WO2014156624A1 - 位相差フィルムの製造方法および円偏光板の製造方法 - Google Patents

位相差フィルムの製造方法および円偏光板の製造方法 Download PDF

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Publication number
WO2014156624A1
WO2014156624A1 PCT/JP2014/056403 JP2014056403W WO2014156624A1 WO 2014156624 A1 WO2014156624 A1 WO 2014156624A1 JP 2014056403 W JP2014056403 W JP 2014056403W WO 2014156624 A1 WO2014156624 A1 WO 2014156624A1
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WO
WIPO (PCT)
Prior art keywords
film
clip
pitch
stretching
clip pitch
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/JP2014/056403
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
清水　享
平田　聡
近藤　誠司
村上　奈穗
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.)
Nitto Denko Corp
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Nitto Denko Corp
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 Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to EP14773926.2A priority Critical patent/EP2980613B1/en
Priority to US14/780,695 priority patent/US9804313B2/en
Priority to CN201480017726.4A priority patent/CN105051579B/zh
Priority to KR1020157026546A priority patent/KR101759014B1/ko
Publication of WO2014156624A1 publication Critical patent/WO2014156624A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • 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
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00788—Producing optical films
    • 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
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • 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
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0031—Refractive
    • B29K2995/0032—Birefringent

Definitions

  • the present invention relates to a method for producing a retardation film and a method for producing a circularly polarizing plate.
  • circularly polarizing plates are used for the purpose of improving display characteristics and preventing reflection.
  • a circularly polarizing plate typically, a polarizer and a retardation film (typically ⁇ / 4 plate) form an angle of 45 ° between an absorption axis of the polarizer and a slow axis of the retardation film. Thus, they are laminated.
  • a retardation film is typically produced by uniaxially or biaxially stretching in the machine direction and / or the transverse direction, so that the slow axis is often the transverse direction of the original film. Appears in the direction (width direction) or longitudinal direction (long direction).
  • the present invention has been made to solve the above-described conventional problems.
  • the object of the present invention is to have excellent axial accuracy, small phase difference change and dimensional change during heating, and a slow axis in an oblique direction.
  • the object is to provide a method capable of producing a retardation film with high production efficiency.
  • Another object of the present invention is to provide a method capable of producing a circularly polarizing plate having excellent optical properties with high production efficiency.
  • the left and right ends of the film are respectively held by variable-pitch left and right clips whose longitudinal clip pitches change; the film is preheated; The clip pitch of the clip is changed independently, and the film is obliquely stretched; the clip pitch of the left and right clips is decreased, and the film is contracted in the vertical direction; and the clip that holds the film Freeing.
  • the manufacturing method is performed while reducing the clip pitch of the left and right clips to shrink the film in the longitudinal direction. And further stretching.
  • the oblique stretching is performed such that a position where the clip pitch of one of the left and right clips starts to increase and a position where the clip pitch of the other clip starts increasing are different positions in the vertical direction.
  • the clip pitch of each clip is expanded to a predetermined pitch.
  • the oblique stretching comprises (i) increasing the clip pitch of one of the left and right clips and decreasing the clip pitch of the other clip, and (ii) Increasing the reduced clip pitch to the same pitch as the enlarged clip pitch, and setting the clip pitch of each clip to a predetermined pitch.
  • the contraction rate in the longitudinal direction is 0.1% to 30%.
  • a retardation film is provided.
  • This retardation film is obtained by the above-described manufacturing method, has a long shape, and has a slow axis in a direction that forms a predetermined angle with respect to the long direction.
  • the manufacturing method of a circularly-polarizing plate is provided. This manufacturing method includes aligning the longitudinal direction of the retardation film and the long polarizing plate, and continuously bonding them together.
  • the film is stretched obliquely and then contracted in the longitudinal direction, thereby providing excellent axial accuracy, small phase difference change and dimensional change during heating, and phase difference having a slow axis in the oblique direction.
  • a film can be obtained with high production efficiency.
  • a circularly polarizing plate excellent in optical properties can be obtained with high production efficiency by laminating the retardation film and the polarizing plate thus obtained by so-called roll-to-roll. .
  • the left and right ends of the film to be stretched are each gripped by variable-pitch left and right clips whose longitudinal clip pitches change (step A: gripping step); Preheating the film (step B: preheating step); changing the clip pitch of the left and right clips independently and stretching the film diagonally (step C: stretching step); Reducing the clip pitch and shrinking the film in the longitudinal direction (step D: shrinking step); and releasing the clip holding the film (step E: releasing step).
