JP2015127830A - Retardation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a retardation film with excellent axis accuracy, with smaller phase difference change and dimensional change at heating, and having a slow axis in an oblique direction.SOLUTION: A retardation film is long-sized and has a slow axis in a direction at a certain angle to a longer direction. An absolute value of a change rate of an in-plane phase difference is 4.1% or lower. In one embodiment, the in-plane phase difference satisfies a relation of Re(450)<Re(550)<Re(650). Here, Re(λ) denotes an in-plane phase difference of the film measured with light of a wavelength λnm at 23°C.

Description

The present invention relates to a retardation film .

  In an image display device such as a liquid crystal display device (LCD) or an organic electroluminescence display device (OLED), a circularly polarizing plate is used for the purpose of improving display characteristics and preventing reflection. In a circularly polarizing plate, typically, a polarizer and a retardation film (typically λ / 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. Conventionally, 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). As a result, in order to produce a circularly polarizing plate, it was necessary to cut the retardation film so as to form an angle of 45 ° with respect to the horizontal direction or the vertical direction and to bond them one by one.

  In order to solve such a problem, a technique has been proposed in which the slow axis of the retardation film is expressed in the oblique direction by stretching in the oblique direction. However, all of the techniques proposed up to now have a problem that the optical characteristics and / or mechanical characteristics of the obtained retardation film are uneven, and the problem is particularly remarkable in the width direction.

Japanese Patent No. 4845619

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 retardation film .

The retardation film of the present invention is long and has a slow axis in a direction forming a predetermined angle with respect to the long direction, and the absolute value of the rate of change of in-plane retardation is 4.1. % Or less.
In one embodiment, the in-plane retardation satisfies a relationship of Re (450) <Re (550) <Re (650). Here, Re (λ) represents the in-plane retardation of the film measured with light having a wavelength of λ nm at 23 ° C.
In one embodiment, the absolute value of the dimensional change rate of the retardation film is 0.22% or less.
In one embodiment, the distribution width of the distribution in the direction of the slow axis is within 3 °.
In this specification, the left and right end portions of the film are respectively held by variable pitch type left and right clips whose longitudinal clip pitches change; the film is preheated; the clip pitch of the left and right clips The film is obliquely stretched; the clip pitch of the left and right clips is reduced to shrink the film in the longitudinal direction; and the clip holding the film is released. A method for producing a retardation film including the following will be described as a method for producing a retardation film of the present invention.
In one embodiment, after the film is stretched obliquely and before shrinking in the longitudinal direction, 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.
In one embodiment, 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. In this state, the clip pitch of each clip is expanded to a predetermined pitch.
In one embodiment, 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.
In one embodiment, the contraction rate in the vertical direction is 0.1% to 30%.
Further, in the present specification, a long retardation film is obtained by the above-described production method, and the long direction retardation film and the long polarizing plate are conveyed while transporting the obtained long retardation film. A method for producing a circularly polarizing plate, which includes continuously laminating and bonding together, will be described as a method for producing the circularly polarizing plate of the present invention.

According to the present invention, it is possible to provide a retardation film having excellent axial accuracy, small retardation change and dimensional change during heating, and having a slow axis in an oblique direction.

It is a schematic plan view explaining the whole structure of an example of the extending | stretching apparatus which can be used for the manufacturing method of this invention. It is a principal part schematic plan view for demonstrating the link mechanism which changes a clip pitch in the extending | stretching apparatus of FIG. 1, and shows the state where a clip pitch is the minimum. It is a principal part schematic plan view for demonstrating the link mechanism which changes a clip pitch in the extending | stretching apparatus of FIG. 1, and shows a state with the largest clip pitch. It is a schematic diagram explaining one embodiment of diagonal stretch in the manufacturing method of this invention. It is a graph which shows the relationship between each zone of the extending | stretching apparatus in the case of the diagonal extending | stretching shown in FIG. 4, and a clip pitch. It is a graph which shows the relationship between each zone of the extending | stretching apparatus in the case of diagonal extending | stretching of another embodiment, and a clip pitch. It is a schematic diagram explaining another embodiment of the manufacturing method of this invention. It is a graph which shows the relationship between each zone and the clip pitch of the extending | stretching apparatus in embodiment shown in FIG. It is a schematic sectional drawing of the circularly-polarizing plate using the phase difference film obtained by the manufacturing method of this invention. It is the schematic explaining the manufacturing method of the circularly-polarizing plate by one Embodiment of this invention.

  Hereinafter, although preferable embodiment of this invention is described, this invention is not limited to these embodiment.

