Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
  • G02F1/133637—Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion

Definitions

• Retardation plate consisting of one polymer film [Technical field]
• the present invention relates to a retardation plate made of one polymer film. Further, the present invention also relates to a reflection type liquid crystal display device including a circularly polarizing plate, a touch panel, and a guest-host type using a retardation plate made of one polymer film.
• the ⁇ / 4 plate has many applications related to antireflection films, touch panels, and liquid crystal displays, and is already in practical use. However, even though they were called LZ4 plates, most of them achieved ⁇ 4 at a certain specific wavelength. In a ⁇ 4 plate used for an image display device, if the wavelength region in which ⁇ 4 can be achieved is narrow, there is a problem that the contrast of a displayed image is reduced.
• JP-A-5-27118 and JP-A-5-27119 each disclose a birefringent film having a large retardation and a birefringent film having a small retardation so that their optical axes are orthogonal to each other.
• a phase difference plate laminated as described above is disclosed. If the difference in retardation of the two films is ⁇ 4 over the entire visible light range, then the retarder theoretically functions as an L / 4 plate over the entire visible light range.
• Japanese Patent Application Laid-Open No. 10-68816 discloses that a polymer film having a thickness of 4 at a specific wavelength and a polymer film of the same material and having the same wavelength; A phase difference plate that can obtain ⁇ / 4 is disclosed.
• Japanese Patent Application Laid-Open No. H10-90521 also discloses a retardation plate capable of achieving 1/4 in a wide wavelength range by laminating two polymer films.
• ⁇ / 4 By laminating two polymer films, ⁇ / 4 can be achieved in a wide wavelength range. For that purpose, it is necessary to laminate the two polymer films while strictly adjusting the angle.
• the present inventor has found that the wavelength dispersion of the polymer film depends on the measurement angle. That is, compare the chromatic dispersion measured from the normal direction of the film with the value of 550 nm and the chromatic dispersion measured from the direction different from the normal direction of the film and the chromatic dispersion similarly normalized. Then they found that they did not match. This phenomenon is the same even when a plasticizer used for improving the processability of the polymer is added. It was manufactured using such a material; when an L / 4 plate is used for a liquid crystal display device, there is a problem that the viewing angle characteristics are deteriorated.
• a stretched film of a synthetic polymer is used as a conventional LZ 4 plate.
• variation in the slow axis direction (axis shift) due to stretching unevenness is likely to occur. If the axis misalignment is large, light leaks and the contrast is reduced.
• a liquid crystal display device using a retardation plate made of a polymer film has a problem that picture frame-like “unevenness” occurs at the time of energization and visual characteristics are deteriorated.
• this light leakage is caused by the fact that the expansion or contraction of the polymer film due to the change of the wet heat condition is suppressed as a whole retardation plate, and the optical characteristics of the polymer film are changed. It was revealed. In particular, it was found that the influence of humidity was great for polymers having hydroxyl groups such as cellulose esters. It is an object of the present invention to provide a retardation plate that achieves ⁇ or ⁇ ⁇ over a wide wavelength region using a single polymer film and has no angle dependence in wavelength dispersion. .
• Another object of the present invention is to provide a retardation plate ( ⁇ 4 plate) or a circularly polarizing plate capable of improving the viewing angle and display quality of a reflection type liquid crystal display device.
• Still another object of the present invention is to apply a single polymer film that realizes LZ4 over the entire visible light range to a touch panel.
• Still another object of the present invention is to provide a reflective liquid crystal display device with a touch panel or a guest-host type liquid crystal display device with a touch panel, which has improved display quality such as contrast and color.
• the retardation value (R e (450)) measured at a wavelength of 450 nm is from 100 to 125 nm
• the retardation value (R e (5 90)) is from 120 to 160 nm, and is composed of one polymer film satisfying a relationship of R e (5 0 0) -R e (4 5 0) ⁇ 4 nm, DR20 (1)-DR0 ( ⁇ )
• R e ( ⁇ ) is the retardation value measured in the normal direction of the film surface
• R e 20 ( ⁇ ) is the normal of the film surface. It is a retardation value measured at an angle of 20 ° from the direction.
• the retardation value (Re (450)) measured at a wavelength of 450 nm is from 100 to 125 nm
• the retardation value measured at a wavelength of 590 nm ( R e (5 90)) is from 120 to 160 nm, and is composed of one polymer film satisfying a relationship of H e (5 90) — Re (4 5 0) ⁇ 2 nm, DR 0 and DR 20 defined by the above formulas (I) and (II) are 1 DR20 ( ⁇ ) and 1 DR0 ( ⁇ )
• the retardation plate that satisfies the relationship 2 above, the polarizing film and the force
• the slow axis in the plane of the retardation plate and the polarization axis also provided is a circularly polarizing plate laminated so that the angle between the polarizers is substantially 45 °.
• the retardation value (R e (450)) measured at a wavelength of 450 nm is from 200 to 250 nm
• the retardation value (R e) measured at a wavelength of 590 nm is (R e (450)).
• e (590)) is 240 to 320 nm, and is composed of one polymer film satisfying the relationship of Re (590)-Re (450) ⁇ 2 nm.
• DR 0 and DR 20 defined by the above formulas (I) and (II).
• ⁇ 0. A retardation plate satisfying the relationship of 02 is also provided.
• two transparent conductive substrates provided with a transparent conductive film on at least one side are arranged so that the transparent conductive films face each other, and at least one of the transparent conductive substrates is an LZ 4 plate.
• the touch panel is also characterized in that 20 satisfies the relationship of I DR 20 (1) -DR 0 ( ⁇ ) ⁇ ⁇ 0.02 at a wavelength of 450
• the present invention relates to a reflection type liquid crystal display device comprising a polarizing film, a plate, a touch panel and a reflection type liquid crystal cell, wherein the ⁇ / 4 plate has a letter value (R) measured at a wavelength of 450 nm. e (450)) is from 100 to 125 nm, and the retardation value (R e (590)) measured at a wavelength of 590 nm is from 120 to 160 nm. , Re (590) —Re (450) ⁇ 2 nm, consisting of one polymer film, and DR0 and DR defined by the above formulas (I) and (II). 20 is a reflective liquid crystal display device characterized by satisfying a relationship of 1 DR 20 (1) DR 0 ( ⁇ ) I ⁇ 0.02 at a wavelength of 450 nm and a wavelength of 750 nm. Also provide.
• the present invention relates to a four-panel, a touch panel and a guest-host type liquid crystal cell.
• a ⁇ / 4 plate having a retardation value (R e (450)) of 100 to 125 nm measured at a wavelength of 450 nm and a wavelength of 590 nm measured at a wavelength of 590 nm.
• the film has a retardation value (Re (590)) of 120 to 160 nm, and a polymer film satisfying the relationship of Re (590) -Re (450) ⁇ 2 nm.
• DR0 and DR20 defined by I) and (II) satisfy the relationship of 1 DR20 (1) -DR0 (1) I ⁇ 0.02 at 450 nm wavelength and 750 nm wavelength.
• a guest-host type liquid crystal display device is also provided.
• the present inventor found that by adjusting the material, additives, and manufacturing method of the polymer film, it was possible to produce a transparent retardation plate achieving LZ 4 or LZ 2 in a wide wavelength range. Successful. Further, when this retardation plate was used by attaching it to a reflection type liquid crystal display device, the viewing angle and the contrast were remarkably improved. A phase difference plate that can achieve ⁇ 4 or ⁇ / 2 in a wide wavelength range using a single polymer film has been obtained.Laminating two conventional polymer films while strictly adjusting the angle The process is no longer needed. Further, when the retardation plate according to the present invention is attached to a reflection type liquid crystal display device, a wide viewing angle can be achieved.
• the thickness is small and light attenuation is small.
• a liquid crystal display device having high reflection luminance can be obtained.
• the touch panel according to the present invention using the four plates (retardation plate) works well.
• display quality such as contrast and color of the reflective liquid crystal display device is improved, and visibility is improved.
• FIG. 1 is a schematic diagram showing a basic configuration of a reflective liquid crystal display device.
• FIG. 2 is a schematic diagram illustrating a basic configuration of a reflective liquid crystal display device using a touch panel.
• FIG. 3 is a schematic cross-sectional view showing a typical embodiment of a guest-host reflection type liquid crystal display device.
• FIG. 4 is a schematic sectional view showing another typical embodiment of the guest-host reflection type liquid crystal display device.
• the retardation value (Re (450)) measured at a wavelength of 45 O nm is 1 ⁇ 0 to 125 nm, and the retardation value measured at a wavelength of 590 nm
• the value (Re (590)) is from 120 to 160 nm, and the relationship of Re (590) -Re (450) ⁇ 2 nm is satisfied. More preferably, Re (590) -Re (450) ⁇ 5 nm, most preferably Re (590) -Re (450) ⁇ 10 nm.
• the retardation value (Re (450)) measured at a wavelength of 450 nm is from 108 to 12 O nm, and the retardation value (Re (550)) measured at a wavelength of 550 nm is from 125 to 142. nm, the retardation value (Re (590)) measured at a wavelength of 590 nm is 130 to 152 nm, and the relationship of Re (590) —Re (550) ⁇ 2 nm is satisfied.
• Re (590) -Re (550) ⁇ 5 nm most preferably Re (590) -Re (550) ⁇ 10 nm. It is also preferable that Re (550) -Re (450) ⁇ 10 nm.
• the retardation value (Re (450)) measured at a wavelength of 45 O nm is 200 to 250 nm
• the retardation value (Re (450) measured at a wavelength of 590 nm is used.
• 590)) is 240 to 320 ⁇ m, and satisfies the relationship of Re (590) -Re (450) ⁇ 4 nm. More preferably, Re (590) -Re (450) ⁇ 10 nm, most preferably Re (590) -Re (450) ⁇ 20 nm
• the retardation value (Re (450)) measured at a wavelength of 450 nm is from 2 16 to 24 O nm, and the retardation value (Re (550)) measured at a wavelength of 550 nm is 25 ° to 284.
• R e (5 0 0) —R e (5 0) ⁇ 10 nm is more preferable, and R e (5 0 0) -R e (5 0) ⁇ 20 nm is most preferable. preferable. It is also preferable that R e (550) -R e (450) ⁇ 20 nm.
• the retardation value (R e ) is calculated according to the following equation.
• nx is the refractive index in the in-plane slow axis direction of the retardation plate (maximum in-plane refractive index); ny is the refraction in the direction perpendicular to the in-plane slow axis of the retardation plate And d is the thickness of the retarder (nm).
• the phase difference plate according to the present invention has a DR 0 and a DR 20 force defined by the following formulas (I) and ( ⁇ ): 1 DR 2 0 ( ⁇ ) at a wavelength of 450 nm and a wavelength of 7500 nm. ) -DR 0 (1) Satisfies the relationship of I ⁇ 0.02.