  • step A gripping step
  • preheating step changing the clip pitch of the left and right clips independently and stretching the film diagonally
  • step D shrinking step
  • step E releasing the clip holding the film
  • FIG. 1 is a schematic plan view illustrating the overall configuration of an example of a stretching apparatus that can be used in the production method of the present invention.
  • 2 and 3 are schematic plan views of main parts for explaining a link mechanism for changing the clip pitch in the stretching apparatus of FIG. 1, respectively, FIG. 2 shows a state in which the clip pitch is minimum, and FIG. Indicates the maximum clip pitch.
  • the stretching device 100 has an endless loop 10L and an endless loop 10R having a large number of clips 20 for gripping the film on both the left and right sides in a plan view.
  • the left endless loop as viewed from the film entrance side is referred to as the left endless loop 10L
  • the right endless loop is referred to as the right endless loop 10R.
  • the clips 20 of the left and right endless loops 10L and 10R are guided by the reference rail 70 and move in a loop.
  • the left endless loop 10L rotates in a counterclockwise direction
  • the right endless loop 10R rotates in a clockwise direction.
  • a gripping zone A, a preheating zone B, a stretching zone C, a contraction zone D, and a release zone E are provided in this order from the inlet side to the outlet side of the sheet.
  • Each of these zones means a zone where the film to be stretched is substantially gripped, preheated, obliquely stretched, shrunk and released, and does not mean a mechanically and structurally independent section. . It should also be noted that the length ratio of each zone is different from the actual length ratio.
  • the left and right endless loops 10R and 10L are configured to be substantially parallel to each other at a separation distance corresponding to the initial width of the film to be stretched.
  • the distance between the left and right endless loops 10R and 10L is gradually increased from the preheating zone B side toward the contraction zone D until it corresponds to the width after stretching of the film.
  • the left and right endless loops 10R and 10L are configured to be substantially parallel to each other at a separation distance corresponding to the width after stretching of the film.
  • the left and right endless loops 10R and 10L may be configured to gradually expand or contract from the stretched width of the film (not shown).
  • the clip of the left endless loop 10L (left clip) 20 and the clip of the right endless loop 10R (right clip) 20 can each move independently.
  • the driving sprockets 11 and 12 of the left endless loop 10L are rotationally driven counterclockwise by the electric motors 13 and 14, and the driving sprockets 11 and 12 of the right endless loop 10R are clocked by the electric motors 13 and 14. It is driven to rotate around.
  • traveling force is applied to the clip carrying member 30 of the drive roller (not shown) engaged with the drive sprockets 11 and 12.
  • the left endless loop 10L cyclically moves in the counterclockwise direction
  • the right endless loop 10R cyclically moves in the clockwise direction.
  • the left endless loop 10L clip (left clip) 20 and the right endless loop 10R clip (right clip) 20 are each of variable pitch type. That is, the left and right clips 20 and 20 can independently change the clip pitch (distance between clips) in the vertical direction (MD) with movement.
  • the variable pitch type can be realized by any appropriate configuration.
  • a link mechanism pin mechanism
  • an elongated rectangular clip carrying member 30 is provided in the lateral direction in plan view for carrying the clips 20 individually.
  • the clip carrying member 30 is formed into a solid frame structure with a closed cross section by an upper beam, a lower beam, a front wall (wall on the clip side), and a rear wall (wall on the side opposite to the clip).
  • the clip carrying member 30 is provided so as to roll on the traveling road surfaces 81 and 82 by the traveling wheels 38 at both ends thereof. 2 and 3, the traveling wheels on the front wall (the traveling wheels that roll on the traveling road surface 81) are not shown.
  • the traveling road surfaces 81 and 82 are parallel to the reference rail 70 over the entire area.
  • a long hole 31 is formed along the longitudinal direction of the clip carrying member on the rear side (the side opposite to the clip) of the upper and lower beams of the clip carrying member 30, and the slider 32 can slide in the longitudinal direction of the long hole 31. Is engaged.
  • a single first shaft member 33 is vertically provided so as to penetrate the upper beam and the lower beam.
  • a single second shaft member 34 is vertically provided through the slider 32 of the clip carrying member 30.
  • One end of a main link member 35 is pivotally connected to the first shaft member 33 of each clip carrying member 30.
