TW200415373A - Process for producing phase difference plate and phase difference plate produced by the process - Google Patents

Abstract

The purpose of the present invention is to provide a process for easily producing a phase difference plate at low cost, which has high precision of liquid crystal orientation and less orientation deficiency. The present invention relates to a process for producing a phase difference plate which has a long roll-type transparent support and on at least one side thereof two optically anisotropic layers of liquid crystalline compound, the process comprising the steps of coating an orientation film on a continuously moving support, (a) rubbing a surface of support having the orientation film, (b) coating a liquid crystalline compound-containing composition on the rubbed surface, and (c) curing the coated composition in step (b) to form an optically anisotropic layer, and (d) repeating steps (a) to (c) at least one times without rolling up the support, and (e) rolling up the support.

Description

200415373 (1) Technical description of the invention: The present invention relates to a method for manufacturing a retardation plate having two or more optically anisotropic layers made of a liquid crystal compound. Furthermore, the present invention relates to a retardation plate obtained by the above method, particularly a retardation plate which is extremely effective as a reflection type liquid crystal display device, a disc recording pickup, or an λ / 4 plate for an antireflection film. (2) Prior art The phase difference plate of the present invention, that is, the λ / 4 plate, has many uses' and has been actually used. A conventional technique capable of achieving λ / 4 in a wide wavelength range includes a method of laminating two polymer films having optical anisotropy (for example, refer to Patent Documents 1 and 2), and providing at least two optical layers containing a liquid crystal compound. A method of the anisotropic layer (for example, refer to Patent Documents 3 to 6). However, in the method of laminating two polymer films having optical anisotropy, when the optical direction (optical axis and late phase axis) of one polymer film in the g week is used, the two polymer films must be cut to a predetermined angle. , The resulting wafers are bonded. When the retardation plate is manufactured by wafer bonding, the processing is complicated, the quality is lowered due to the detachment of the shaft, the handleability is lowered, the cost is increased, and the deterioration is easily caused by pollution. Furthermore, the 'polymer film does not easily adjust the λ / 4 plate to the necessary hysteresis. In addition, the method of providing at least two optically anisotropic layers containing a liquid crystal compound can provide a relatively simple wide-range λ / 4 plate, but providing two or more optically anisotropic layers made of a liquid crystal compound When laminating an optically anisotropic layer made of the liquid crystalline compound, it is necessary to set the alignment film every time-200415373 'There is a problem in manufacturing cost. In addition, when the second optically anisotropic layer is not coated under the alignment film, the accuracy or uniformity of the liquid crystal alignment will be reduced, and there will be problems of multiple alignment defects. Therefore, the optical anisotropy formed by the liquid crystal compound in the laminate The alignment film must be applied each time the layer is applied. [Patent Document 1] Japanese Patent Application Laid-open No. 1 0-6 8 8 1 6 [Patent Literature 2] Japanese Patent Application Laid-open No. 1 0-9 0 5 2 1 Japanese Patent Application [Patent Literature 3] Japanese Patent Laid-Open No. 2 0 0 0-2 0 6 3 3 1 [Patent Document 4] Japanese Patent Publication No. 2 0 0 1-4 8 3 7 [Patent Literature 5] Japanese Patent Publication No. 200 1-2 1 720 [Patent Literature 6] Japanese Patent Application Laid-Open No. 200 1-9 1 74 (3) Summary of the Invention The subject of the present invention is a production method for solving the above problems, in other words, providing an optical anisotropy formed by a liquid crystal compound in two or more layers In the case of a layer, a manufacturing method with high alignment accuracy and uniformity of the liquid crystal, fewer alignment defects, and favorable cost. Another object of the present invention is to provide a retardation plate obtained by the manufacturing method. The problems of the present invention are solved by the following methods. In other words, by the method of manufacturing the retardation plate (1) to (4) below and the retardation plate (5) below, it can be achieved by -7-200415373. (1) A method for manufacturing a retardation plate having a long roll-shaped transparent carrier and an optically anisotropic layer made of two or more liquid crystal compounds on one side thereof, the method comprising: An alignment film is coated on the continuously moving carrier, (a) rubbing the surface of the carrier on which the alignment film is formed, (b) coating the rubbed surface with a composition containing a liquid crystal compound, and (c) applying the steps (B) the coated composition is hardened to form an optically anisotropic layer, (d) without taking off the carrier, repeat steps (a) to (c) at least once, (e) a step of winding the carrier, . (2) The method according to (1), wherein when steps (a) to (c) are repeated, the surface of the optically anisotropic layer is rubbed at least once in step (a), and the optical anisotropy The layer contains modified polyvinyl alcohol having a hydrocarbon group having 9 or less carbon atoms. (3) The method according to (1) or (2), wherein the liquid crystal compound used in step (b) at least once is a rod-like liquid crystal compound having a polymerizable group. (4) The method according to (1) or (2), wherein the liquid crystal compound used in step (b) at least once is a discotic liquid crystal compound having a polymerizable group. (5) A phase difference plate manufactured by the method of 8-200415373 as described in any one of (1) to (4). In this specification, the "substantially" of the angle refers to a range smaller than the tight angle ± 5 °. The tight angle error is preferably less than 4 °, and more preferably less than 3 °. Moreover, in this specification, "substantially vertical alignment" refers to not only strict vertical alignment but also alignments with an average angle (average tilt angle) of 50 ° to 90 °, and "substantially horizontal alignment" refers to not only strict horizontal alignment. And includes an orientation with an average angle (average tilt angle) of 0 ° ~ 40 °. In addition, the "late phase axis" in this specification means the direction in which the refractive index is the largest. (4) Embodiment [Method of manufacturing retardation plate] An example of the method of manufacturing the retardation plate of the present invention is shown in FIG. Fig. 1 is a manufacturing example of a retardation plate having two optically anisotropic layers. First, a long roll-shaped (not shown) transparent carrier ′ is continuously moved, and the transparent carrier 1 is coated with an alignment film-forming coating liquid containing modified polyvinyl alcohol or the like to form an alignment film 2. Next, the surface of the alignment film 2 is rubbed using, for example, a rubbing roller 3 or the like (step (a)). A composition containing a liquid crystalline compound is coated on the rubbed surface to form a coating layer 4 '(step (b)). The liquid crystal compound in the coating layer 4 'forms a predetermined alignment state depending on the surface properties of the alignment film 2 and depending on the rubbing direction. Then, the coating layer 4 is irradiated with heat and / or active radiation to fix the liquid crystal compound in the alignment state to form the optically anisotropic layer 4. In this way, a retardation plate having two optically anisotropic layers can be continuously produced. After the optically anisotropic layer 5 is formed, the retardation plate is rolled into a roll shape and cut into various shapes depending on its needs after storage and transportation, etc.-9-200415373 'for use. The first example is a production example of a retardation plate having two optically anisotropic layers. The steps (a) to (c) can be performed η times (η is the same as an integer greater than or equal to 2) and continuously A phase difference plate having an n-layer optically anisotropic layer was produced. In the present invention, until all the optically anisotropic layers are formed, _ has not been rolled into a roll shape (ie, step (e) has not been implemented), even between the optically anisotropic layers (the first figure is layers 4 and 5) In the case where an alignment film is not formed, an optically anisotropic layer that maintains the alignment accuracy and alignment uniformity of the liquid crystal at a high level and has a small number of defects (¾). As a result, formation of an alignment between the optically anisotropic layers can be omitted. Film to reduce manufacturing costs. In the present invention, the first to nth steps (a) to (c) can be independently selected for conditions and materials. For example, the rubbing direction in step (a), or the step ( b) The type and the like of the liquid crystalline compound used may be the same or different from the 1st to η times. Each step and the various materials and materials used in each step will be described in more detail below. [Transparent carrier [The transparent carrier is used in the present invention. A transparent carrier refers to a carrier having a light transmittance of 80% or more. In addition, it is preferable that the wavelength dispersion of the transparent carrier is small, and specifically, θ R e 4 0 0 / R e 7 〇〇 Ratio is less than 1.2 In addition, the transparent carrier is preferably one with small optical anisotropy, and specifically, the in-plane hysteresis (Re) is preferably 20 nm or less, and more preferably 10 nm or less. The polymer carrier is thinner than the carrier. Polymers such as cellulose, a carbon phthalate ester, polymaple, polyether mill, polyacrylate, and polymethacryl-1 0-200415373. Cellulose ester is preferred, and the more preferred is ethyl acetate. Cellulose is the best, and triethyl cellulose is the best. Especially when triethyl cellulose is used, the degree of vinegarization is preferably 60.25 to 61.5. The polymer film is prepared by The solvent casting method is preferred. The invention uses a long roll carrier to continuously coat the optically anisotropic layer. After forming the optically anisotropic layer, it is preferably cut to the necessary size. The thickness of the transparent carrier is 20 ~ 500 μηι is better and more preferably 40 ~ 200. In addition, in order to improve the