• ⁇ is the measured wavelength
• R e ( ⁇ ) is the retardation value measured in the normal direction of the film surface
• R e 20 ( ⁇ ) is the method of the film surface. This is the retardation value measured at an angle of 20 ° from the line direction.
• DR40 defined by the following formula (III) is:
• DRa defined by the following formula (IV) is such that, at a wavelength of 45 ° nm and a wavelength of 750 nm, ⁇ a ( ⁇ )-DR 0 ( ⁇ )
• DR a defined by the equation (IV) is, in the wavelength 4 5 0 nm and the wavelength 7 5 0 nm, alpha is at all angles of 6 0 ° or less, I It is preferable to satisfy the relationship of DRa (1) —DRO ( ⁇ )
• DRa defined by the above formula (IV) is such that, at a wavelength of 45 O nm and a wavelength of 700 nm, at all angles at which ⁇ can be measured, 1 DR and ( ⁇ ) 1 It is preferable that the relationship of DR O (E) I ⁇ 0.02 be satisfied, and it is more preferable that the relationship of i DRa ( ⁇ ) -DRO ( ⁇ ) I ⁇ 0.01 be satisfied.
• the retardation plate according to the present invention has a DRO and a DR20 force defined by the above formulas (I) and (II) in all wavelength ranges from 380 nm to 780 nm. It is preferable to satisfy the relationship of ( ⁇ ) —DRO ( ⁇ ) I ⁇ 0.02, and it is even more preferable that the relationship of
• the retardation plate according to the present invention has the following characteristics: DR40 ( ⁇ ) —DR0 ( ⁇ ) in all wavelength ranges from the DR400 force of 380 nm to 780 nm defined by the above formula (III). ) It is preferable to satisfy the relationship of I ⁇ 0.02, and it is still more preferable that the relationship of 1 DR40 (1) —D R0 ( ⁇ ) I ⁇ 0.01 is satisfied.
• the DRa defined by the above formula (IV) is less than 60 ° in all wavelength regions from 380 nm to 780 nm. At all angles, it is preferable to satisfy the relationship of
• the DRa defined by the above formula (IV) is such that
• the retardation plate according to the present invention is preferably made of one polymer film satisfying the following expression.
• nx is the in-plane retardation index in the plane of the retarder measured at 550 nm
• ny is the direction perpendicular to the in-plane retardation axis of the retarder measured at 550 nm
• nz is the refractive index in the thickness direction measured at 550 nm.
• the thickness of one polymer film constituting the retardation plate is preferably 5 to 1000 / m, more preferably 10 to 50 ⁇ , further preferably 40 to 200 ⁇ , and 70 Most preferably, it is from 120 ⁇ to 120 ⁇ .
• Hygroscopic expansion coefficient of the retardation plate is preferably not more than 30 X 10- 5 / cm 2 / % RH.
• the coefficient of hygroscopic expansion is indicated by the amount of change in sample length when the relative humidity is changed at a constant temperature.
• the hygroscopic expansion coefficient is 20 more preferably X 10- 5 ZCM is 2 /% RH or less, 15 X 10 - is preferably a further at 5 / cm 2 /% RH or less.
• the direction of the slow axis in the plane of the film is indicated by the angle formed with the stretching direction.
• the angle between the average direction of the slow axis and the stretching direction is an angle equal to the average value of the angle between the slow axis direction and the stretching direction at any ten locations in the film.
• the average direction of the slow axis is preferably within ⁇ 5 °, more preferably ⁇ 2 °, and most preferably ⁇ 1 ° from the stretching direction.
• the standard deviation is preferably within 2.0, more preferably within 1.5, more preferably within 0.8, and most preferably 5.
• the retardation plate having the above optical properties can be manufactured by the following materials and methods.
• the retardation plate according to the present invention is composed of one polymer film.
• a cellulose ester is preferable, and a lower fatty acid ester of cellulose is more preferable.
• Lower fatty acids refer to fatty acids having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. Cellulose acetate propionate ⁇ Mixed fatty acid esters such as cellulose acetate butylate may be used.
• the average degree of acetylation (acetylation degree) of cellulose acetate is preferably 45.0 to 62.5%, more preferably 55.0 to 61.0%, and 56.0 to 60%. More preferably, it is 5%.
• Two or more cellulose acetates may be used for adjusting the average degree of acetylation.
• the difference in the degree of acetylation of each cellulose acetate is preferably from 2.0 to 6.0%, more preferably from 2.0 to 4.0%.
• the ratio (P 2 / P 1) of the largest viscosity average degree of polymerization (P 1) and the smallest degree of viscosity polymerization (P 2) is preferably 1 to 3, More preferably, it is 1 or 2.
• the hydroxyl groups at the 2-, 3-, and 6-positions of the cellulose ester are not evenly distributed to 1/3 of the total degree of substitution, and the degree of substitution of the 6-position hydroxyl group tends to decrease.
• the degree of substitution of the hydroxyl group at the 6-position of the cellulose ester is preferably higher than that at the 2- and 3-positions.
• the hydroxyl group at the 6-position is substituted with an acyl group in an amount of 30% or more and 40% or less with respect to the total degree of substitution, more preferably 31% or more, particularly preferably 32% or more. Good.
• the substitution degree of the 6-position acyl group of the cellulose ester is preferably 0.88 or more.
• the 6-position hydroxyl group may be substituted with an acetyl group such as a propionyl group, a propyloyl group, a valeroyl group, a benzoyl group, an atalyloyl group, etc. other than the acetyl group.
• the degree of substitution at each position can be measured by NMR.
• Examples of the cellulose ester include Synthesis Example 1 described in Paragraph Nos. ⁇ ⁇ 43 to 0044 of JP-A-11-58151, Synthesis Example 2 described in Paragraph Nos. 0048 to 0049, and Paragraph Nos. 0051 to 0052 described in Paragraphs 0051 to 0052. Cell acetate obtained by the method of Synthesis Example 3 can be used.
• a retardation increasing agent can be added to the cellulose acetate film to adjust the retardation value at each wavelength, and to adjust the value of i DRo; (2) one DR0 (1) I.
• the retardation raising agent is preferably used in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer. It is more preferably used in the range of 5 to 10 parts by mass, and most preferably used in the range of 0.5 to 3 parts by mass. Two or more letter risers may be used in combination.
• the retardation enhancer preferably has a maximum absorption wavelength in the wavelength region of 230 to 360 nm. Further, it is preferable that the retardation raising agent has substantially no absorption in the visible region.
• a compound having at least two aromatic rings is preferably used.
• aromatic ring includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
• the aromatic hydrocarbon ring is a six-membered ring (ie, a benzene ring).
• Aromatic heterocycles are generally unsaturated heterocycles.
• the aromatic heterocyclic ring is 5 It is preferably a membered ring, a six-membered ring or a seven-membered ring, and more preferably a five-membered ring or a six-membered ring.
• Aromatic heterocycles generally have the most double bonds.
• a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.
• aromatic hetero ring examples include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a triazole ring, a pyran ring, and a pyridin ring. Ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.
• aromatic ring examples include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. Is preferred.
• the number of aromatic rings contained in the retardation raising agent is preferably from 2 to 20, more preferably from 2 to 12, and even more preferably from 2 to 8. Most preferably, it is from 6 to 6.
• the bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connected by a single bond, and (c) when connecting via a linking group. A spiro bond cannot be formed).
• the associative relationship may be any of (a) to (c).
• Examples of the condensed ring of (a) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an asenafthylene ring, and a biphenylene ring , Naphthacene ring, pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzoimidazole ring, benzotriazole ring, purine ring, indazole ring, Chromene ring, quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthal
• the single bond in (b) is preferably a bond between carbon atoms of two aromatic rings.
• Two aromatic rings may be linked by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.
• the linking group (c) is also preferably bonded to carbon atoms of two aromatic rings.
• the linking group is preferably an alkylene group, alkenylene group, alkynylene group, one CO—, one O—, one NH—, one S— or a combination thereof. Examples of the linking group consisting of the combinations are shown below. Note that the left and right relationships in the following examples of linking groups may be reversed.
• the aromatic ring and the linking group may have a substituent.
• substituents examples include a halogen atom (F, Cl, Br, I), hydroxyl, carboxylone, cyano, amino, nitro, sulfo, carbamoinole, sulfamoinole, ureido, alkyl, alkenyl, alkynyl.
• halogen atom F, Cl, Br, I
• hydroxyl carboxylone
• cyano amino, nitro, sulfo, carbamoinole, sulfamoinole, ureido, alkyl, alkenyl, alkynyl.
• the alkyl group preferably has 1 to 8 carbon atoms.
• a chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable.
• the alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group).
• Examples of alkyl groups (including substituted alkyl groups) include: methyl, ethynole, n-ptynole, n-hexynole, 2-hydroxyethynole, 4-carboxybutyl, 2-methoxyl, and 2-methynoleamino Includes Echinore.
• the alkenyl group preferably has 2 to 8 carbon atoms.
• a chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable.
• the alkenyl group may further have a substituent. Examples of alkenyl groups include butyl, aryl and 11-hexenyl.
• the alkynyl group preferably has 2 to 8 carbon atoms.
• a chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable.
• the alkynyl group may further have a substituent. Examples of alkynyl groups include ethur, 1-butynyl and 1-hexyl.
• the number of carbon atoms of the aliphatic acyl group is preferably 1 to 10.
• Examples of the aliphatic acyl group include acetyl, propanoyl, and butanoyl.
• the aliphatic acyloxy group preferably has 1 to 10 carbon atoms.
• Examples of the aliphatic acyloxy group include acetoxy.
• the alkoxy group preferably has 1 to 8 carbon atoms.
• the alkoxy group may further have a substituent (eg, an alkoxy group).
• alkoxy groups include methoxy, ethoxy, butoxy and methoxyshethoxy.
• the alkoxycarbonyl group preferably has 2 to 10 carbon atoms.
• alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl Included.
• the alkoxycarbonylamino group preferably has 2 to 10 carbon atoms.
• Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.
• the alkylthio group preferably has 1 to 12 carbon atoms.
• Examples of the alkylthio group include methylthio, ethylthio and octylthio.
• the alkylsulfonyl group preferably has 1 to 8 carbon atoms.
• Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl.
• the aliphatic amide group preferably has 1 to 10 carbon atoms.
• Examples of the aliphatic amide group include acetoamide.
• the aliphatic sulfone amide group preferably has 1 to 8 carbon atoms.
• Examples of the aliphatic sulfonamide group include methanesulfonamide, butanesulfonamide and n-octanesulfonamide.