  • the main link member 35 is pivotally connected to the second shaft member 34 of the adjacent clip carrier member 30 at the other end.
  • one end of the sub link member 36 is pivotally connected to the first shaft member 33 of each clip carrying member 30.
  • the sub link member 36 is pivotally connected at the other end to the intermediate portion of the main link member 35 by a pivot shaft 37.
  • the clip pitch increases.
  • Positioning of the slider 32 is performed by the pitch setting rail 90. As shown in FIGS. 2 and 3, the larger the clip pitch, the smaller the separation distance between the reference rail 70 and the pitch setting rail 90. Since the link mechanism is well known in the art, a more detailed description is omitted.
  • a retardation film having a slow axis in an oblique direction (for example, a direction of 45 ° with respect to the longitudinal direction) can be produced by obliquely stretching the film using the stretching apparatus as described above.
  • the gripping zone A the entrance of the film take-in of the stretching apparatus 100
  • the left and right endless loops 10R, 10L are gripped by the clips 20 of the film to be stretched at a constant clip pitch.
  • the film is sent to the preheating zone B by the movement of the endless loops 10 ⁇ / b> R and 10 ⁇ / b> L (substantially, the movement of each clip holding member 30 guided by the reference rail 70).
  • the left and right endless loops 10R, 10L are configured to be substantially parallel to each other at a separation distance corresponding to the initial width of the film to be stretched as described above. Basically, neither transverse stretching nor longitudinal stretching is performed, and the film is heated. However, the distance between the left and right clips (distance in the width direction) may be slightly increased in order to avoid problems such as film deflection due to preheating and contact with the nozzles in the oven.
  • the film is heated to a temperature T1 (° C.). It is preferable that temperature T1 is more than the glass transition temperature (Tg) of a film, More preferably, it is Tg + 2 degreeC or more, More preferably, it is Tg + 5 degreeC or more. On the other hand, the heating temperature T1 is preferably Tg + 40 ° C. or lower, more preferably Tg + 30 ° C. or lower. Depending on the film used, the temperature T1 is, for example, 70 ° C. to 190 ° C., preferably 80 ° C. to 180 ° C.
  • the temperature raising time to the temperature T1 and the holding time at the temperature T1 can be appropriately set according to the constituent material of the film and the manufacturing conditions (for example, the film conveyance speed). These temperature raising time and holding time can be controlled by adjusting the moving speed of the clip 20, the length of the preheating zone, the temperature of the preheating zone, and the like.
  • the stretching zone C Stretching process
  • the clip pitch of the left and right clips 20 is changed independently, and the film is stretched obliquely.
  • the oblique stretching can be performed while increasing the distance between the left and right clips (distance in the width direction), for example, as in the illustrated example. This will be specifically described below.
  • the stretching zone C is described as being divided into an inlet-side stretching zone (first oblique stretching zone) C1 and an outlet-side stretching zone (second oblique stretching zone) C2.
  • the lengths of the first oblique stretching zone C1 and the second oblique stretching zone C2 and the ratio of the lengths to each other can be appropriately set according to the purpose.
  • the oblique stretching is performed such that a position where the clip pitch of one of the left and right clips starts to increase and a position where the clip pitch of the other clip starts increasing are different positions in the vertical direction.
  • the clip pitch of each clip is expanded to a predetermined pitch.
  • P 1 is the clip pitch at the time of gripping the film.
  • the increase of the clip pitch of one (right side in the illustrated example) clip is started. In the first oblique stretching zone C1, increases the clip pitch of the right clip to the P 2.
  • the clip pitch of the left clip is maintained at P1 in the first oblique stretching zone C1. Therefore, the end portion of the first oblique stretching zone C1 in (beginning of the second oblique stretching zone C2), left clip moves the clip pitch P 1, right clip is a moving clip pitch P 2 ing. Next, as soon as the film enters the second oblique stretching zone C2, the clip pitch of the left clip starts to increase. In the second oblique stretching zone C2, it increases the clip pitch of the left clip to the P 2. On the other hand, the clip pitch of the right clip is maintained at P2 in the second oblique stretching zone C2.
  • the position where the clip pitch of the right clip begins to increase is the start of the first oblique stretching zone C1
  • the position where the clip pitch of the left clip begins to increase is the second oblique stretching zone.
  • the position at which the clip pitch of the left clip begins to increase may be the middle portion of the first oblique stretching zone C1, or may be the middle portion of the second oblique stretching zone C2, and the clip pitch of the right clip begins to increase.