  In the method for producing a retardation film of the present invention, 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). Hereinafter, each step will be described in detail.

A. First, a stretching apparatus that can be used in the manufacturing method of the present invention including this process will be described with reference to FIGS. 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. In this specification, the left endless loop as viewed from the film entrance side is referred to as the left endless loop 10L, and 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 10R moves in a counterclockwise direction, and the right endless loop 10R moves in a clockwise direction. In the stretching apparatus, 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.

  In the gripping zone A and the preheating zone B, 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. In the stretching zone C, 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. In the illustrated example, in the contraction zone D, 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. In the contraction zone D, 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 20L on the left endless loop 10L (left clip) and the clip 20R on the right endless loop 10R (right clip) can each move independently. For example, 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. As a result, traveling force is applied to the clip carrying member 30 of the drive roller (not shown) engaged with the drive sprockets 11 and 12. As a result, the left endless loop 10L cyclically moves in the counterclockwise direction, and the right endless loop 10R cyclically moves in the clockwise direction. By driving the left electric motor and the right electric motor independently of each other, the left endless loop 10L and the right endless loop 10R can be cyclically moved independently.

  Further, the clip (left clip) 20 of the left endless loop 10L and the clip (right clip) 20 of the right endless loop 10R are each of a 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. Hereinafter, a link mechanism (pantograph mechanism) will be described as an example.

  As shown in FIGS. 2 and 3, an elongated rectangular clip carrying member 30 is provided in the lateral direction in plan view for carrying the clips 20 individually. Although not shown, 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. In the vicinity of the end portion of the clip carrying member 30 on the clip 20 side, a single first shaft member 33 is vertically provided so as to penetrate the upper beam and the lower beam. On the other hand, 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. In addition to the main link member 35, 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. As shown in FIG. 2, as the slider 32 moves to the rear side of the clip carrying member 30 (opposite the clip side) by the link mechanism using the main link member 35 and the sub link member 36, the clip carrying members 30 are connected to each other. As the slider 32 moves to the front side (clip side) of the clip carrier member 30 as shown in FIG. 3, 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.

  By performing oblique stretching of the film using the stretching apparatus as described above, 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. First, in 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).

B. Preheating process In the preheating zone (preheating process) B, 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 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.

  In the preheating step, 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. Although it changes with films to be used, temperature T1 is 70 to 190 degreeC, for example, Preferably it is 80 to 180 degreeC.

  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.

C. Stretching process In the stretching zone (stretching process) C, 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. In the following description, for convenience, 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.

In one embodiment, 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. In the state, the clip pitch of each clip is expanded to a predetermined pitch. This embodiment will be specifically described with reference to FIGS. 4 and 5. First, in the preheating zone B, 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. Next, as soon as the film enters the first oblique stretching zone C1, 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. On the other hand, 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. Therefore, the end portion of the second oblique stretching zone C2 in (end of extension zone C), the left clip and right clips together, there is a moving clip pitch P _2. In the illustrated example, for the sake of simplicity, the position where the clip pitch of the right clip begins to increase is the start of the first oblique stretching zone C1, and the position where the clip pitch of the left clip begins to increase is the second oblique stretching zone. Although it is a start part of C2, the position can be set at any appropriate position in the stretching zone. For example, 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.

  As described above, 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.

In the present embodiment, 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, and more. Preferably it is 1.4-1.7. 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.

In another embodiment, 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. This embodiment will be specifically described with reference to FIG. First, in the preheating zone B, 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. Next, as soon as the film enters the first oblique stretching zone C1, 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. 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. 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, 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. Therefore, the end portion of the second oblique stretching zone C2 in (end of extension zone C), the left clip and right clips together, there is a moving clip pitch P _2. In the illustrated example, for the sake of simplicity, 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.

In the present embodiment, the clip pitch change rate (P ₂ / P ₁ ) is preferably 1.2 to 1.9, more preferably 1.4 to 1.7. When P ₂ / P ₁ is in such a range, there is an advantage that the film can be prevented from being broken. Furthermore, 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.

  In the oblique stretching in the production method of the present invention, 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 (stretching in the first oblique stretching zone C1). However, it is preferably 1.0 to 1.7. When 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, more preferably Tg-10 ° C to Tg + 20 ° C, and particularly preferably about Tg with respect to the glass transition temperature (Tg) of the resin film. Although it changes with resin films to be used, the temperature T2 is, for example, 70 ° C to 180 ° C, and preferably 80 ° C to 170 ° C. The difference (T1-T2) between the temperature T1 and the temperature T2 is preferably ± 2 ° C. or more, 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. In other words, 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. Needless to say, the illustrated example shows an embodiment including transverse stretching. When the oblique stretching includes lateral stretching as in the illustrated example, 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 It is 0.0-4.0, More preferably, it is 1.3-3.0. 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.