• the aliphatic substituted amino group preferably has 1 to 10 carbon atoms.
• Examples of the aliphatic substituted amino group include dimethylamino, getylamino and 2-carboxyshetylamino.
• the number of carbon atoms of the aliphatic substitution power rubamoyl group is preferably 2 to 10.
• Examples of the aliphatic-substituting rubamoyl group include methylcarbamoyl and getylcarbamoyl.
• the number of carbon atoms of the aliphatic substituted sulfamoyl group is preferably 1 to 8.
• Examples of the aliphatic-substituted sulfamoyl group include methylsulfamoyl and getyl sulfamoyl.
• the aliphatic substituted ureido group preferably has 2 to 10 carbon atoms.
• Examples of the aliphatic-substituted ureido group include methinourelide.
• non-aromatic heterocyclic group examples include piperidino and morpholino.
• Retardation Chillon molecular weight of raising agent specific examples of preferably from 300 to 800 Retardation Chillon increasing agent, JP 2 000 1 1914 JP, the
• an infrared absorbing agent can be added to the polymer film.
• the infrared absorber is preferably used in a range of 0.01 to 5 parts by mass, more preferably in a range of 0.02 to 2 parts by mass, based on 100 parts by mass of the polymer. It is more preferably used in the range of 0.05 to 1 part by mass, and most preferably used in the range of 0.1 to ⁇ 5 parts by mass. Two or more infrared absorbers may be used in combination.
• the infrared absorber preferably has a maximum absorption in a wavelength range of 750 to 100 nm, and more preferably has a maximum absorption in a wavelength range of 800 to 1,000 nm. Preferably, the infrared absorber has substantially no absorption in the visible region.
• infrared absorbing dye or an infrared absorbing pigment as the infrared absorbing agent, and it is particularly preferable to use an infrared absorbing dye.
• Infrared absorbing dyes include organic compounds and inorganic compounds. It is preferable to use an infrared absorbing dye which is an organic compound.
• Organic infrared absorbing dyes include cyanine compounds, metal chelate compounds, aluminum compounds, dimonium compounds, quinone compounds, squarium compounds, and methine compounds. Infrared absorbing dyes are described in Coloring Materials, 61 [4] 215-226 (1988), and Chemical Industry, 43-53 (1986, May).
• Infrared absorbing dyes developed in the technical field of silver halide photographic materials include dihydroperimidine squaridum dyes (US Pat. No. 5,380,635 and Japanese Patent Application No. 8-189817). ), Cyanine dyes (JP-A-62-123454, JP-A-3-138640, JP-A-3-221542, JP-A-226736, JP-A-5-313305, JP-A-6-43583) Publications, Japanese Patent Application No. 7-26 909 7 Specification and European Patent No.
• a film is produced using a solution (dope) of a polymer dissolved in an organic solvent.
• the organic solvent is selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to include a solvent.
• Ethers, ketones and esters may have a cyclic structure.
• Compounds having two or more functional groups of ether or ketone ester that is, —O—, —CO— and —CO ⁇
• the organic solvent may have another functional group such as an alcoholic hydroxyl group.
• the number of carbon atoms may be within the specified range of the compound having any one of the functional groups.
• ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxetane, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, azole and phenetole Is included.
• ketones having 3 to 12 carbon atoms include acetone, methylethyl ketone, getyl ketone, diisobutyl ketone, hexahexanone, and methylcyclohexyl. Hexanone is included.
• esters having 3 to 12 carbon atoms examples include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.
• organic solvent having two or more kinds of functional groups examples include 2-ethoxyshetyl acetate, 2-methoxyethanol and 2-butoxyethanol.
• the number of carbon atoms in the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1.
• the halogen of the halogenated hydrocarbon is preferably chlorine.
• the proportion of halogen atoms substituted by halogen atoms in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is 40 to 60 mol%, most preferably 40 to 60 mol%.
• Methylene chloride is a typical halogenated hydrocarbon. Two or more organic solvents may be used as a mixture.
• the polymer solution can be prepared by a general method.
• the general method means treating at a temperature of 0 ° C or higher (normal temperature or high temperature).
• the solution can be prepared using a dope preparation method and apparatus in a usual solvent casting method.
• the amount of the polymer is adjusted so that the obtained solution contains 10 to 40% by mass. More preferably, the amount of polymer is from 10 to 30% by weight. Any additives described below may be added to the organic solvent (main solvent).
• the solution can be prepared by stirring the polymer and the organic solvent at room temperature (0 to 40 ° C). Highly concentrated solutions may be stirred under pressure and heating conditions. Specifically, the polymer and the organic solvent are put in a pressurized container, sealed, and stirred while heating under pressure to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil.
• the heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.
• Each component may be roughly mixed in advance and then placed in a container. Alternatively, they may be sequentially charged into a container.
• the container must be configured to be able to stir. Inactivation of nitrogen gas, etc.
• the container can be pressurized by injecting a neutral gas. Further, an increase in the vapor pressure of the solvent due to heating may be used. Alternatively, the components may be added under pressure after the container is sealed.
• a jacket type heating device can be used.
• a plate heater may be provided outside the container, and the entire container may be heated by circulating the liquid through piping.
• a stirring blade inside the container and stir using the stirring blade is preferably long enough to reach near the container wall. It is preferable to provide a collecting blade at the end of the stirring blade in order to renew the liquid film on the container wall.
• Instruments such as a pressure gauge and a thermometer may be installed in the container. Dissolve each component in the solvent in a container. The prepared dope is taken out of the container after cooling, or a certain dope is taken out and then cooled using a heat exchanger or the like.
• the solution can be prepared by the cooling dissolution method.
• the cooling dissolution method the polymer can be dissolved even in an organic solvent that is difficult to dissolve by a normal dissolution method. Even if the solvent can dissolve the polymer by the usual dissolution method, the cooling dissolution method has an effect that a uniform solution can be obtained quickly.
• a polymer is gradually added to an organic solvent at room temperature with stirring.
• the amount of the polymer is preferably adjusted so as to be contained in the mixture at 10 to 40% by mass. More preferably, the amount of polymer is from 10 to 30% by weight. Further, an optional additive described later may be added to the mixture.
• the mixture is then brought to a temperature of between 10 ° C and 110 ° C (preferably between 180 ° C and 110 ° C, more preferably between 150 ° C and 120 ° C, most preferably between 150 ° C and 110 ° C. Cool to 30 ° C). The cooling can be performed, for example, in a dry ice-methanol bath ( ⁇ 75 ° C.) or a cooled diethylene glycol solution (130 ° C. to 120 ° C.). Upon cooling, the mixture of the cellulose ester and the organic solvent solidifies.
• the cooling rate is preferably at least 4 ° C / min, more preferably at least 8 ° CZ, most preferably at least 12 ° CZ. Cooling rate is fast
• the preferred upper limit is 100,000 ° C / sec
• the upper limit is 100,000 o ° cz seconds is the technical upper limit
• the upper limit is 100,000 ° C / sec. It is.
• the cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.
• the organic solvent The polymer dissolves in it.
• the temperature may be raised simply by leaving it at room temperature or may be heated in a warm bath.
• the heating rate is preferably at least 4 ° C / min, more preferably at least 8 ° C / min, most preferably at least 12 ° CZ.
• the heating rate is preferably as fast as possible, but 100 ° C osec. Is the theoretical upper limit, 100 ° C ° Cz is the technical upper limit, and 100 ° C / sec. Is a practical upper limit.
• the heating rate is a value obtained by dividing the difference between the temperature at which heating is started and the final heating temperature by the time from when heating is started until the final heating temperature is reached. is there.
• the dissolution As described above, a uniform solution is obtained. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined only by visually observing the appearance of the solution.
• the cooling dissolution method it is desirable to use a closed container to avoid water contamination due to condensation during cooling. Further, in the cooling and heating operation, if the pressure is increased during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to carry out pressurization and decompression, it is desirable to use a pressure-resistant container.
• the dope is cast on a drum or band and the solvent is evaporated to form a film.
• concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. It is preferred that the surface of the drum or band be finished to a mirror surface.
• the casting and drying methods in the solvent casting method see U.S. Patent Nos. 2336310, And JP-B-736892, JP-B-45-4554, JP-B-49-15614, JP-A-60-176834, JP-B-60-203430, and JP-B-62-115035. is there.
• the dope is preferably cast on a drum or band having a surface temperature of 10 ° C or less. It is preferable to dry it by blowing it for 2 seconds or more.
• the resulting film can be peeled off from the drum or band and dried with high-temperature air with successively varying temperatures from 100 to 160 ° C to evaporate residual solvent.
• the above method is described in Japanese Patent Publication No. 5-17844. According to this method, the time from casting to stripping can be shortened. In order to carry out this method, the dope needs to gel at the surface temperature of the drum or band during casting.
• the solution (dope) prepared as described above satisfies this condition.
• the thickness of the film to be produced is preferably from 40 to 140 / m, more preferably from 70 to 120 / m, even more preferably from 70 to 100 ⁇ .
• a plasticizer can be added to the polymer film to improve mechanical properties or to increase the drying speed.
• a plasticizer a phosphoric acid ester or a carboxylic acid ester is used.
• phosphate esters include triphenyl phosphate ( ⁇ ) and tricresyl phosphate (TCP).
• Representative carboxylic esters are phthalic esters and citrates.
• phthalates include dimethyl phthalate (DMP), Includes ethyl phthalate (DEP), dibutyl phthalate (DBP), octyl phthalate (DOP), diphenyl phthalate (DPP) and getylhexyl phthalate (DEHP).
• citrate esters examples include triethyl O-acetyl citrate (OACTE) and tributyl O-acetyl citrate (OA CTB).
• carboxylic esters examples include butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, and various trimellitate esters.
• Phthalate plasticizers DMP, DEP, DBP, DOP, DPP, DEHP
• DEP and DPP are particularly preferred.
• the addition amount of the plasticizer may affect the chromatic dispersion, so it is necessary to adjust the addition amount together with the addition amount of the retardation increasing agent.
• the amount is preferably from 0.1 to 25% by mass, more preferably from 1 to 20% by mass, most preferably from 3 to 15% by mass of the amount of the polymer.
• Degradation inhibitors eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines
• the deterioration inhibitor is described in JP-A-3-199201, JP-A-5-1907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854.
• the amount of the deterioration inhibitor added is 0.01 to 1 mass of the prepared solution (dope). / 0 , more preferably 0.01 to 0.2% by mass. If the amount is less than 0.01% by mass, the effect of the deterioration inhibitor is hardly recognized.
• the addition amount exceeds 1% by mass, pre-adhesion (bleeding) of the deterioration inhibitor to the film surface may be observed.
• the deterioration inhibitor include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).
• polymer films have hydrophobic compounds.