  • the position may be an intermediate portion of the first oblique stretching zone C1.
  • the clip pitch ratio can generally correspond to the clip moving speed ratio. Therefore, the ratio of the clip pitch of the left and right clips can generally correspond to the ratio of the stretching ratio in the MD direction between the right side edge and the left side edge of the film.
  • the clip pitch can be adjusted by positioning the slider by adjusting the distance between the pitch setting rail of the stretching device and the reference rail as described above.
  • the ratio P 2 / P 1 (hereinafter also referred to as clip pitch change rate) between the clip pitch P 1 and the clip pitch P 2 is preferably 1.2 to 1.9. It is preferably 1.4 to 1.7. If the clip pitch change rate is in such a range, there is an advantage that the film can be prevented from being broken and the film is less likely to be wrinkled.
  • the diagonal stretching (i) increases the clip pitch of one of the left and right clips and decreases the clip pitch of the other clip, and (ii) reduces the clip Increasing the clip pitch to the same pitch as the enlarged clip pitch, and setting the clip pitch of each clip to a predetermined pitch.
  • the right and left clip pitch are both set to P 1.
  • P 1 is the clip pitch at the time of gripping the film.
  • the clip pitch of one (right side in the illustrated example) starts to increase, and the clip pitch of the other (left side in the illustrated example) Start decreasing.
  • the first oblique stretching zone C1 In the first oblique stretching zone C1, it increases the clip pitch of the right clip to the P 2, to reduce the clip pitch of the left clip to the P 3. Therefore, the end portion of the first oblique stretching zone C1 in (beginning of the second oblique stretching zone C2), left clip moves the clip pitch P 3, right clip is a moving clip pitch P 2 ing.
  • the clip pitch of the left clip starts to increase.
  • the clip pitch of the right clip is maintained at P2 in the second oblique stretching zone C2.
  • the decrease start position of the clip pitch of the left clip and the increase start position of the clip pitch of the right clip are both set as the start portion of the first oblique extension zone C1, but these positions are shown in the above figure. Similar to the embodiment of FIGS. 4 and 5, it can be set at any suitable position in the stretching zone.
  • the clip pitch change rate (P 2 / P 1 ) is preferably 1.2 to 1.9, and more preferably 1.4 to 1.7.
  • P 2 / P 1 is in such a range, there is an advantage that the film can be prevented from being broken.
  • the clip pitch change rate (P 3 / P 1 ) is preferably 0.5 to 0.9, and more preferably 0.6 to 0.8. If P 3 / P 1 is in such a range, there is an advantage that wrinkles are unlikely to enter the film.
  • the product of the clip pitch change rate of one clip and the clip pitch change rate of the other clip at the end of the first oblique stretching is preferably 1.0 to 1.7.
  • the product of the change rates is within such a range, a retardation film having excellent axial accuracy, small retardation unevenness, and small dimensional change can be obtained.
  • the oblique stretching can typically be performed at a temperature T2.
  • the temperature T2 is preferably Tg ⁇ 20 ° C. to Tg + 30 ° C. with respect to the glass transition temperature (Tg) of the resin film, more preferably Tg ⁇ 10 ° C. to Tg + 20 ° C., and particularly preferably about Tg.
  • the temperature T2 is, for example, 70 ° C. to 180 ° C., preferably 80 ° C. to 170 ° C., depending on the resin film used.
  • the difference (T1 ⁇ T2) between the temperature T1 and the temperature T2 is preferably ⁇ 2 ° C. or more, and more preferably ⁇ 5 ° C. or more. In one embodiment, T1> T2, and thus the film heated to temperature T1 in the preheating step can be cooled to temperature T2.
  • the oblique stretching described above may include stretching in the lateral direction, and may not include stretching in the lateral direction.
  • the width of the film after oblique stretching may be larger than the initial width of the film, or may be substantially the same as the initial width.
  • the illustrated example shows an embodiment including transverse stretching.
  • the transverse stretching ratio (ratio W 2 / W 1 between the initial width W 1 of the film and the width W 2 of the film after oblique stretching) is preferably 1 0.0 to 4.0, more preferably 1.3 to 3.0. If the draw ratio is too small, tin-like wrinkles may occur in the resulting retardation film. When the draw ratio is too large, the biaxiality of the obtained retardation film becomes high, and the viewing angle characteristics may be deteriorated when applied to a circularly polarizing plate or the like.