adhesion between the transparent carrier and the layer (adhesive layer, horizontal alignment film, vertical alignment film, or optically anisotropic layer) provided thereon, Surface treatment (such as glow discharge treatment, corona discharge) on a transparent carrier Treatment, ultraviolet (UV) treatment, flame treatment, saponification treatment), or an adhesive layer (undercoat layer) can be provided on a transparent carrier. The surface treatment is preferably a lane treatment. [Alignment film] The present invention continuously moves the above-mentioned transparent A support, and an alignment film is formed on the surface of the support. The alignment film has a function of making the liquid crystal compound in the optically anisotropic layer into a desired alignment state. The alignment film is produced by rubbing treatment of an organic compound (preferably a polymer). Alignment film with alignment function. The type of polymer that forms the alignment film is determined by the alignment of the liquid crystal compound (especially the average tilt angle). When the liquid crystal compound is aligned horizontally, the polymer whose surface energy does not decrease (General alignment polymer). Polymers which are better in the rubbing treatment such as polyvinyl alcohol, polyimide derivatives, and nylon. The rubbing treatment can change the pretilt angle of the liquid crystal compound with respect to the plane of the film by rubbing the surface of these polymer layers with paper or cloth several times in a certain direction. -11- 200415373 In order to improve the adhesion with the liquid crystal compound layer formed above, the 'alignment film preferably has a polymerizable group. The polymerizable group may introduce a repeating unit having a polymerizable group into a side chain, or introduce a substituent as a cyclic group. It is more preferable to use an alignment film that forms a chemical bond with a liquid crystal compound at the interface. 'This alignment film is described in Japanese Patent Application Laid-Open No. 9-15 2 5 0 9. The thickness of the alignment film is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μΐΏ. In the present invention, the surface of the alignment film formed on the surface of the transparent support or the optically anisotropic layer formed through steps (a) to (c) is rubbed (step (a)). [Friction treatment] The friction treatment can be performed at an arbitrary angle with respect to the MD direction of the long roll-shaped carrier. For the MD direction, the angle of the rubbing direction is preferably the same as the MD direction or the oblique direction. The angle of the tilt direction is preferably _ 4 5 degrees to + 45 degrees. The rubbing treatment can be performed by any method, but it is preferably performed by at least one rubbing roller. For example, a rubbing roller can be arranged on the table for conveying the long film in the MD direction at an arbitrary angle to the MD direction of the long film, and the film can be conveyed in the MD direction and the rubbing roller can be rotated to align the transparent carrier The film surface is rubbed. It is preferable to have a mechanism capable of freely adjusting the angle formed by the movement direction of the friction roller and the table. The rubbing roller refers to a roller that covers the surface with a suitable rubbing cloth. Next, a composition containing a liquid crystal compound is coated on the rubbed surface (step (b)), and the composition is hardened to form an optically anisotropic layer (step (c)). [Optical anisotropic layer made of liquid crystal compound]-12- 200415373 The liquid crystal compound used in step (b) of the present invention is preferably a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound, more preferably A rod-shaped liquid crystalline compound or a disc-shaped liquid crystalline compound having a polymerizable group. As the rod-like liquid crystalline compound, an azomethine group, a cyanobiphenyl group, a cyanophenyl ester group, a benzoate group, a cyclohexanecarboxylic acid benzoyl group, and a cyano basic group are used. 5 Hexamidines, cyano-substituted phenylpyrimidines, oxo-substituted phenylpyrimidines, phenyldioxanes, diphenylacetylenes, and -cyclohexylbenzonitrile are preferred. Not only the above low-molecular liquid crystal molecules but also local molecular liquid crystal molecules can be used. More preferably, the rod-like liquid crystalline compound having a low-molecular polymerizable group is a compound represented by the following general formula (I). Formula (I) Q1 — L1 — A ^ L3 — M — L4 — A2 — L2 — Q2 (where Q1 and Q2 each represent an independent polymerizable group, and L1, L2, L3, and L4 each represent a single bond or two Valence bonding group, at least one of L3 and l4 represents -0-C0-0 ·. A1 and A2 each represent a spacer with 2 to 20 carbon atoms, and μ represents a spacer) will be described in more detail below. This is a rod-shaped liquid crystalline compound having a polymerizable group represented by the formula (丨). However, each of Q1 and Q2 represents an independent polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. It is preferred that the polymerizable group of g is a functional group capable of addition polymerization reaction or condensation polymerization reaction. The following are examples of polymerizable groups. [化 1]-1 3- 200415373 Η h3c.c ^ c. Η Η Et, 〇 ~ C ’Η