• a substance may be added.
• the material having hydrophobicity is not particularly limited as long as the material has a hydrophobic group such as an alkyl group or a phenyl group in the molecule. It is preferably used.
• Addition amount is preferably 0.01 to 10 wt% of the solvent liquid for adjusting (dope), 0.1 preferably to 1 to 5 wt 0/0 Gasara, 1 to 3 wt. / 0 is most preferred.
• the polymer film may be provided with a matting layer containing a matting agent and a polymer on one or both sides to improve the handleability during production.
• a matting agent and a polymer the materials described in JP-A-10-44327 can be suitably used.
• the polymer film can be further subjected to a stretching treatment (preferably 1.1 to 2 times, more preferably 1.1 to 1.5 times) by a refractive index (refractive index nx in the in-plane slow axis direction, in-plane It is preferable to adjust the refractive index ny in the direction perpendicular to the slow axis and the refractive index nz) in the thickness direction.
• the refractive index increases in the direction in which the polymer chains are oriented.
• the refractive index usually becomes nx> 117 112. This is because in the polymer chains oriented in the in-plane direction, the X component increases by stretching and the z component becomes the smallest.
• the stretching ratio is a relative value when the length before stretching is set to 1. SB may be less than 1 (in other words, shrink). If the relationship of the above expression is satisfied, SB may be a value less than 1.
• the stretching ratio can also be adjusted so that the front retardation is L / 4.
• the stretching temperature is preferably at least 10 ° C higher than the glass transition temperature of the polymer, preferably at least 20 ° C lower than the crystallization temperature, more than 10 ° C higher than the glass transition temperature, and at least 40 ° C higher than the crystallization temperature. Lower temperatures are more preferred.
• the glass transition temperature and the crystallization temperature are values measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° CZ.
• the stretching method is not particularly limited, but a roll stretching method is preferred.
• the stretching treatment may be performed a plurality of times, and may be simultaneous treatment or sequential treatment.
• the stretched film may be heat-treated.
• the heat treatment is preferably performed at a temperature 20 ° C lower than the glass transition temperature of the polymer film to 10 ° C higher.
• the heat treatment time is preferably from 1 second to 3 minutes, more preferably from 1 second to 2 minutes, and most preferably from 1 second to 1 minute.
• the heating method may be zone heating or partial heating using a heat source such as an infrared heater.
• a polarizing plate is one in which a polarizing film is sandwiched between transparent protective films. Substantially 45 ° means 40 to 50 °.
• the angle between the average direction of the slow axis in the plane of the ⁇ / 4 plate and the polarization axis of the polarizing film is preferably 41 to 49 °, and more preferably 42 to 48 °. More preferably, it is 43 to 47 °, even more preferably, 44 to 46 °. Is most preferred.
• a circular polarizing plate can also be obtained by laminating a ⁇ / 4 plate and a polarizing film such that the angle between the slow axis in the plane of the ⁇ / plate and the polarizing axis of the polarizing film is substantially 45 °. Is obtained.
• the polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film.
• the iodine-based polarizing film and the dye-based polarizing film are generally produced using a polyvinyl alcohol-based film.
• the polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film.
• a transparent protective film on the surface of the polarizing film opposite to the quarter plate. It is preferable to provide a hard coat layer on the transparent protective film. It is preferable to provide an antireflection layer as the outermost layer.
• the touch panel is composed of a fixed substrate near the display element and a movable substrate facing the fixed substrate.
• a transparent electrode is provided on each of the opposing surfaces of the fixed substrate and the movable substrate.
• the fixed substrate and the movable substrate are preferably formed of a transparent optical material in order to improve display quality. Examples of the material used for the fixed substrate and the movable substrate include glass, an amorphous film, polyether sulfone, polycarbonate, polyarylate, polyethylene terephthalate, and polymer finolem such as senorellose estenolle.
• the Z4 plate is composed of a polymer film (preferably a cellulose ester film); the Z4 plate may be provided separately from the touch panel, or may be used for one or both of a fixed substrate and a movable substrate. It is particularly preferable to use a quarter plate composed of a polymer film as a movable substrate.
• a gap is formed between the two transparent electrodes. There is usually an air layer between the gaps, but a liquid with a refractive index close to that of the transparent electrode can be filled for optical matching. Further, an undercoat layer may be provided on the substrate side of the transparent electrode film, or an overcoat layer may be provided on the side opposite to the substrate to reduce light reflection. The surface of the transparent electrode film may be roughened to eliminate sticking and improve the keying life.
• a spacer can be provided between the gaps. As the spacer, a dot-shaped spacer or a bonding material provided around a fixed substrate and a movable substrate is used.
• Touch panels are used in both digital and analog types.
• the digital method it is possible to detect the contact between the transparent electrodes by pressing and the data position corresponding to the contact position.
• electrodes are formed at both ends in the X-axis direction of the fixed substrate and both ends in the Y-axis direction of the movable substrate, and the transparent electrodes come into contact with each other by pressing, and the X and Y directions generated by the contact position
• the data input position can be detected by detecting the resistance value in the direction.
• the touch panel is preferably used with a display element.
• Touch panel part The display unit may be separate from the display unit, or both may be integrated.
• the polarizing plate may be provided between the touch panel and the display element, or the polarizing plate may be an inner type provided outside the touch panel (on the observer side). It is preferable to use a touch panel that has reduced anti-reflection of external light and excellent anti-glare properties as an inner type.
• the transparent conductive film used as Tatsuchipaneru, surface resistivity, 1 0 is preferably 4 Omega / D or less, 1 0 0 0 Omega / more preferably mouth or less, below 5 0 0 Omega Zeta port Most preferably.
• a transparent conductive film is provided on at least one surface of the IZ4 plate to be used as an inner type touch panel.
• the transparent conductive film In order to set the surface resistivity of the transparent conductive film to the above value, it may be provided by applying a conductive fine particle dispersion or the like, or may be provided by co-casting at the time of film casting. . Further, the transparent conductive film may be formed by a vacuum film forming method such as sputtering, vacuum evaporation, or ion plating. A transparent conductive film may be provided on one side of the film, or may be provided on both sides. Also, these methods can be used in combination.
• the method for applying the conductive fine particle dispersion basically includes a layer containing fine particles composed of at least one or more metals and / or metal oxides and metal nitrides.
• the fine particles composed of one or more metals include metals such as gold, silver, copper, aluminum, iron, nickel, palladium, and platinum, and alloys thereof.
• silver is preferable, and an alloy of palladium and silver is more preferable from the viewpoint of weather resistance.
• the content of palladium is preferably 5 to 3 wt%. If the amount of palladium is small, the weather resistance is poor, and if the amount of palladium is large, the conductivity is reduced.
• Methods for preparing metal fine particles include a method for preparing fine particles by a low-vacuum evaporation method and a method for reducing an aqueous solution of a metal salt with a reducing agent such as an amine such as iron (II), hydrazine, boron hydride, or hydroxyxylamine.
• a reducing agent such as an amine such as iron (II), hydrazine, boron hydride, or hydroxyxylamine.
• the metal oxide I us ⁇ 3 system (including doped products such as S n), S N_ ⁇ 2 system (F Includes such doped article S b), including doped products such as Z n O system (A 1, G a), T i O 2, A 12 ⁇ 3, S i O 2, MgO , B aO, Mo O s, V 2 O s or a composite of these.
• the metal nitride include TiN.
• the average particle size of these conductive fine particles is preferably from 1.0 to 700 nm, more preferably from 2.0 to 300 nm, most preferably from 5.0 to 100 nm.
• the conductive fine particle layer can be formed by applying a paint in which conductive fine particles are dispersed in a solution mainly composed of water or an organic solvent. Before application, a surface treatment or undercoating can be applied.
• Examples of the surface treatment include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet process), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
• Examples of the material of the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate and vinyl ester, or latex, and water-soluble polymers such as gelatin, but are not particularly limited.
• a solution mainly composed of water is preferable for stabilizing the dispersion of the conductive fine particles.
• Examples of the solvent that can be mixed with water include ethyl alcohol, n-propyl alcohol, i-propyl alcohol, butyl alcohol, methylcellosolve, and ptinoresel.
• the coating amount of the conductive fine particles is preferably 10 to 1000 mg / m 2, more preferably 20 to 5 00111 8/131 2, and most preferably 5 0 to 1 50 mg / m 2. If the coating amount is small, the conductivity cannot be obtained, and if the coating amount is large, the permeability is poor.
• the transparent conductive layer may contain a binder, may contain no binder, and may be formed substantially only of conductive fine particles.
• a binder When a binder is used, a hydrophilic binder, a hydrophobic binder, or latex can be used.
• hydrophilic binders include gelatin, gelatin derivatives, agar, sodium alginate, starch, polybutyl alcohol, polyacrylic acid copolymer, water-free maleic acid copolymer, carboxymethylcellulose, and carboxymethyl cellulose. Includes glucose, hydroxymethinorese / rerose, and hydroxyxetinoresenorelose.
• hydrophobic binder examples include cellulose esters (eg, cellulose nitrate, senorelose diacetate, senorelostriacetate), senorelose acetate (eg, methylcellulose), vinyl polymers (eg, butyl chloride, vinylidene chloride, vinyl) Atalylate '), polyamides and polyesters.
• cellulose esters eg, cellulose nitrate, senorelose diacetate, senorelostriacetate
• senorelose acetate eg, methylcellulose
• vinyl polymers eg, butyl chloride, vinylidene chloride, vinyl
• Heat treatment or water treatment can be performed to improve the conductivity and transparency of the transparent conductive layer.
• the heat treatment depends on the heat resistance of the polymer film, but is preferably 150 ° C. or lower.
• the temperature is preferably from 100 ° C to 150 ° C. Above 150 ° C, the polymer film is likely to be deformed by heat, and below 100 ° C, the effect of the heat treatment is difficult to achieve, and a long processing time is required.
• the heat treatment method it is preferable to perform the treatment while passing through a heating zone in a web state, since uniform treatment can be performed.
• the stay time can be adjusted by the length of the heating zone and the transport speed. It is also possible to heat the rolled film in a thermostat, but it is necessary to set the time in consideration of the variation in heat conduction.
• the transparent conductive layer is subjected to water treatment such as washing with water, so that the heat treatment can be further efficiently performed.
• Water treatment such as water washing includes application of only water using a normal application method, specifically, dip coating, application of water using a wire bar, etc.
• water is sprayed or showered using a transparent conductive material. After applying water to the transparent conductive layer, excess water can be removed with a wire bar or rod bar or with an air knife as needed.
• These water treatments can further reduce the surface resistance of the transparent conductive tank after the heat treatment, increase the transmittance, flatten the transmission spectrum, and reflectivity after the anti-reflection layer is deposited. The effect on the reduction of the amount becomes significant.