  • shrinkage step D the clip pitch of the left and right clips is reduced to shrink the film in the machine direction (MD) (hereinafter referred to as MD shrinkage treatment).
  • MD shrinkage treatment by performing MD shrinkage treatment after oblique stretching, a retardation film having excellent axial accuracy, small retardation unevenness, small dimensional change, and having a slow axis in an oblique direction is obtained. Can do.
  • the clip pitch change rate (P 4 / P 2 ) is preferably 0.7 to 0.999, more preferably 0.7 to 0.995, and still more preferably 0.8 to 0.99. .
  • the shrinkage ratio in the MD shrinkage treatment is preferably 0.1% to 30%, more preferably 0.5% to 30%, and further preferably 1% to 20%. If the clip pitch change rate and the shrinkage rate are within such ranges, the effects of the present invention can be more remarkable.
  • the MD shrinkage treatment can be typically performed at a temperature T3.
  • the temperature T3 typically satisfies the relationship T2 ⁇ T3, and the difference between the temperatures T2 and T3 (T2 ⁇ T3) is preferably 0 to 50 ° C.
  • the manufacturing method of the present invention reduces the clip pitch of the left and right clips after the stretching process (diagonal stretching process) C and before the shrinking process D. Is further stretched in the transverse direction while shrinking in the longitudinal direction. Therefore, in this embodiment, a longitudinal shrinkage / lateral stretching zone D ′ is provided between the stretching zone C and the shrinking zone D of the stretching apparatus. This embodiment will be specifically described with reference to FIGS. As described above, in the end of the stretching zone, the left clip and right clips together, there is a moving clip pitch P 2.
  • the clip pitches of the left clip and the right clip are both reduced to P 4 ′.
  • the clip pitch change rate (P 4 ′ / P 2 ) is preferably 0.7 to 0.995, and more preferably 0.8 to 0.99. If the clip pitch change rate is in such a range, there is an advantage that wrinkles during contraction can be suppressed.
  • the final clip pitch change rate (P 4 / P 2 ) and shrinkage rate in the MD shrinkage treatment are as described in D above regardless of whether or not the longitudinal shrinkage / lateral stretching treatment is performed according to the present embodiment.
  • the transverse draw ratio in the longitudinal shrinkage / lateral stretching according to the present embodiment is preferably 1. 0.03 to 1.5, more preferably 1.05 to 1.2. If the said horizontal stretch ratio is such a range, there exists an advantage that a fracture
  • the longitudinal shrinkage / lateral stretching treatment can typically be performed at a temperature T3 ′.
  • the temperature T3 ′ is, for example, a temperature in the range of the above temperatures T2 to T3.
  • the film is subjected to the MD shrinkage treatment.
  • the present embodiment is illustrated as conforming to the embodiment referring to FIG. 6, but it is needless to say that the present embodiment may conform to the embodiment referring to FIG. 5.
  • the width W 3 of the film after longitudinal shrinkage / lateral stretching corresponds to the width of the obtained retardation film (FIG. 7).
  • the width W 2 of the film after oblique stretching corresponds to the width of the resulting retardation film (FIG. 4).
  • the width of the obtained retardation film is substantially equal to the initial width of the film.
  • Films to be stretched and retardation films obtained by stretching Films suitably used in the production method of the present invention are used as retardation films. Any suitable film obtained may be mentioned.
  • the material constituting the film include polycarbonate resin, polyvinyl acetal resin, cycloolefin resin, acrylic resin, cellulose ester resin, cellulose resin, polyester resin, polyester carbonate resin, olefin resin, and polyurethane resin. Examples thereof include resins. Polycarbonate resins, polyvinyl acetal resins, cellulose ester resins, polyester resins, and polyester carbonate resins are preferable. This is because with these resins, a retardation film showing the wavelength dependence of reverse dispersion can be obtained. These resins may be used alone or in combination according to desired properties.
  • any appropriate polycarbonate resin is used as the polycarbonate resin.
  • a polycarbonate resin containing a structural unit derived from a dihydroxy compound is preferable.
  • the dihydroxy compound include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3- Ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy) -3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9, 9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-bis
  • the polycarbonate resin includes isosorbide, isomannide, isoidet, spiroglycol, dioxane glycol, diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG), bisphenols, and the like.
  • a structural unit derived from a dihydroxy compound may be included.
