to 100% by mass of the optical film resin. More preferred.
  • a peeling accelerator may be added to the optical film of the present invention in order to improve the peelability during film production.
  • preferable release agents include phosphate ester type surfactants, carboxylic acid or carboxylate type surfactants, A sulfonic acid or sulfonate surfactant and a sulfate ester surfactant are effective.
  • a fluorine-based surfactant in which part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is substituted with fluorine atoms is also effective. Examples of the release agent are given below.
  • RZ-1 C 8 H 17 O—P ( ⁇ O) — (OH) 2 RZ-2 C 12 H 25 O—P ( ⁇ O) — (OK) 2 RZ-3 C 12 H 25 OCH 2 CH 2 O—P ( ⁇ O) — (OK) 2 RZ-4 C 15 H 31 (OCH 2 CH 2 ) 5 O—P ( ⁇ O) — (OK) 2 RZ-5 ⁇ C 12 H 25 O (CH 2 CH 2 O) 5 ⁇ 2 -P ( O) -OH RZ-6 ⁇ C 18 H 35 (OCH 2 CH 2 ) 8 O ⁇ 2 —P ( ⁇ O) —ONH 4 RZ-7 (tC 4 H 9 ) 3 —C 6 H 2 —OCH 2 CH 2 O—P ( ⁇ O) — (OK) 2 RZ-8 (iso-C 9 H 19 —C 6 H 4 — O— (CH 2 CH 2 O) 5 —P ( ⁇ O) — (OK) (OH) RZ-9 C 12 H 25 SO 3 Na RZ-10 C 12 H
  • optical film containing the polyimide resin of the present invention can be used as a transparent film of an image display device.
  • it can be preferably applied to a flexible image display device.
  • the device to be applied is not particularly limited, and examples thereof include an organic electroluminescence (EL) image display device, a liquid crystal image display device (LCD), an organic photoelectric conversion device, a touch panel, a polarizing plate, and a retardation film.
  • EL organic electroluminescence
  • LCD liquid crystal image display device
  • an organic photoelectric conversion device a touch panel
  • a polarizing plate a retardation film.
  • it is preferably used for a flexible television receiver such as an organic electroluminescence (EL) image display device and a liquid crystal image display device (LCD), and a front member for flexible display.
  • the glass transition temperature Tg of the polyimide resin is a midpoint glass transition temperature (Tmg) measured according to JIS K7121 (1987), measured at a rate of temperature increase of 20 ° C./min. According to JIS K7121 (1987), Seiko Instruments ( It measured using the differential scanning calorimeter DSC220 made from Corporation
  • polyimide solution A containing polyimide resin A.
  • the weight average molecular weight of the polyimide resin A was 140,000.
  • a main dope having the following composition was prepared. First, dichloromethane (boiling point 40 ° C.) was added to the pressure dissolution tank. The prepared polyimide solution A was charged into a pressure dissolution tank containing a solvent while stirring. While this was heated and stirred, it was completely dissolved, and this was dissolved in Azumi Filter Paper No. The dope was prepared by filtration using 244.
  • composition of dope Dichloromethane 350 parts by weight Polyimide solution A 100 parts by weight Matting agent (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.) 0.5 parts by mass (casting process)
  • the dope was uniformly cast on a stainless steel belt support at a temperature of 30 ° C. and a width of 1500 mm so as to have a predetermined dry film thickness.
  • the temperature of the stainless steel belt was controlled at 30 ° C.
  • the pre-dried cast film is 1.50 times in the width direction using a clip type tenter while maintaining the temperature from the start of stretching (described as “initial” in Table 1) to the end of stretching at 250 ° C. Stretched. The amount of residual solvent at the time of stretching was 15% by mass.
  • the stretched film is dried at a drying temperature of 120 ° C. until the residual solvent amount is less than 0.5% by mass with a conveying tension of 100 N / m and a drying time of 15 minutes while being conveyed by a large number of rollers.
  • a polyimide film in the form of a long film having a width of 1900 mm and a length of 5000 m was obtained.
  • the obtained polyimide film was wound up to obtain a polyimide film 101.
  • polyimide films 102 to 109 were produced in the same manner except that the temperature at the start and end of stretching and the amount of residual solvent at the time of stretching were changed as shown in Table 1.
  • a polyimide film 110 was produced in the same manner except that the solvent used for dope preparation was changed to methyl isobutyl ketone (solvent boiling point 116 ° C.).
  • polyimide solution B containing polyimide resin B.
  • the weight average molecular weight of the polyimide resin B was 130,000.
  • polyimide films 120-137 ⁇ Preparation of polyimide films 120-137>
  • the solvent was changed to 1,3-dioxolane instead of dichloromethane, polyimide solution A and polyimide solution B were used, and the temperature at the start and end of stretching and the amount of residual solvent at the time of stretching were displayed.
  • Polyimide films 120 to 137 were produced in the same manner except that the change was made as described in 2.
  • the measurement was performed using a spectrophotometer U-3300 of Hitachi High-Technologies Corporation and the attached saturation calculation program, etc., and the average value of 10-point measurement was obtained. Any film using any resin was yellow.
  • the index value (YI value) was 6.0 or less.
  • ⁇ Dissolved amount in dichloromethane or dioxolane is 1 g or more ⁇ : Dissolved amount in dichloromethane or dioxolane is less than 1 g ⁇ 5>
  • Retardation unevenness In-plane retardation of each polyimide film was measured at 10 points in the width direction.
  • the standard deviation ( ⁇ ) of the phase difference value Ro was obtained and evaluated according to the following evaluation criteria. If it was ⁇ , it was judged that the phase difference unevenness was excellent.
  • ⁇ The standard deviation ( ⁇ ) of Ro is less than 5 nm.
  • X The standard deviation ( ⁇ ) of Ro is 5 nm or more.
  • the in-plane retardation value Ro is the retardation value Ro defined by the equation (i).
  • phase difference value Ro in the in-plane direction is determined by using an automatic birefringence meter Axoscan (AxoScan Mueller Matrix Polarimeter: manufactured by Axometrics) at a wavelength of 590 nm in a 23 ° C./55% RH environment. was measured, it was calculated from the refractive index resulting n x and n y.
  • the standard deviation ( ⁇ ) of the phase difference value Ro is the square root of the variance ⁇ 2 with respect to the average value of the measured values.
  • the average value is calculated by the following formula (where xi is each measured value and n is the number of measurement points).
  • the variance ⁇ 2 is calculated by the following formula.
  • the polyimide film of the present invention is excellent in returning material suitability and retardation unevenness.
  • the method for producing an optical film of the present invention produces an optical film containing soluble polyimide as a main component, which is easy to reuse as a recycle material and has reduced retardation unevenness due to the bowing phenomenon and retardation development during stretching. Therefore, the optical film is suitably used for a flexible television receiver such as an organic electroluminescence (EL) image display device and a liquid crystal image display device (LCD), and a front member for flexible display.
  • a flexible television receiver such as an organic electroluminescence (EL) image display device and a liquid crystal image display device (LCD)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Materials Engineering (AREA)
  • Moulding By Coating Moulds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un procédé de fabrication d'un film optique qui a un polyimide soluble en tant que composé principal, qui est facilement réutilisé en tant que déchet de retour, et qui a une non-uniformité de différence de phase réduite résultant d'une aptitude au développement de différence de phase et de phénomènes de courbure pendant un étirement. Le procédé de fabrication d'un film optique contenant une résine polyimide transparente soluble est caractérisé en ce qu'il comprend une étape consistant à couler un dopant sur un corps de support et former un film coulé, une étape consistant à détacher le film coulé du corps de support, et une étape consistant à étirer le film coulé détaché. Le procédé est en outre caractérisé en ce que la température d'étirement pendant l'étape d'étirement se situe dans la plage de (Tg-250°C) à (Tg-100°C), Tg (°C) étant la température de transition vitreuse de la résine polyimide. Le procédé est en outre caractérisé en ce que le changement de température du film du début à la fin de l'étirement ne dépasse pas 70°C, et la température d'étirement est au moins 50°C supérieure au point d'ébullition Tb (ºC) du solvant principal.
PCT/JP2017/006409 2016-03-31 2017-02-21 Procédé de fabrication de film optique Ceased WO2017169306A1 (fr)