• Film metal oxides I n 2 O a system as (S n such doped products, including ITO), (including F, doped products such as S b) S n 0 2 system, Z N_ ⁇ system (A 1, G a, etc.), or a composite of these, In 2 ⁇ 3 — Z ⁇ ⁇ system.
• S n such doped products, including ITO
• F doped products
• S b S n 0 2 system
• Z N_ ⁇ system Z N_ ⁇ system
• the metal nitride include TiN.
• a film may be formed together with silver or the like.
• Sputtering such as a polymer film fluoric the its surface when forming on the resin, acrylic resin, silicone resin, propylene resin, and a high molecule such as vinyl resin, S I_ ⁇ 2, T I_ ⁇ 2 , Z R_ ⁇ 2, and an inorganic substance on the court child such as S N_ ⁇ 2 is preferred.
• the coating thickness is preferably from 10 nm to 100, more preferably from 10 nm to 50 ⁇ m, and particularly preferably from 10 nm to 10 ⁇ .
• the temperature is preferably from -30 ° C to 30 ° C, more preferably from 130 ° C to 20 ° C, particularly preferably from 130 ° C to 10 ° C.
• reactive sputtering using a metal target containing indium as a main component or a target which is a sintered body mainly containing syndium oxide is used.
• an inert gas such as argon is used as a sputtering gas, and oxygen is used as a reactive gas.
• DC magnetron sputtering, RF magnetron sputtering, etc. can be used as a discharge type.
• a method for controlling the flow rate of oxygen it is preferable to use a plasma emission monitor method.
• the light transmittance of the polymer film provided with the transparent conductive layer is preferably at least 50%, more preferably at least 60%, particularly preferably at least 70%, and preferably at least 80%. Is most preferred.
• the touch panel can be used in combination with various display devices. Examples include force sword-ray tubes (CRTs), plasma displays (PDPs), fino-red 'emission' displays (FEDs), inorganic EL devices, organic EL devices, and liquid crystal displays.
• CTRs force sword-ray tubes
• PDPs plasma displays
• FEDs fino-red 'emission' displays
• inorganic EL devices organic EL devices
• liquid crystal displays liquid crystal displays.
• FIG. 1 is a schematic diagram showing a basic configuration of a reflective liquid crystal display device.
• the reflective liquid crystal display device shown in FIG. 1 includes, in order from the bottom, a lower substrate (a), a reflective electrode (b), a lower alignment film (c), a liquid crystal layer (d), an upper alignment film (e), and a transparent electrode ( f), upper substrate
• the lower substrate (a) and the reflective electrode (b) constitute a reflector.
• the lower alignment film (c) to the upper alignment film (e) constitute a liquid crystal cell.
• the L / 4 plate (h) can be arranged at any position between the reflector and the polarizing film (i).
• one color filter is further provided.
• One color filter is preferably provided between the reflective electrode (b) and the lower alignment film (c) or between the upper alignment film (e) and the transparent electrode ( ⁇ ).
• a transparent electrode may be used instead of the reflective electrode (b) shown in Fig. 1, and a separate reflector may be attached.
• a metal plate is preferable. If the surface of the reflector is smooth, only the specular reflection component is reflected and the viewing angle may be narrowed. Therefore, it is preferable to introduce an uneven structure (described in Japanese Patent No. 275620) on the surface of the reflector. If the surface of the reflector is flat (instead of introducing an uneven structure on the surface), a light diffusion film may be attached to one side (cell side or outside) of the polarizing film.
• FIG. 2 is a schematic diagram illustrating a basic configuration of a reflective liquid crystal display device using a touch panel.
• the reflection type liquid crystal display device using the touch panel shown in FIG. 2 includes, in order from the bottom, a lower substrate (a), a reflective electrode (b), a lower alignment film (c), a liquid crystal layer (d), and an upper alignment film (e). , Transparent electrode (f), upper substrate (g), transparent conductive film ( ⁇ ), transparent conductive film (k), ⁇ 4 plate
• a gap is formed between the transparent conductive film (j) and the transparent conductive film (k), and functions as a touch panel.
• the liquid crystal mode used is not particularly limited, but the TN (twisted nematic) type, It is preferably of STN (Supper Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, or GH (Guest Host) type.
• the twist angle of the TN type liquid crystal cell is preferably from 40 to 100 °, more preferably from 50 to 90 °, and most preferably from 60 to 80 °.
• the value of the product (An d) of the refractive index anisotropy ( ⁇ ) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.1 to 0.5 im, and 0.2 to 0.5 im. More preferably, it is 4 ⁇ m.
• the twist angle of the STN type liquid crystal cell is preferably from 180 to 360 °, more preferably from 220 to 270 °.
• the value of the product (An d) of the refractive index anisotropy ( ⁇ n) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably from 0.3 to 1.2 ⁇ , and from 0.5 to 1.2 ⁇ . 1. ⁇ / zm is more preferable.
• the liquid crystal is substantially vertically aligned on one substrate and the pretilt angle on the other substrate is 0 to 45 °.
• the value of the product (An d) of the refractive index anisotropy ( ⁇ ) of the liquid crystal layer and the thickness (d) of the liquid crystal layer is preferably 0.1 to 1.0 ⁇ , and 0.3 to 0 ⁇ . More preferably, it is 8 ⁇ .
• the substrate on the side where the liquid crystal is vertically aligned may be a substrate on the reflector side or a substrate on the transparent electrode side.
• the liquid crystal layer is composed of a mixture of liquid crystal and a dichroic dye.
• the director of the liquid crystal and the long axis direction of the dichroic dye are parallel.
• the dichroic dye also changes in the long-axis direction like the liquid crystal.
• a Heil meir type, a White-Tay 1 or type using a cholesteric liquid crystal, a two-layer type, and a type using a ⁇ / 4 plate are known. In the present invention, it is preferable to use a method using a ⁇ / 4 plate.
• JP-A-6-222350, JP-A-8-36174, JP-A-10-268300, JP-A-10-292175, JP-A-10-293301, and JP-A-10-294, JP-A-6-222350, JP-A-8-36174, JP-A-6-222350 It is described in the respective publications of 31 1 976, 10-31 9442, 10-325953, 10-331 3338, and 11-38410.
• the four plates are provided between the liquid crystal layer and the reflector.
• the liquid crystal layer can use either horizontal or vertical alignment Preferably, a vertical orientation is used. It is preferable that the dielectric anisotropy of the liquid crystal is negative.
• the polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film.
• the iodine-based polarizing film and the dye-based polarizing film are generally produced using a polyvinyl alcohol-based film.
• the polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film.
• the reflective liquid crystal display device should be used in the normally white mode, in which the display is bright when the applied voltage is low, and dark when the applied voltage is high, or in the normally black mode in which the display is dark when the applied voltage is low and bright when the applied voltage is high. Can be. Normally white mode is preferred.
• FIG. 3 is a schematic cross-sectional view showing a typical embodiment of a guest-host reflection type liquid crystal display device.
• the guest-host reflective liquid crystal display device shown in Fig. 3 consists of a lower substrate (1), an organic interlayer insulating film (2), a metal reflector (3), a ⁇ / 4 plate (4), a lower transparent electrode (5), and a lower transparent electrode (5).
• the lower substrate (1) and the upper substrate (2) having a different structure are made of a glass plate or a plastic film.
• the TFT (13) is mounted between the lower substrate (1) and the organic interlayer insulating film (2).
• the liquid crystal layer (7) is composed of a mixture of liquid crystal and dichroic dye.
• the liquid crystal layer is obtained by injecting a mixture of liquid crystal and a dichroic dye into the cell gap formed by the spacer (14).
• the metal reflection plate (3) may have a light diffusion function by making the surface of the metal reflection plate (3) uneven.
• the antireflection layer (12) preferably has an antiglare function in addition to the antireflection function.
• FIG. 4 is a schematic sectional view showing another typical embodiment of the guest-host reflection type liquid crystal display device.
• the guest-host reflective liquid crystal display device shown in Fig. 4 consists of a lower substrate (1) ', an organic interlayer insulating film (2), a cholesteric color reflector (3), a ⁇ 4 plate (4), a lower transparent electrode (5), and a lower transparent electrode (5).
• the lower substrate (1) and the upper substrate (2) are made of a glass plate or a plastic film.
• the TFT (13) is mounted between the lower substrate (1) and the organic interlayer insulating film (2).
• the Z4 plate (4) may function as a light diffusion plate.
• the liquid crystal layer (7) is composed of a mixture of liquid crystal and dichroic dye.
• the liquid crystal layer is obtained by injecting a mixture of liquid crystal and a dichroic dye into the cell gap formed by the spacer (14).
• a black matrix (15) is attached between the upper transparent electrode (9) and the upper substrate (11).
• the antireflection layer (12) preferably has an antiglare function in addition to the antireflection function.
• the ⁇ / 4 plate according to the present invention can be used as the LZ4 plate (4) of the guest-host reflection type liquid crystal display device described with reference to FIGS.
• the quarter-plate according to the present invention can also be used for the guest-host reflection type liquid crystal display device described in each of the above publications.
• the refractive index ⁇ ⁇ in the in-plane slow axis direction at a wavelength of 550 nm, the direction perpendicular to the in-plane slow axis And the refractive index ⁇ ⁇ in the thickness direction were calculated, and the value of ( ⁇ ⁇ — ⁇ ⁇ ) / (n x ny) was calculated.
• the angle between the direction of the slow axis and the stretching direction of the polymer film (retardation film) was measured with an automatic birefringence meter (KOBRA-21 ADH, Oji Scientific Instruments). Each measurement was performed at an arbitrary point in the film, and the average direction was determined. The standard deviation was also calculated for the angle between the direction of the slow axis at 10 points and the average slow axis direction.
• a sample of 5 mm width and 2 Omm length was cut out from the prepared polymer film (retardation plate), and one end was fixed and hung under an atmosphere of 25 ° C and 20% RH. A 0.5 g weight was hung on the other end and left for a certain period of time. Next, while keeping the temperature constant, the humidity was set to 80% RH, and the length deformation was measured. The measurement was performed on 10 samples of the same sample, and the average value was adopted.
• a solution (dope) was prepared by mixing 1.20 parts by mass, 704 parts by mass of methylene chloride and 61.2 parts by mass of methanol. (Lettering agent)
• the obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and dried at 45 ° C for 5 minutes.
• the residual amount of the solvent after drying was 30% by mass.
• the cellulose acetate film was peeled off from the glass plate and dried at 100 ° C for 20 minutes and at 130 ° C for 10 minutes. After the film was cut into a suitable size, it was stretched at 130 ° C. in a direction parallel to the casting direction. The direction perpendicular to the stretching direction was allowed to shrink freely. After stretching and cooling to room temperature, the stretched film was taken out.