  • the glass transition temperature of the polycarbonate resin is preferably 110 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 230 ° C. or lower. If the glass transition temperature is excessively low, the heat resistance tends to deteriorate, and there is a possibility of causing a dimensional change after film formation. If the glass transition temperature is excessively high, the molding stability at the time of film molding may deteriorate, and the transparency of the film may be impaired.
  • the glass transition temperature is determined according to JIS K 7121 (1987).
  • any appropriate polyvinyl acetal resin can be used as the polyvinyl acetal resin.
  • the polyvinyl acetal resin can be obtained by a condensation reaction of at least two types of aldehyde compounds and / or ketone compounds and a polyvinyl alcohol resin.
  • Specific examples of the polyvinyl acetal resin and a detailed production method thereof are described in, for example, Japanese Patent Application Laid-Open No. 2007-161994. The description is incorporated herein by reference.
  • the retardation film obtained by stretching the film to be stretched preferably has a refractive index characteristic of nx> ny. Further, the retardation film can preferably function as a ⁇ / 4 plate.
  • the in-plane retardation Re (550) of the retardation film is preferably 100 nm to 180 nm, more preferably 135 nm to 155 nm.
  • nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction)
  • ny is the direction orthogonal to the slow axis in the plane (that is, the fast phase) (Axial direction)
  • nz is the refractive index in the thickness direction.
  • Re ( ⁇ ) is an in-plane retardation of the film measured with light having a wavelength of ⁇ nm at 23 ° C. Therefore, Re (550) is the in-plane retardation of the film measured with light having a wavelength of 550 nm at 23 ° C.
  • the retardation film shows any appropriate refractive index ellipsoid as long as it has a relationship of nx> ny.
  • the refractive index ellipsoid of the retardation film exhibits a relationship of nx> ny ⁇ nz.
  • the Nz coefficient of the retardation film is preferably 1 to 2, more preferably 1 to 1.5, and still more preferably 1 to 1.3.
  • the retardation film preferably exhibits the so-called reverse dispersion wavelength dependency.
  • the in-plane retardation satisfies the relationship Re (450) ⁇ Re (550) ⁇ Re (650).
  • Re (450) / Re (550) is preferably 0.8 or more and less than 1.0, and more preferably 0.8 to 0.95.
  • Re (550) / Re (650) is preferably 0.8 or more and less than 1.0, and more preferably 0.8 to 0.97.
  • the retardation film has an absolute value of its photoelastic coefficient of preferably 2 ⁇ 10 ⁇ 12 (m 2 / N) to 100 ⁇ 10 ⁇ 12 (m 2 / N), more preferably 10 ⁇ 10 ⁇ 12. (M 2 / N) to 50 ⁇ 10 ⁇ 12 (m 2 / N).
  • FIG. 9 is a schematic cross-sectional view of an example of such a circularly polarizing plate.
  • the circularly polarizing plate 300 in the illustrated example includes a polarizer 310, a first protective film 320 disposed on one side of the polarizer 310, a second protective film 330 disposed on the other side of the polarizer 310, And a retardation film 340 disposed outside the two protective films 330.
  • the retardation film 340 is a retardation film obtained by the production method of the present invention.
  • the second protective film 330 may be omitted.
  • the retardation film 340 can function as a protective film for the polarizer.
  • the angle formed by the absorption axis of the polarizer 310 and the slow axis of the retardation film 340 is preferably 30 ° to 60 °, more preferably 38 ° to 52 °, still more preferably 43 ° to 47 °, particularly preferably. It is about 45 °.
  • a polarizer and a protective film is well-known in the industry, detailed description is abbreviate
  • omitted since the structure of a polarizer and a protective film is well-known in the industry, detailed description is abbreviate
  • the circularly polarizing plate may further include any appropriate optical member or optical function layer in any appropriate position depending on the purpose.
  • the outer surface of the first protective film 320 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, antisticking treatment, antiglare treatment, and light diffusion treatment.
  • another retardation film showing any appropriate refractive index ellipsoid may be arranged on at least one side of the retardation film 340 according to the purpose.
  • an optical member such as a front substrate (for example, a transparent protective substrate or a touch panel) may be disposed outside the first protective film 320.
  • the retardation film obtained by the production method of the present invention is very suitable for producing a circularly polarizing plate. Details are as follows.
  • This retardation film is long and has a slow axis in an oblique direction (as described above, for example, a direction of 45 ° with respect to the long direction).