D. Shrinkage Step In the shrinkage zone (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). According to the present invention, 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.

Specifically, as described above, in the beginning of the contraction zone (end of extension zone), left clip and right clips together, there is a moving clip pitch P _2. In MD shrinkage treatment are both reduced to P ₄ of the clip pitches of the left clip and right clip. The clip pitch change rate (P ₄ / P ₂ ) is preferably 0.7 to 0.999, more preferably 0.7 to 0.995, and further preferably 0.8 to 0.99. . The shrinkage rate 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 process can typically be performed at a temperature T3. The temperature T3 typically satisfies the relationship T2 ≧ T3, and the difference (T2−T3) between the temperatures T2 and T3 is preferably 0 to 50 ° C.

D '. Longitudinal Shrinkage / Horizontal Stretching Process In one embodiment, 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. In the longitudinal shrinkage process in the longitudinal shrinkage / lateral stretching zone D ′, 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. Note that 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 (ratio W ₂ / W ₃ of the width W ₂ of the film after oblique stretching and the width W ₃ of the film after longitudinal shrinkage / lateral stretching) is preferably 1. 0.03 to 1.5, and more preferably 1.05 to 1.2. If the said horizontal stretch ratio is such a range, there exists an advantage that a fracture | rupture of a film can be prevented. 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. After the longitudinal shrinkage / lateral stretching treatment, the film is subjected to the MD shrinkage treatment. As is apparent from FIG. 8, 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.

E. Release process Finally, the clip holding the film is released to obtain a retardation film. In addition, when performing the longitudinal shrinkage / lateral stretching treatment of D ′, the width W ₃ of the film after longitudinal shrinkage / lateral stretching corresponds to the width of the obtained retardation film (FIG. 7). When not performing a longitudinal shrinkage and transverse stretching process, the width W ₂ of the film after oblique stretching corresponds to the width of the resulting retardation film (FIG. 4). When the longitudinal shrinkage / lateral stretching treatment is not performed and the oblique stretching does not include the transverse stretching, the width of the obtained retardation film is substantially equal to the initial width of the film.

F. Film to be stretched and retardation film obtained by stretching As a film suitably used in the production method of the present invention (substantially, the stretching method described in the above items A to E), it is used as a retardation film. Any suitable film obtained may be mentioned. Examples of 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. For example, a polycarbonate resin containing a structural unit derived from a dihydroxy compound is preferable. Specific examples of 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-hydroxy-3-phenyl) Enyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxy Ethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl ) Fluorene and the like. In addition to the structural unit derived from the dihydroxy compound, 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.

  Details of the polycarbonate resin as described above are described in, for example, Japanese Patent Application Laid-Open No. 2012-67300 and Japanese Patent No. 3325560. The description of the patent document is incorporated herein by reference.

  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. Typically, 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 and detailed production methods of the polyvinyl acetal resin are described, for example, in JP-A-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 λ / 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. In the present specification, nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), and ny is the direction orthogonal to the slow axis in the plane (that is, the fast phase). (Axial direction) and nz is the refractive index in the thickness direction. Re (λ) is an in-plane retardation of the film measured with light having a wavelength of λ 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. Re (λ) is determined by the formula: Re (λ) = (nx−ny) × d, where d (nm) is the thickness of the film.

  The retardation film exhibits any suitable refractive index ellipsoid as long as it has a relationship of nx> ny. Preferably, 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 Nz coefficient is obtained by Nz = Rth (λ) / Re (λ). Here, Rth (λ) is a retardation in the thickness direction of the film measured with light of wavelength λnm at 23 ° C., and is obtained by the formula: Rth (λ) = (nx−nz) × d.

  The retardation film preferably exhibits the so-called reverse dispersion wavelength dependency. Specifically, 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 absolute value of the photoelastic coefficient of the retardation film is preferably 2 × 10 ⁻¹² (m ² / N) to 100 × 10 ⁻¹² (m ² / N), and more preferably 10 × 10 ^−12. (M ² / N) to 50 × 10 ⁻¹² (m ² / N).

G. Circularly polarizing plate and method of manufacturing circularly polarizing plate The retardation film obtained by the above-described manufacturing method of the present invention can typically be suitably used for a circularly polarizing plate. 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. In that case, 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 °, and particularly preferably. It is about 45 °. In addition, since the structure of a polarizer and a protective film is well-known in the industry, detailed description is abbreviate | omitted.