• the residual solvent amount after stretching was ⁇ .2% by mass.
• the thickness of the obtained film was 103 ⁇ .
• the stretching ratio was 1.42 times.
• a retardation plate was produced in the same manner as in Example 1 except that the obtained dope was used.
• the thickness of the obtained film was ⁇ ⁇ ⁇ ⁇ .
• the stretching ratio was 1.41.
• cellulose acetate having an average degree of acetylation of 59.4% 1 17.87 parts by mass, the retardation increasing agent used in Example 1 1.16 parts by mass, trifeninole phosphate 9.10 parts by mass, bihue A solution (dope) was prepared by mixing 4.50 parts by mass of dirdiphenyl phosphate, 2.36 parts by mass of tribenzylamine, 609.37 parts by mass of methylene chloride, and 53.0 parts by mass of methanol.
• the obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 45 ° C for 5 minutes.
• the cellulose acetate film was peeled off from the glass plate, dried at 100 ° C for 10 minutes, and then dried at 120 ° C for 2 minutes.
• the amount of residual solvent after drying is 2. It was 1%.
• the dried film was cut into an appropriate size, it was stretched at 130 ° C. in a direction parallel to the casting direction. The direction perpendicular to the stretching direction was allowed to shrink freely. After stretching, the film was taken out under an atmosphere at room temperature and cooled.
• the thickness of the obtained film was 102 ⁇ .
• the residual amount of the solvent was 0.1% by mass.
• Example 1 In another mixing tank, the retardation raising agent used in Example 1 1.18 parts by mass, tribenzylamine 2.36 parts by mass, methylene chloride 16.0 parts by mass methanol 1. 39 parts by mass were charged and stirred while heating to prepare a retardation increasing agent solution.
• the entire retardation raising agent solution was charged into the cellulose acetate solution, and the mixture was sufficiently stirred to prepare a dope.
• the obtained dope was cast and uniaxially stretched using a dope casting machine provided with a multi-stage roll stretching zone in a drying zone after casting.
• the residual solvent content of the film immediately before the stretching zone was 2.0%.
• the stretching zone was covered with a casing to keep the temperature uniform, and the temperature was set to 130 ° C on the membrane surface.
• the stretching temperature of the film was adjusted by the temperature of the roll and an infrared heater provided between the rolls.
• the stretching ratio was adjusted to 1.42 times by adjusting the rotation speed of the roll.
• the stretched film was gradually cooled to room temperature and wound up.
• the film thickness of the obtained film was 101 / m.
• the residual solvent content was 0.2%.
• 1.18 parts by mass, triphenyl phosphate 9.19 parts by mass, biphenyldiph 4.60 parts by mass of enyl phosphate, 2.36 parts by mass of tribenzylamine, 529.90 parts by mass of methyl acetate, 99.4 parts by mass of ethanol, and 33.1 parts by mass of butanol were mixed with stirring.
• the mixed solution was cooled in a freezer at 170 ° C, and the temperature was raised to 40 ° C again to dissolve the cellulose acetate.
• a stretched film was produced in the same manner as in Example 1.
• the stretching ratio was 1.41 times.
• the thickness of the obtained film was 100 ⁇ .
• the residual solvent content of the film was 0 : 4%.
• the obtained solution (dope) was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 45 ° C for 5 minutes.
• the cellulose acetate film was peeled off from the glass plate, dried at 100 ° C for 20 minutes, and then dried at 130 ° C for 10 minutes.
• Example 1 450 nrn DD 0 nm 590 nm (nx—ny)
• Example 1 1 16.8 nm 1 375 nm 143.3 nm 1 53
• Example 2 1 1 5.7 nm 1 365 5 nm 142.3 nm 1 53
• Example 3 1 16.3 nm 1 36 9 nm 142.5 nm 1 52
• Example 4 1 1 7.1 nm 1 37 9 nm 143.3 nm 1 48
• Example 5 1 1 6.4 nm 1 37 0 nm 142.5 nm 1 52 Comparative Example 2 147.8 nm 1 37 5 nm 1 34.9 nm 1 1 2
• Example 4 ⁇ 0.9 '0.9
• the transparent protective film, the polarizing film and the retardation film produced in Example 2 were laminated in this order to obtain a circularly polarizing plate.
• the angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °.
• the transparent protective film, the polarizing film and the retardation film produced in Example 4 were laminated in this order to obtain a circularly polarizing plate.
• the angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °.
• the transparent protective film, the polarizing film and the retardation film produced in Comparative Example 2 were laminated in this order to obtain a circularly polarizing plate.
• the angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °.
• the circularly polarizing plates prepared in Examples 6, 7 and Comparative Example 3 were mounted on a reflective liquid crystal panel, and the viewing angle characteristics were measured using a measuring device (EZ Contrast 160D, manufactured by ELDIM). Table 3 shows the results. Using the circularly polarizing plates prepared in Examples 6 and 7, a wide field of view Table 3 viewing angle t the corner is obtained (contrast 3)
• a glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared.
• Polyimide alignment films SE-7992, manufactured by Nissan Chemical Co., Ltd.
• Two substrates were stacked via a 2.5 / zm spacer so that the alignment films faced each other.
• the directions of the substrates were adjusted so that the rubbing directions of the two alignment films intersect at an angle of 117 °.
• Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer.
• a TN type liquid crystal cell having a twist angle of 63 ° and a value of ⁇ d of 198 nm was produced.
• the ⁇ 4 plate prepared in Example 3 was attached to the side of the glass substrate provided with the ITO transparent electrode via an adhesive. On top of that, a polarizing plate (a polarizing film in which a protective film whose surface is AR-treated was laminated) was further adhered.
• a polarizing plate a polarizing film in which a protective film whose surface is AR-treated was laminated
• a 1 kHz rectangular wave voltage was applied to the manufactured reflection type liquid crystal display device. Visual evaluation was performed with a white display of 1.5 V and a black display of 4.5 V. As a result, it was confirmed that neutral gray was displayed without coloration in both white display and black display.
• the contrast ratio of the reflected luminance was measured using a measuring instrument (E Zcontrastl60D, manufactured by E1dim), the contrast ratio from the front was 23, and the viewing angle at which the contrast ratio was 3 was up and down. It was 120 ° or more, and left and right 120 ° or more.
• a glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared.
• Polyimide alignment films SE-7992, manufactured by Nissan Chemical Co., Ltd.
• Two substrates were stacked via a spacer of 4 jum so that the alignment films faced each other.
• the directions of the substrates were adjusted so that the rubbing directions of the two alignment films intersect at an angle of 110 °.
• a liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer.
• a TN type liquid crystal cell having a twist angle of 70 ° and a value of ⁇ d of 269 nm was produced.
• the ⁇ / 4 plate produced in Example 3 was attached to the side of the glass substrate provided with the ITO transparent electrode via an adhesive. On top of that, a polarizing plate (a polarizing film in which a protective film whose surface is AR-treated was laminated) was further adhered.
• a polarizing plate a polarizing film in which a protective film whose surface is AR-treated was laminated
• a 1 kHz rectangular wave voltage was applied to the manufactured reflection type liquid crystal display device. Visual evaluation was performed with white display at 1.5 V and black display at 4.5 V. Neither white display nor black display was colorless and neutral gray was displayed. .
• the contrast ratio of the reflected luminance was measured using a measuring instrument (E Zcontrastl60D, manufactured by Eldim), the contrast ratio from the front was 25, and the viewing angle at which the contrast ratio was 3 was 120 ° or more, and left and right 120 ° or more.
• the circularly polarizing plate prepared in Example 7 was adhered to a glass substrate, and left for 100 hours in an environment of 60 ° C. and 90% RH. Using this sample on the front of the reflective liquid crystal cell, A reflective liquid crystal display device was manufactured. As a result of making the front of the display screen of the display device a black display and visually observing, almost no unevenness due to light leakage was observed.
• a solution of a polymer for forming a vertical alignment film (LQ-1800, manufactured by Hitachi Chemical Dubon Microphone Systems Co., Ltd.) was applied onto a glass substrate provided with an ITO transparent electrode, dried, and rubbed.
• the ⁇ / 4 plate (retardation plate) produced in Example 3 was adhered with an adhesive on a glass substrate on which aluminum was deposited as a reflection plate.
• An SI layer was provided on the ⁇ S4 plate by sputtering, and an ITO transparent electrode was provided thereon.
• a solution of a polymer for forming a vertical alignment film (LQ-1800, manufactured by Hitachi Chemical DuPont Microsystems) is applied on the transparent electrode, dried, and then rubbed in the direction of 45 ° from the slow axis direction of the ⁇ 4 plate. was performed.
• a rectangular wave voltage of 1 kHz was applied between the IT ⁇ electrodes of the fabricated guest-host reflection type liquid crystal display device.
• the transmittances at white display IV and black display 10V were 65% and 6%, respectively.
• the transmittance ratio (contrast ratio) between the white display and the black display was 11: 1.
• the angle at which a contrast ratio of 2: 1 was obtained in the upper, lower, left, and right directions was measured, the angle was 120 ° or more in both the upper, lower, left, and right directions.
• the transmittance was measured while increasing and decreasing the voltage, but no hysteresis was observed in the transmittance-voltage curve.
• a cellulose acetate film was produced in the same manner as in Example 1 except that the amount of the dope was changed so that the dry film thickness of the whole film was 200 ⁇ m.
• the obtained cellulose acetate film (retardation plate) was analyzed using an ellipsometer (M-150, manufactured by JASCO Corporation) at a wavelength of 450 nm, at a wavelength of 550 nm and at a wavelength of 590 nm. Re) was 225.6 nm and 275.111111 ⁇ 290.2 nm, respectively.
• this cellulose acetate film achieved L / 2 in a wide wavelength range;
• Lb was measured from the refractive index by Abbe refractometer and the angle dependence of the retardation.
• the refractive index nx in the direction of the slow axis in the plane, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction are calculated, and the value of (nx—nz) / (n xny) is calculated.
• the calculated value was 1.60.
• Example 2 At room temperature, 120 parts by mass of cellulose acetate having an average degree of acetylation of 59.7%, 9.36 parts by mass of trifeninolephosphate, 4.68 parts by mass of bifeninolethiopheninolephosphate, and the retardation used in Example 1.
• a solution (dope) was prepared by mixing 1.00 parts by mass of the raising agent, 543.14 parts by mass of methylene chloride, 99.35 parts by mass of methanol and 19.87 parts by mass of n-butanol.
• the obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 45 ° C for 5 minutes. The residual solvent amount after drying was 30% by mass.
• the thickness of the obtained film was 102 ⁇ .