  • a long polarizer has an absorption axis in the longitudinal direction or the width direction, so if the retardation film obtained by the production method of the present invention is used, a so-called roll-to-roll can be used.
  • a circularly polarizing plate can be produced with extremely excellent production efficiency.
  • the retardation film obtained by the production method of the present invention has excellent axial accuracy, small retardation unevenness, and small dimensional change, so that a circularly polarizing plate having very excellent optical characteristics is obtained. be able to.
  • the roll-to-roll refers to a method of continuously laminating long films while aligning their long directions while roll-feeding them.
  • reference numerals 811 and 812 are rolls for winding the polarizing plate and the retardation film, respectively, and reference numeral 822 is a transport roll.
  • a polarizing plate (first protective film 320 / polarizer 310 / second protective film 330) and a retardation film 340 are sent out in the direction of the arrows, and are bonded together with their respective longitudinal directions aligned. In that case, it bonds together so that the 2nd protective film 330 of a polarizing plate and the phase difference film 340 may adjoin.
  • a circularly polarizing plate 300 as shown in FIG.
  • polarizing plate first protective film 320 / polarizer 310
  • retardation film 340 are bonded so that the polarizer 310 and the retardation film 340 are adjacent to each other, and the retardation film 340 is formed.
  • a circularly polarizing plate that functions as a protective film can also be produced.
  • the criteria are as follows: ⁇ ⁇ ⁇ ⁇ Wrinkles and undulations are not observed throughout the film ⁇ ⁇ ⁇ ⁇ Width direction end of the film is crumpled and wrinkled, but the central part is undulated The wrinkles are in, and the film is wavy. (5) Thickness It measured using the micro gauge type thickness meter (made by Mitutoyo Corporation). (6) Retardation reliability The retardation films obtained in Examples and Comparative Examples were cut into 26 mm ⁇ 50 mm and bonded to a glass plate with an adhesive. The in-plane retardation of the sample attached to the glass was measured at a wavelength of 550 nm and 23 ° C. using a product name “Axoscan” manufactured by Axometrics.
  • BHEPF 9,9- [4- (2-hydroxyethoxy) phenyl] fluorene
  • ISB isosorbide
  • DEG diethylene glycol
  • DPC diphenyl carbonate
  • magnesium acetate tetrahydrate in a molar ratio of BHEPF / IS
  • Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Subsequently, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was obtained.
  • the obtained polycarbonate resin was vacuum-dried at 80 ° C. for 5 hours, and then a single-screw extruder (manufactured by Isuzu Chemical Industries, screw diameter 25 mm, cylinder set temperature: 220 ° C.), T-die (width 900 mm, set temperature: 220). ° C), a chill roll (set temperature: 120 to 130 ° C), and a film forming apparatus equipped with a winder, a 195 ⁇ m thick polycarbonate resin film was produced.
  • a single-screw extruder manufactured by Isuzu Chemical Industries, screw diameter 25 mm, cylinder set temperature: 220 ° C.
  • T-die width 900 mm, set temperature: 220.
  • a chill roll set temperature: 120 to 130 ° C
  • a film forming apparatus equipped with a winder a 195 ⁇ m thick polycarbonate resin film was produced.
  • the polycarbonate resin film obtained as described above was subjected to pre-heat treatment, oblique stretching and MD shrinkage treatment with a clip pitch profile as shown in FIG. 5 using an apparatus as shown in FIGS. A retardation film was obtained.
  • the polycarbonate resin film (thickness 195 ⁇ m, width 765 mm) was preheated to 145 ° C. in the preheating zone of the stretching apparatus.
  • the clip pitch of the left and right clips was 125 mm.
  • the clip pitch of the right clip began to increase and increased from 125 mm to 200 mm in the first diagonal stretching zone C1.
  • the clip pitch change rate was 1.6.
  • the clip pitch of the left clip was maintained at a clip pitch of 125 mm in the preheating zone.
  • the clip pitch of the left clip started to increase and increased from 125 mm to 200 mm in the second oblique stretching zone C2.
  • the clip pitch of the right clip was maintained at 200 mm in the second oblique stretching zone C2.
  • stretching in the width direction was performed 1.9 times.
  • the oblique stretching was performed at 138 ° C.
  • the film width after oblique stretching was 1419 mm.