H5C ch3 h2c

Cl, h3c, c々c, ch3 Η f > Pr, c ~ C, Η HC〆 人 〇 / \ h2c-ch,

H

N / \ h2c-ch.

• OH

—SH

One C

OH

--S // v O OH N = C = 0

N = C = S The divalent bond bases shown by L1, L2, L3, and L4 start with

, -C〇-, -NR2-, -C0-0-, -〇-C〇-0-, -c〇, -0-C◦-, -0-C0-NR2- > -NR2-C〇 -0-, -NR

Bivalent bond groups are preferred. The R2 is a carbon atom and a hydrogen atom. At this time, at least one of L3 and L4 is -0-C. In the above formula (I), Qi-L1- and Q2-L2-with CH2 = C (CH3) -C0-0- and CH2 = C (Cl)- C0-0- vs. CH2 = CH-C0-〇-. A1 and A2 indicate that they have a carbon number of 2 to 20 and a child number of 2 to 12. 2 Aliphatic radicals are preferred, and more preferred are alkylenes selected from -0, -s, -NR2-, -NR2-C〇- 2-CO-NR2- and the alkyl group of single bond 1 to 7) -CO- (carbonate group) CH2 = CH-C0-0-, preferably, more preferably a spacer. Based on carbon. The spacer is preferably in the form of a chain -14-200415373 'and may contain no adjacent oxygen or sulfur atoms. The spacer may have a substituent, or may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom), a cyano group, a methyl group, or an ethyl group. The spacers shown by M are, for example, all conventional spacers. In particular, a base represented by the following formula (I I) is preferred. Formula (II) One (one W1-L5) — wherein W1 and W2 each represent an independent divalent cyclic aliphatic group, a divalent aromatic group, or a divalent heterocyclic group, and L5 represents a single bond or a bond Specific examples of the group and the bonding group include specific examples of the groups represented by L1 to L4 in the formula (I), and _CH2-0-, -0-CH2-. η means 1 or 2 or 3. W1 and W2 are, for example, 1,4-cyclohexyldiyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3,4-thiadi Azole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5- Diji, Dagen-3, 6-diji. In the case of 1,4-cyclohexanediyl, there are trans and sequential structural isomers. The present invention may be any isomers or mixtures of any proportion. It is better to use a trans structure. W1 and W2 may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group (methyl, ethyl, propyl, etc.) having 1 to 10 carbon atoms, and a carbon atom. An oxy group (such as methoxy, ethoxy, etc.) having a number of 1 to 10, an acid group (such as a methyl group, an ethoxy group, etc.) having 1 to 10 atoms, and an alkoxy group having 1 to 10 carbon atoms Carbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), fluorenyloxy (acetoxy, propionyloxy, etc.) having 1 to 10 carbon atoms, nitro, trifluoromethyl, difluoromethyl, etc. . The basic structure of the spacer shown in the above formula (11) is compared with the following example-1 5-200415373

-16- 200415373 The following are specific examples of the compound represented by the above formula (i), but the present invention is not limited thereto. The compound represented by the formula (I) can be synthesized by the method described in Japanese Patent Publication No. 11-5 1 3 0 1. [Chemical 3]