• the stretching ratio was 1.41 times.
• a retardation plate was produced in the same manner as in Example 13 except that the obtained dope was used.
• the thickness of the obtained film was ⁇ ⁇ ⁇ .
• the stretching ratio was 1.41.
• the dried film was cut into an appropriate size, it was stretched 1.4 times in a direction parallel to the casting direction at 130 ° C.
• the direction perpendicular to the stretching direction can be freely contracted.
• the film was taken out under an atmosphere at room temperature and cooled.
• the thickness of the obtained film was 102 ⁇ .
• the residual amount of the solvent was 0.1% by mass.
• Example 1 In another mixing tank, the retardation raising agent used in Example 1 1.18 parts by mass, tribenzi ⁇ / amine 2.36 parts by mass, methylene chloride 16.0 parts by mass methanol 1.39 A part by mass was charged and stirred while heating to prepare a retardation increasing agent solution.
• the entire retardation raising agent solution was charged into the cellulose acetate solution, and the mixture was sufficiently stirred to prepare a dope.
• the obtained dope was cast and uniaxially stretched using a band casting machine provided with a multistage roll stretching zone in a drying zone after casting.
• the residual solvent amount of the film immediately before the stretching zone was 1.0%.
• the stretching zone was covered with a casing to keep the temperature uniform, and the temperature was set to 135 ° C.
• the stretching temperature of the film was adjusted to 130 ° C using a roll temperature and an infrared heater provided between the rolls.
• the stretching ratio was 1.4 times depending on the rotation speed of the roll.
• the stretched film was gradually cooled to room temperature and wound up.
• the film thickness of the obtained film was 101 ⁇ .
• the residual solvent content was 0.2%.
• Example 15 The dope obtained in Example 15 was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 45 ° C for 5 minutes. The amount of residual solvent after drying was 25% by mass. The produced film was peeled off from the glass plate and dried at 100 ° C for 2 minutes and at 120 ° C for 10 minutes. The residual solvent content after drying was 2.5%.
• the film was stretched 1.30 times at 130 ° C. in a direction parallel to the casting direction.
• the direction perpendicular to the stretching direction can be freely contracted.
• heat treatment was performed at 110 ° C for 5 seconds using an infrared heater. After heat treatment, the sample was cooled and removed.
• Polycarbonate having a weight average molecular weight of 100,000 was dissolved in methylene chloride to obtain a 7% by mass solution. This solution was cast on a glass plate so as to have a dry film thickness of 80 ⁇ m, dried at room temperature for 30 minutes, and then dried at 70 ° C. for 30 minutes. The polycarbonate film was peeled from the glass plate and stretched 4% at 158 ° C to obtain a stretched birefringent film of polycarbonate.
• Example 13 1 16.8 nm 1 37.8 nm 1 43.3 nm 1.60
• Example 14 1 15.8 nm 1 36.7 nm 1 4 2.2 nm 1.55
• Example 15 1 1 6.3 nm 1 3 6.9 nm 1 4 2.5 nm 1.52
• Example 16 1 1 6.3 nm 1 36.9 nm 1 4 2.6 nm 1.53
• Example 17 1 1 6.4 nm 1 37.0 nm 1 42.5 nm 1.52 Comparative example 4 1 4 7.8 nm 1 37.5 nm 1 34.9 nm 1. 1 2
• the transparent protective film, the polarizing film and the retardation plate produced in Example 14 were laminated in this order to obtain a circularly polarizing plate.
• the angle between the slow axis of the retarder and the polarizing axis of the polarizing film is adjusted to 45 °. It was adjusted.
• the transparent protective film, the polarizing film and the retardation film produced in Example 16 were laminated in this order to obtain a circularly polarizing plate. 45.
• the angle between the slow axis of the phase difference plate and the polarization axis of the polarizing film is 45. Was adjusted.
• the transparent protective film, the polarizing film, and the retardation plate produced in Comparative Example 4 were laminated in this order to obtain a circularly polarizing plate.
• the angle between the slow axis of the retardation plate and the polarization axis of the polarizing film was adjusted to 45 °.
• the circularly polarizing plates produced in Examples 18 and 19 and Comparative Example 5 were mounted on a reflective liquid crystal panel, and the viewing angle characteristics were measured using a measuring device (EZ Contrast 160D, manufactured by ELDIM). The results are shown in Table 6. When the circularly polarizing plates produced in Examples 18 and 19 are used, a wide viewing angle can be obtained. Table 6 Viewing angle (Contrast 3)
• a glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared.
• Polyimide alignment films SE-7992, manufactured by Nissan Chemical Co., Ltd.
• Two substrates were stacked through a 5 / m spacer so that the alignment films faced each other.
• the orientation of the substrate was adjusted so that the rubbing directions of the two alignment films intersect at an angle of 117 °.
• Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer.
• a TN type liquid crystal cell having a twist angle of 63 ° and a value of ⁇ nd of 198 nm was produced.
• the ⁇ 4 plate prepared in Example 15 was attached to the side of the glass substrate provided with the ITO transparent electrode via an adhesive. On top of that, a polarizing plate (a polarizing film with a protective film laminated on the surface of which was subjected to AR treatment) was further adhered.
• a polarizing plate a polarizing film with a protective film laminated on the surface of which was subjected to AR treatment
• a 1 kHz rectangular wave voltage was applied to the manufactured reflection type liquid crystal display device. Visual evaluation was performed with white display at 1.5 V and black display at 4.5 V. Neither white display nor black display was colorless and neutral gray was displayed. .
• a glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared.
• a polyimide alignment film (SE_7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on each electrode side of the two glass substrates, and a rubbing treatment was performed.
• the two substrates were stacked so that the alignment films faced each other via the spacer described in 3.4.
• the directions of the substrates were adjusted so that the rubbing directions of the two alignment films intersect at an angle of 110 °.
• Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer. In this way, a TN type liquid crystal cell having a twist angle of 70 ° and a value of nd of 269 nm was produced.
• the quarter plate prepared in Example 15 was attached via an adhesive. On top of that, a polarizing plate (a polarizing film with a protective film laminated on the surface of which was subjected to AR treatment) was further adhered.
• a rectangular wave voltage of 1 k ⁇ was applied to the manufactured reflective liquid crystal display device. Visual evaluation was performed with a white display of 1.5 V and a black display of 4.5 V. As a result, it was confirmed that neutral gray was displayed without coloration in both white display and black display.
• the contrast ratio of the reflected luminance was measured using a measuring instrument (E Zcontrastl60D, manufactured by Eldim), the contrast ratio from the front was 25, and the viewing angle at which the contrast ratio was 3 was 120 ° or more, left or right 120 ° or more.
• the circularly polarizing plate prepared in Example 19 was attached to a glass substrate, and left for 100 hours in an environment of 60 ° C. and 90% RH. Using this sample on the front surface of a reflective liquid crystal cell, a reflective liquid crystal display device was manufactured. As a result of making the front of the display screen of the display device a black display and visually observing, unevenness due to light leakage was hardly observed. [Example 23]
• a solution of a polymer for forming a vertical alignment film (LQ-1800, manufactured by Hitachi Chemical DuPont Microsystems) was applied onto a glass substrate provided with an ITO transparent electrode, dried, and rubbed.
• Example 15 An L / 4 plate (retardation plate) prepared in Example 15 was adhered with an adhesive on a glass substrate on which aluminum was deposited as a reflection plate. On the No. 4 plate, an SI layer was provided by sputtering, and an ITO transparent electrode was provided thereon. A solution of a polymer for vertical alignment film (LQ_1800, manufactured by Hitachi Chemical DuPont Microsystems) is applied on the transparent electrode, dried, and rubbed in the direction of 45 ° from the slow axis direction of the ⁇ 4 plate. went.
• LQ_1800 manufactured by Hitachi Chemical DuPont Microsystems
• a rectangular wave voltage of 1 kHz was applied between the ITO electrodes of the fabricated guest-host reflection type liquid crystal display device.
• the transmittances at white display IV and black display 10V were 65% and 6%, respectively.
• the transmittance ratio (contrast ratio) between the white display and the black display was 11: 1.
• the angle at which a contrast ratio of 2: 1 was obtained in the upper, lower, left, and right directions was measured, the angle was 120 ° or more in both the upper, lower, left, and right directions.
• the transmittance was measured while increasing and decreasing the voltage, but no hysteresis was observed in the transmittance-voltage curve.
• a cellulose acetate film was produced in the same manner as in Example 13, except that the amount of the dope was changed so that the thickness of the obtained film was 200 ⁇ .
• the obtained cellulose acetate film (retardation film) was analyzed using an ellipsometer (M-150, manufactured by JASCO Corporation) at a wavelength of 450 nm, 550 nm and 590 nm to determine the letter value (Re ) Was 233.6 nm, 275.6 nm and 286.6 nm, respectively. Therefore, this cellulose acetate film achieved 1/2 in a wide wavelength range.
• the in-plane at a wavelength of 550 nm was obtained.
• measurement of the moisture Rise expansion coefficient was 1 2. 0 X 1 0- 5 Zcm 2 /% RH.
• cellulose acetate having an average acetylation degree of 59.7% 120 parts by mass, the retardation enhancer used in Example 1 1.2 parts by mass, triphenylene phosphate 9.36 parts by mass, biphenyldiphenyl A solution (dope) was prepared by mixing 4.68 parts by mass of phosphate, 2.0 parts by mass of tribenzylamine, 538.2 parts by mass of methylene chloride, and 46.8 parts by mass of methanol.
• the obtained dope was cast on a stainless steel band, and the film was dried until it had self-supporting properties, and then was peeled off from the band.
• the remaining volatile matter at that time was 30 mass. / 0 .
• the film was dried at 120 ° C for 15 minutes to reduce the residual volatile content to 2% by mass or less, and then stretched at 130 ° C in a direction parallel to the casting direction.
• the direction perpendicular to the stretching direction The direction can be freely contracted.
• the film was dried at 120 ° C. for 30 minutes as it was, and the stretched film was taken out.
• the residual amount of the solvent after stretching was 0.1% by mass.
• the thickness of the film thus obtained was 108 ⁇ .
• the obtained cellulose acetate film ( ⁇ / 4 plate) was analyzed using an ellipsometer ( ⁇ -150, manufactured by JASCO Corporation) at wavelengths of 450 nm, 55500 nm, and 59 °.
• the retardation values (Re) at nm were measured, they were 121.2 nm, 137.5 nm, and 142.7 nm, respectively. Therefore, this cellulose acetate film achieved L / 4 in a wide wavelength range; L550 was obtained from the refractive index measurement by Abbe refractometer and the measurement of the angle dependence of the retardation.