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Cited By (2)

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JP2020003781A (ja) * 2018-06-22 2020-01-09 住友化学株式会社 樹脂フィルム及びその製造方法
JP2020125463A (ja) * 2019-01-31 2020-08-20 住友化学株式会社 光学フィルム、フレキシブル表示装置、及び樹脂組成物

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JP7161359B2 (ja) * 2018-09-27 2022-10-26 東京応化工業株式会社 加熱処理装置、イミド系樹脂膜製造システム、及び加熱処理方法
JP7284650B2 (ja) * 2019-06-27 2023-05-31 グンゼ株式会社 巻取体
JP7326956B2 (ja) * 2019-07-18 2023-08-16 コニカミノルタ株式会社 光学フィルム製造方法
JP7356895B2 (ja) * 2019-12-24 2023-10-05 株式会社カネカ 透明ポリイミド樹脂を含む光学フィルム並びにその製造方法
CN111217999B (zh) * 2020-02-20 2022-07-26 哈尔滨工程大学 柔性聚酰亚胺隔热泡沫的环保型制备方法及产品
KR102286213B1 (ko) * 2020-07-30 2021-08-06 에스케이이노베이션 주식회사 폴리이미드계 필름 및 이를 포함하는 플렉서블 디스플레이 패널
JP7541943B2 (ja) * 2021-03-10 2024-08-29 信越ポリマー株式会社 非晶性熱可塑性樹脂シート及びその製造方法
JPWO2023249053A1 (fr) * 2022-06-23 2023-12-28

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JP2006117903A (ja) * 2004-09-24 2006-05-11 Fuji Photo Film Co Ltd ポリマー、該ポリマーの製造方法、光学フィルムおよび画像表示装置
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JP2020125463A (ja) * 2019-01-31 2020-08-20 住友化学株式会社 光学フィルム、フレキシブル表示装置、及び樹脂組成物

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