200415373 [Chem 4] 1-8 Ο

-18- 200415373

M6 〇

-19- 200415373 In the present invention, it is preferable to use a discotic liquid crystalline compound as the liquid crystalline compound. The discotic liquid crystalline compound is preferably aligned at a substantially vertical angle (average inclination angle in the range of 50 to 90 degrees) to the polymer film surface. Discotic liquid crystalline compounds have been published in various literatures (C. Destradeeta 1, M ο 1. C 1. ysr. Liq. Cryst., Vol. 71, pagelll (1981); edited by the Chemical Society of Japan, quarterly journal of general chemistry, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Pagel794 (1985); J. Zhang et al. J. Am. Chem. Soc., Vol. 116, page 26 5 5 (19 94)). The discotic liquid crystalline compound is described in Japanese Patent Application Laid-Open No. 8-2 7284. It is preferred that the discotic liquid crystalline compound has a polymerizable group under polymerization. For example, a structure in which a polymerizable group as a substituent is bonded to a discotic core of a discotic liquid crystalline compound. However, when a polymerizable group is directly bonded to the discotic core, it is difficult to maintain an alignment state during a polymerization reaction. Here, a structure having a bonding group between the disc-shaped core and the polymerizable group is preferred. In other words, a discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula (I I I). In the original formula (III) of P15, D is a disc-shaped core, L is a divalent bonding group, P is a polymerizable group, and η is an integer of 4 to 12. Preferable specific examples of the disc-shaped core (D), the divalent bonding group (L), and the polymerizable group (P) in the above formula (III) are each described in Japanese Patent Application Laid-Open No. 200 1-48 37 ( D1) to (D15), (L1) to (L2 5), (P1) to (P18), the content described in the bulletin can be used preferably. -20-200415373 These liquid crystal compounds are preferably substantially uniformly aligned in the optically anisotropic layer, more preferably, they are fixed in a substantially uniformly aligned state, and the best is to fix the liquid crystal molecules by polymerization. In the case of a rod-like liquid crystalline compound having a polymerizable group, it is preferable to be fixed by substantially horizontal alignment. Substantially horizontal means that the average angle (average tilt angle) of the major axis direction of the rod-like liquid crystalline compound and the optically anisotropic plane is in the range of ~ 4 (Γ. The rod-like liquid crystalline compound can be tilted or slowly Change the tilt angle (mixed alignment). When tilted alignment or mixed alignment, the average tilt angle is from 0 ° to 40. It is preferred. When it is a discotic liquid crystalline compound with a polymerizable group, it is preferably aligned substantially vertically. Substantially vertical means that the average angle (average tilt angle) between the disc surface and the optically anisotropic plane of the discotic liquid crystalline compound is in the range of 50. to 90 °. The tilt angle (mixed alignment) can be changed slowly. When tilted alignment or mixed alignment, the average tilt angle is 50 ° ~ 90. It is preferred. In the present invention, η steps (a) to (c) (n is 2 or more) (Integer)) to form the η layer optically anisotropic layer, but each of the first to the first ^! The next step (a) to step (c) to form the optically anisotropic layer has the second to nth Sub-step (a) ~ When the function of the alignment film of the optically anisotropic layer formed in step (c) is used in step (b), a composition containing modified polyvinyl alcohol containing a liquid crystal compound and a hydrocarbon group having a carbon number of 9 or less is used, It is better to form the optically anisotropic layer through step (0), and then to rub the surface of the optically anisotropic layer in the subsequent step (a). It will be explained that the above-mentioned carbon atom-2 which is used simultaneously with the liquid crystalline compound is used. 1-200415373 Modified polyvinyl alcohol having a hydrocarbon group of 9 or less. A preferred modified polyvinyl alcohol is one represented by the following formula (PX). (PX)-(VA1) (HyD) y-(VAc) z — Among them, VA1 is a repeating unit of vinyl alcohol, HyD is a repeating unit having a hydrocarbon group having a carbon number of 9 or less, vac is a vinyl acetate repeating unit, and X is 20 to 95% by mass (preferably 25 to 25%) 90% by mass), y is 2 to 98% by mass (preferably 丨 0 to 80% by mass), and z is 0 to 30% by mass (preferably 2 to 20% by mass).

The hydrocarbon group contained in HyD is an aliphatic group, an aromatic group, or a combination thereof. The aliphatic group may be cyclic, branched, or linear. The aliphatic group is preferably an alkyl group (which may be a cycloalkenyl group) or an alkenyl group (which may be a cycloalkenyl group). The hydrocarbon group may have a substituent. The number of carbon atoms of the above-mentioned hydrocarbon group is 1 to 9, and 1 to 8 is preferred. Comparative soil is represented by the following formulae (HyD-I) and (HyD-II), for example. (HyD-I)

(HyM)

Where 'L1 is a bivalent bonding group selected from _〇-, -co-, -S〇2_, -NH-, alkylene, arylene, and combinations thereof, and L2 is selected from a single bond , Or, -C0-, -S02-, -NH-, alkylene, arylene, and divalent bonding groups of these combinations, R1 and R2 are each a hydrocarbon fluorene having 9 or less carbon atoms. The following is an example of a divalent bond formed by the above combination. L1: -22- 200415373 L2: -0- C〇-alkylene- 〇-L3: -0-C0-alkylene-〇Ο-ΝΗ-ΐ ^: -〇-C〇-alkylene-NH- S02-arylene-0-L5: -arylene-NH-CO-L6: -arylene-Co--0-L7: -arylene-C0-NH-L8: -arylene -〇- L9: -0-C0-NH-arylene-NH-C0- The following are specific examples of HyD.