  • MD shrinkage treatment Next, MD shrinkage treatment was performed in the shrinkage zone. Specifically, both the clip pitches of the left clip and the right clip were reduced from 200 mm to 187.5 mm. The shrinkage rate in the MD shrinkage treatment was 6.2%.
  • Example 2 A polycarbonate resin film (thickness: 155 ⁇ m, width: 765 mm) obtained in the same manner as in Example 1 except that the thickness was different was subjected to oblique stretching with a clip pitch profile as shown in FIG. 6 to obtain a retardation film. .
  • the clip pitch of the right clip started to increase and increased from 125 mm to 177.5 mm in the first oblique stretching zone C1.
  • the clip pitch change rate was 1.42.
  • the clip pitch of the left clip started to decrease and decreased from 125 mm to 90 mm in the first oblique stretching zone C1.
  • the clip pitch change rate was 0.72.
  • the clip pitch of the left clip started to increase and increased from 90 mm to 177.5 mm in the second oblique stretching zone C2.
  • the clip pitch of the right clip was maintained at 177.5 mm in the second oblique stretching zone C2.
  • stretching in the width direction was performed 1.9 times.
  • MD shrinkage treatment was performed in the shrinkage zone. Specifically, the clip pitches of the left clip and right clip were both reduced from 177.5 mm to 165 mm.
  • the shrinkage rate in the MD shrinkage treatment was 7.0%.
  • a retardation film (thickness 60 ⁇ m) was obtained as described above. The obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 3 The polycarbonate resin film (thickness 165 ⁇ m, width 765 mm) obtained in the same manner as in Example 1 except that the thickness was different was used, and the longitudinal shrinkage after oblique stretching (including lateral stretching) and before MD shrinking treatment A retardation film (thickness 63 ⁇ m) was obtained in the same manner as in Example 2 except that lateral stretching (lateral stretching ratio: 1.05 times) was performed.
  • the shrinkage in the longitudinal direction is the sum of the shrinkage of the longitudinal shrinkage and the longitudinal shrinkage of the transverse stretching and the shrinkage of the MD shrinkage treatment, and the shrinkage was 7.0% as in Example 2. .
  • the obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 4 Except that the polycarbonate resin film (thickness 200 ⁇ m, width 765 mm) obtained in the same manner as in Example 1 was used except that the thickness was different, and that the shrinkage rate in MD shrinkage treatment after oblique stretching was 18.7% Obtained a retardation film (thickness 75 ⁇ m) in the same manner as in Example 1. The obtained retardation film was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 5 Use of cycloolefin resin film (“ZEONOR ZF-14 film” manufactured by ZEON Corporation, thickness 100 ⁇ m, width 765 mm) instead of polycarbonate resin film, preheating to 150 ° C. in the preheating zone, and oblique stretching A retardation film (thickness: 40 ⁇ m) was obtained in the same manner as in Example 1 except that (including lateral stretching) was performed at 150 ° C. The obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • the obtained polymer had a repeating unit represented by the following formula (XI) as measured by 1 H-NMR, and the ratio (molar ratio) of l: m: n: o was 10:25:52. : 11. Moreover, it was 130 degreeC when the glass transition temperature of this polymer was measured.
  • the obtained polymer was dissolved in methyl ethyl ketone (MEK), and the resulting solution was coated on a polyethylene terephthalate film (thickness 70 ⁇ m) with a die coater and dried in an air circulation drying oven. The film was peeled off to obtain a film having a thickness of 225 ⁇ m and a width of 765 mm.
  • MEK methyl ethyl ketone
  • the obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 1 ⁇ Comparative Example 1> Except that the polycarbonate resin film (thickness 190 ⁇ m, width 765 mm) obtained in the same manner as in Example 1 was used except that the thickness was different, and that the MD shrinkage treatment was not performed after oblique stretching, the same as in Example 1. Thus, a retardation film (thickness: 65 ⁇ m) was obtained. The obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • the retardation films obtained by the examples of the present invention have the retardation of the comparative example in terms of axial accuracy (orientation angle variation), phase change after heating, and dimensional change. It is much better than film. That is, it can be seen that such excellent effects can be obtained by performing MD shrinkage treatment after oblique stretching.
  • the retardation film obtained by the production method of the present invention is suitably used for a circularly polarizing plate, and as a result, is suitably used for an image display device such as a liquid crystal display device (LCD) or an organic electroluminescence display device (OLED). .
  • LCD liquid crystal display device
  • OLED organic electroluminescence display device

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