  The circularly polarizing plate may further include any appropriate optical member or optical function layer at any appropriate position depending on the purpose. For example, 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. Further, 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. Furthermore, 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). In many cases, 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. Moreover, 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.

  With reference to FIG. 10, the manufacturing method of the circularly-polarizing plate by one Embodiment of this invention is demonstrated easily. In FIG. 10, 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. In the illustrated example, 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. In this way, a circularly polarizing plate 300 as shown in FIG. 9 can be obtained. Although not illustrated, for example, a polarizing plate (first protective film 320 / polarizer 310) and a 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In addition, the measurement and evaluation method in an Example are as follows.

(1) Orientation angle (expression direction of slow axis)
Samples were prepared by cutting out the central portion of the retardation films obtained in Examples and Comparative Examples into a square shape having a width of 50 mm and a length of 50 mm so that one side thereof was parallel to the width direction of the film. This sample was measured using a Mueller matrix polarimeter (product name “Axoscan” manufactured by Axometrics), and the orientation angle θ at a wavelength of 550 nm and 23 ° C. was measured. The orientation angle θ was measured with a sample placed in parallel on a measurement table.
(2) Orientation angle distribution (variation in orientation angle)
Nine samples were collected from the retardation films (800 mm width) obtained in Examples and Comparative Examples at 100 mm intervals in the film width direction. The sample was prepared by cutting out into a square shape having a width of 50 mm and a length of 50 mm so that one side was parallel to the width direction of the film. Nine samples were measured in the same manner as in (1) above, and the distribution of orientation angles was determined.
(3) In-plane retardation Re
In the same manner as in the above (1), measurement was performed at a wavelength of 550 nm and 23 ° C. using a product name “Axoscan” manufactured by Axometrics.
(4) Wrinkles The state of the retardation film obtained in the examples and comparative examples was confirmed visually. 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. Then, after putting into 85 degree heating oven for 100 hours, the sample affixed on glass was taken out, the in-plane phase difference was measured again, and the change of phase difference was calculated | required.
(7) Dimensional change The retardation films obtained in Examples and Comparative Examples were cut into 100 mm × 100 mm and bonded to a glass plate with an adhesive. The sample affixed to the glass was accurately measured using a Mitutoyo Corporation CNC image measuring device QuickVision (QV606). Then, after putting in an 80 degreeC heating oven for 500 hours, the sample affixed on glass was taken out, the dimension was measured correctly again, and the change of the dimension was calculated | required.

<Example 1>
(Production of polycarbonate resin film)
Polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. 9,9- [4- (2-hydroxyethoxy) phenyl] fluorene (BHEPF), isosorbide (ISB), diethylene glycol (DEG), diphenyl carbonate (DPC), and magnesium acetate tetrahydrate in a molar ratio of BHEPF / ISB / DEG / DPC / magnesium acetate = 0.348 / 0.490 / 0.162 / 1.005 / 1.00 × 10 ⁻⁵ was charged. After sufficiently replacing the inside of the reactor with nitrogen (oxygen concentration 0.0005 to 0.001 vol%), heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C. After 40 minutes from the start of temperature increase, the internal temperature was reached to 220 ° C., and control was performed so as to maintain this temperature. At the same time, pressure reduction was started, and after reaching 220 ° C., the pressure reached 13.3 kPa in 90 minutes. The phenol vapor produced as a by-product with the polymerization reaction was led to a reflux condenser at 100 ° C., and a monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the phenol vapor not condensed was led to a condenser at 45 ° C. and recovered.

  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. Next, 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. When a predetermined power is reached, nitrogen is introduced into the reactor, the pressure is restored, the reaction solution is withdrawn in the form of a strand, pelletized with a rotary cutter, and BHEPF / ISB / DEG = 34.8 / 49.0 / A polycarbonate resin A having a copolymer composition of 16.2 [mol%] was obtained. This polycarbonate resin had a reduced viscosity of 0.430 dL / g and a glass transition temperature of 128 ° C.

  The obtained polycarbonate resin was vacuum-dried at 80 ° C. for 5 hours, and then a single-screw extruder (made 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 μm thick polycarbonate resin film was produced.

(Diagonal stretching)
The polycarbonate resin film obtained as described above is 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. Specifically, it was as follows: A polycarbonate resin film (thickness: 195 μm, width: 765 mm) was preheated to 145 ° C. in the preheating zone of the stretching apparatus. In the preheating zone, the clip pitch of the left and right clips was 125 mm. Next, as soon as the film entered the first diagonal stretching zone C1, 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. In the first oblique stretching zone C1, the clip pitch of the left clip was maintained at a clip pitch of 125 mm in the preheating zone. Next, as soon as the film entered the second oblique stretching zone C2, 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. On the other hand, the clip pitch of the right clip was maintained at 200 mm in the second oblique stretching zone C2. Simultaneously with the oblique stretching, 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%.