• the refractive index nx in the direction of the in-plane slow axis, the refractive index ny in the direction perpendicular to the slow axis in the plane, and the refractive index nz in the thickness direction at nm are calculated as (nx—nz) / (n xny). The calculated value was 1.5.
• the polarizer and the retarder provided on the reflective liquid crystal display device with a touch panel using a TN type liquid crystal cell were peeled off, and the example was replaced.
• the IZ 4 plate and the polarizing plate were attached to the liquid crystal cell using an adhesive in this order.
• the angle between the stretching direction of ⁇ / 4 (parallel to the slow axis direction) and the transmission axis direction of the polarizing plate was 45 °.
• the contrast ratio of the manufactured liquid crystal display device was measured with a measuring device ( ⁇ -Contrast 160D, manufactured by ELDIM), and was found to be 10: 1 at the front. Also, when the viewing angle at which a contrast ratio of 2: 1 was obtained at the top, bottom, left and right was measured, The angle was more than 120 ° both vertically and horizontally.
• Tatsuchipaneru Reflective type liquid crystal display device (Zaurus Color Pocket ML- 3 10, manufactured by Sharp Corp.) for, using a measuring machine (manufactured by EZ- Co ntrastl 60D N ELDIM Inc.), contrast When the ratio was measured, it was 10: 1 at the front.
• the viewing angle at which a contrast ratio of 2: 1 was obtained in the upper, lower, left, and right directions was 100 ° in the vertical direction and 90 ° in the horizontal direction.
• a solution of a polymer for forming a vertical alignment film (LQ-1800, manufactured by Hitachi Chemical DuPont Microphone Systems) was applied onto a glass substrate provided with an ITO transparent electrode, dried, and rubbed.
• Example 25 It was produced in Example 25 on a glass substrate on which aluminum was vapor-deposited as a reflection plate; an IZ4 plate was adhered with an adhesive. On the / 4 plate, a SiO layer was provided by sputtering, and an ITO transparent electrode was provided thereon. A solution of vertical alignment film forming polymer (LQ-1800, manufactured by Hitachi Chemical DuPont Microsystems) is applied on the transparent electrode, dried, and then set at 45 ° from the slow axis direction of the ⁇ / 4 plate. A rubbing treatment was performed.
• LQ-1800 vertical alignment film forming polymer
• Two glass substrates were stacked via a spacer of 7.6 zm such that the alignment films faced each other.
• the orientation of the substrate was adjusted so that the rubbing direction of the alignment film was antiparallel.
• a mixture of 2.5% by mass of dichroic dye (NKX-1366, manufactured by Nippon Kogaku Dyeing Co., Ltd.) and 97.5% by mass of liquid crystal (ZLI-28'06, manufactured by Merck) was added.
• the liquid crystal layer was formed by injection using a vacuum injection method.
• the touch panel used in Example 25 was provided on the observer side of the manufactured guest-host reflective liquid crystal display device.
• a rectangular wave voltage of 1 kHz was applied between the ITO electrodes of the fabricated guest-host reflection type liquid crystal display device.
• the reflectance at white display IV and black display 10 V is 65%, 6%.
• the ratio of the reflectance between the white display and the black display was 11: 1.
• the viewing angle at which a contrast ratio of 2: 1 was obtained in the upper, lower, left, and right directions was measured, the angle was 120 ° or more in both the upper, lower, left and right directions.
• the reflectance was measured while increasing and decreasing the voltage, but no hysteresis was observed in the reflectance-voltage curve.
• a stretched film was prepared in the same manner as in Example 25, and a transparent conductive film was applied as follows.
• I-Propyl alcohol was added to 100 g of the silver colloid dispersion liquid, and the mixture was ultrasonically dispersed and filtered through a polypropylene filter having a pore size of 1 ⁇ m to prepare a coating liquid.
• the above-mentioned silver colloid coating solution was applied using a wire bar so that the coating amount became 70 mg / m 2 , and dried at 40 ° C. Water fed by a pump was sprayed on the silver-coated surface, and excess water was removed with an air knife. Then, treatment was performed for 5 minutes while transporting in a heating zone at 120 ° C. Next, a coating solution L-1 for overcoat was applied to a film thickness of 80 nm, dried, heat-treated at 120 ° C. for 2 hours, and then irradiated with ultraviolet rays to cure the coating film. The thickness of the film thus obtained was 1 ⁇ 2 ⁇ . Further, the surface resistivity of the transparent conductive film side was measured by a four-terminal method, and as a result, it was 400 ⁇ / port, and the light transmittance was 71%.
• the wavelength of the obtained senorelose acetate ( ⁇ / 4) was determined to be 450 nm, 550 nm, and 590 nm.
• the retardation values (R e) at 0 nm were measured, they were 1 1 .4 nm, 1 32 .O nm, and 13.7 O nm, respectively. Therefore, this cellulose acetate film achieved ⁇ / 4 in a wide wavelength range.
• the refractive index ⁇ ⁇ in the in-plane slow axis direction at a wavelength of 550 nm, perpendicular to the in-plane slow axis was obtained, and the value of ( ⁇ ⁇ - ⁇ ⁇ ) / ( ⁇ ⁇ -ny) was calculated to be 1.52.
• a 0.7 mm thick glass plate with a transparent conductive film (IT ⁇ ) with a surface resistivity of 5 ⁇ / port on one side and a surface resistivity of 400 ⁇ / port on the other side was prepared.
• Surface resistivity 5 ⁇ A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on the surface of the Z port and rubbed.
• surface resistivity 400 ⁇ / port On the other side (surface resistivity 400 ⁇ / port), a dot spacer of 1 mm pitch and silver electrodes were printed on both ends.
• Silver electrodes were printed on both ends of the obtained LZ4 plate with a transparent conductive film, and bonded to the transparent conductive glass plate so that the transparent conductive films faced each other.
• a glass substrate provided with an aluminum reflective electrode having fine irregularities was prepared.
• a polyimide alignment film (SE-7992, manufactured by Nissan Chemical Co., Ltd.) was formed on the electrode side of this glass substrate, and rubbing treatment was performed.
• the above touch panel and a glass substrate provided with a reflective electrode were overlapped via a spacer of 3.4 / m such that the alignment films faced each other.
• the orientation of the substrate was adjusted so that the rubbing directions of the two alignment films intersect at an angle of 110 °.
• Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer.
• a TN type liquid crystal cell having a twist angle of 70 ° and an value of And of 269 nm was produced.
• a reflective liquid crystal display using the touch panel was manufactured.
• a rectangular wave voltage of 1 kHz was applied to the manufactured reflective liquid crystal display device.
• Visual evaluation was performed with white display at 1.5 V and black display at 4.5 V. In both white display and black display, the reflective liquid crystal display had no color and neutral gray was displayed.
• the contrast ratio of the reflected luminance was measured using a measuring instrument (E Zcontrastl60D, manufactured by E1dim), the contrast ratio from the front was 25, and the viewing angle at which the contrast ratio was 2 was up and down. 120 ° or more, left and right 120. That was all.
• a stretched film was prepared in the same manner as in Example 25, and a transparent conductive film was applied as follows.
• a UV-curable polyfunctional methacrylate resin (Z 7503, manufactured by JSR) was applied on the stretched film so as to have a thickness of 3 m.
• a film of IT was formed to a thickness of 15 nm by DC magnetron sputtering.
• the thickness of the film thus obtained was 103 ⁇ . Further, the surface resistivity of the transparent conductive film side was measured by a four-terminal method, and as a result, it was 230 ⁇ square, and the light transmittance was 89%.
• the obtained cellulose acetate film ( ⁇ / 4 plate) was analyzed using an ellipsometer ( ⁇ -150, manufactured by JASCO Corporation) at a wavelength of 450 nm, 550 nm, and 590 nm for a retardation value (Re). ) was 119.0 nm, 135. lnm, and 140. lnm, respectively. Therefore, this cellulose acetate film achieved ⁇ 4 in a wide wavelength range.Furthermore, from the measurement of the refractive index by Abbe refractometer and the measurement of the angle dependence of the retardation, the in-plane wavelength at 550 nm was determined.
• the refractive index ⁇ ⁇ in the slow axis direction, the refractive index ny in the direction perpendicular to the in-plane slow axis, and the refractive index ⁇ ⁇ ⁇ in the thickness direction are obtained, and the value of ( ⁇ ⁇ — ⁇ z) / (n xn y) is obtained.
• a reflective liquid crystal display device with a touch panel was produced in exactly the same manner as in Example 27 except that an L / 4 plate was used.
• the contrast ratio of the reflected luminance was measured using a measuring device (E Zcon rastl60D, manufactured by Eldim), the contrast ratio from the front was 28, and the viewing angle at which the contrast ratio was 2 was up and down. It was 120 ° or more, and left and right 120 ° or more.
• the following composition was put into a mixing tank, cooled and melted (at 70 ° C) to prepare a cell acetate solution (dope).
• the method of casting on a stainless steel band was the same as in Example 25.
• the cellulose triacetate used here had a degree of acetylation of 60.9%, a degree of substitution of 2.82, a viscosity average degree of polymerization of 320, a water content of 0.4 % by mass, and 6% in a methylene chloride solution of 0/0.
• the powder has a viscosity of 305 mPa ⁇ s, an average particle size of 1.5 mm and a standard deviation of 0.5 mm, the residual acetic acid content is 0.01% by mass or less, the Was 0.007% by mass, and Fe was 5 ppm.
• the acetyl group at the 6-position was 0.95, which was 32.2% of the total acetyl.
• the acetone extractables were 11% by mass, and the ratio between the weight average molecular weight and the number average molecular weight was 0.5, indicating a uniform distribution.
• the yellowness index is 0.3, the haze is 0.08%, the transparency is 93.5%, the T g is 160 ° C, and the crystallization
• the calorific value was 6.2 jZg c
• the thickness of the film thus obtained was 103 ⁇ .
• the surface resistivity of the transparent conductive film side was measured by a four-terminal method, and as a result, it was 406 ⁇ square, and the light transmittance was 88. /. Met.
• Retardation values (Re) at wavelengths of 450 nm, 550 nm, and 590 nm of the obtained film with a transparent conductive film were measured using an ellipsometer (M-150, manufactured by JASCO Corporation). However, they were 118.0 nm, 134. O nm, and 136. O nm, respectively. Therefore, this cellulose acetate film achieved / 4 in a wide wavelength range.
• the refractive index nx in the in-plane slow axis direction at the wavelength of 550 nm and the in-plane perpendicular direction to the slow axis were measured.
• the refractive index ny and the refractive index nz in the thickness direction were obtained, and the value of (nx—nz) / (nxny) was calculated to be 1.53.
• a touch panel-reflective liquid crystal display device was produced in exactly the same manner as in Example 27 except that a 1/4 plate was used.

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