  A retardation film (thickness 70 μm) was obtained as described above. The obtained retardation film was trimmed at both ends to a width of 800 mm and subjected to the evaluations (1) to (7) above. The results are shown in Table 1.

<Example 2>
A polycarbonate resin film (thickness: 155 μm, 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. . Specifically, as soon as the film entered the first oblique stretching zone C1, 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. In the first oblique stretching zone C1, 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. Furthermore, as soon as the film entered the second oblique stretching zone C2, 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. On the other hand, the clip pitch of the right clip was maintained at 177.5 mm in the second oblique stretching zone C2. Simultaneously with the oblique stretching, stretching in the width direction was performed 1.9 times. Next, 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 μm) 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 μm, width 765 mm) obtained in the same manner as in Example 1 except that the thickness was different was used, and longitudinal shrinkage after oblique stretching (including lateral stretching) and before MD shrinking treatment A retardation film (thickness 63 μm) was obtained in the same manner as in Example 2 except that horizontal stretching (lateral stretching ratio: 1.05 times) was performed. In addition, the shrinkage ratio in the longitudinal direction is the sum of the shrinkage ratio of the longitudinal shrinkage of the longitudinal shrinkage and the lateral stretching and the shrinkage ratio of the MD shrinkage treatment, and the shrinkage ratio was 7.0% as in the second embodiment. . 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 μm, 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 μm) 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 a cycloolefin resin film (“Zeonor ZF-14 film” manufactured by ZEON Corporation, thickness 100 μm, width 765 mm) instead of the polycarbonate resin film, preheating to 150 ° C. in the preheating zone, and oblique stretching A retardation film (thickness: 40 μm) 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.

<Example 6>
(Preparation of polyvinyl acetal resin film)
After 880 g of a polyvinyl alcohol resin (trade name “NH-18” manufactured by Nippon Synthetic Chemical Co., Ltd. (polymerization degree = 1800, saponification degree = 99.0%)) was dried at 105 ° C. for 2 hours, 16 Dissolved in 0.72 kg of dimethyl sulfoxide (DMSO). To this, 298 g of 2-methoxy-1-naphthaldehyde and 80 g of p-toluenesulfonic acid monohydrate were added and stirred at 40 ° C. for 1 hour. To the reaction solution, 318 g of benzaldehyde was added and stirred at 40 ° C. for 1 hour, and then 457 g of dimethylacetal was further added and stirred at 40 ° C. for 3 hours. Thereafter, 213 g of triethylamine was added to terminate the reaction. The obtained crude product was reprecipitated with methanol. The filtered polymer was dissolved in tetrahydrofuran and reprecipitated again with methanol. This was filtered and dried to obtain 1.19 kg of a white polymer.
When the obtained polymer was measured by ¹ H-NMR, it had a repeating unit represented by the following formula (XI), 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 μm) 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 μm and a width of 765 mm.

  A retardation film in the same manner as in Example 2 except that the polyvinyl acetal resin film was used, preheated to 145 ° C. in a preheating zone, and obliquely stretched (including lateral stretching) at 140 ° C. (Thickness 90 μm) 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.

<Comparative Example 1>
Except that the polycarbonate resin film (thickness 190 μm, 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 μm) 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.

<Comparative Example 2>
Except that the polycarbonate resin film (thickness 150 μm, 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 2. Thus, a retardation film (thickness 55 μm) 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.

<Evaluation>
As is clear from 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). .

10L endless loop 10R endless loop 20 clip 30 clip carrying member 70 reference rail 90 pitch setting rail 100 stretching device 300 circularly polarizing plate 310 polarizer 320 first protective film 330 second protective film 340 retardation film

Claims (4)

It has a slow axis in a direction that is long and has a predetermined angle with respect to the long direction,
A retardation film having an absolute value of change rate of in-plane retardation of 4.1% or less. The in-plane retardation satisfies the relationship of Re (450) <Re (550) <Re (650).
The retardation film according to claim 1:
Here, Re (λ) represents the in-plane retardation of the film measured with light having a wavelength of λ nm at 23 ° C. The retardation film of Claim 1 or 2 whose absolute value of a dimensional change rate is 0.22% or less. The retardation film according to any one of claims 1 to 3, wherein a distribution width of the distribution in the direction of the slow axis is within 3 °.