HyD-l Η —C —C a h2 ό aya c2h5 〇

HyD-2

HyD-3

H —C-C— One C-C—

H 2 O C3H7T 〇 V1

HyD-4 H —C-C— C4H9 h2 0 c6h13T o

HyD-5

HyD-6

HyD-7

HyD-8

H

H

H —C-C— 〇

O

O 〇

H -C—C-LJ 11 I bucket m2 〇 N y, c3h7 〇

HyD-9

HyD-10

H

One C one C— H U 1 H2〇 one N -C-C —

TO TO

HyD-11 H2 HyD > 12 H2 HyD-13 H2 ^ CY ^ Y 0 0 0 0 0 O CH3 C3H7 -23 200415373

The polymerization degree of the modified polyvinyl alcohol is preferably 200 to 5,000, and more preferably 300 to 3,000. The molecular weight of the polymer is preferably 900 to 200,000, and more preferably 1 3 0 0 to 1 3 0 0 0. Two or more polymers can be used. Specific examples of preferred modified polyvinyl alcohols are described below, but the present invention is not limited thereto. PX-l :—( VAl) 21— (HyD—13) 77- (VAc) 2 — PX—2:-(VA1) 14- · (HyD- 1 3) S4— (VAc) 2- PX-3: -(VA1) 21 — (HyD-16) 77-(VAc) 2-PX-4 (VA1) 34 — (HyD—l 5) (VAc) 2- PX-5:-(VA1) (HyD ~ l 2) (VAc) 2- PX ~ 6:-(VAl) (HyD-1 4) .52 ~ (VAc) 2- PX—7 :—( VAl) 21- (HyD-2) 77— (VAc) 2 — PX — 8:-(VA I) — (Hy D — 8) S5- (VAc) 2 — PX — 9:-(VA 1) 21- (HyD-1 3) 77- (VAc) 2- PX 一10: — (VAl) 46— (HyD—9) 52— (VAc) 2—The added amount of the modified polyvinyl alcohol described above is added to the liquid crystal compound of the control agent in an amount of 0.5 to 0.5 The mass% is better, and more preferably 0.1 to 5 mass%. 〇-24- 200415373 The above modified polyvinyl alcohol can be used as a condensing agent. The condensing agent is preferably a compound having an isocyanate group or a methyl group at the terminal. The following are specific compounds, but are not limited thereto. Poly (1,4-butanediol), isophorone diisocyanate-terminated poly (1,4-butanediol), methyl-2,4-diisocyanate-terminated poly (ethylene adipate), Methylene-2,4-diisocyanate-terminated poly (propylene glycol), Methylene-2,4-diisocyanate-terminated 1,6-diisocyanate hexane 1,8-diisocyanate octane 1,1,2-diisocyanate Coating of dodecane isophorone diisocyanate glyoxal in step (b) to dissolve the liquid crystalline compound, the modified polyvinyl alcohol as required, and the following polymerization initiator or other additives in a solvent Liquid coating on the friction surface is preferred. The solvent used in the coating solution is preferably an organic solvent. Organic solvents such as ammonium (eg, N, N-dimethylformamide), methylene (eg, dimethyl methylene), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), halogenated alkyl (E.g. chloroform, dichloromethane), esters (e.g. methyl acetate, butyl acetate), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. tetrahydrofuran, 1,2-dimethoxyethane). Halogenated alkyl and ketones are preferred. Two or more organic solvents can be used. The coating liquid can be applied by conventional methods (for example, extrusion coating method, direct photogravure coating method, reversible photogravure coating method, and mold coating method). [Fixing the alignment state of the liquid crystal compound] -25- 200415373 Step (C) is to apply the coating liquid to the friction surface, and then harden to form an optically anisotropic layer. The liquid crystalline compound depends on the nature of the alignment film and the rubbing direction, and becomes a predetermined alignment. While maintaining the alignment state, it is preferable to fix the liquid crystal compound and form an optically anisotropic layer. The immobilization is preferably performed by polymerizing a polymerizable group into which a liquid crystal compound is introduced. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and initiating a polymerization reaction by heat exposure, and a photopolymerization reaction using a photopolymerization initiator and initiating a polymerization reaction by exposure to active radiation, and the photopolymerization reaction is more effective. good. Photopolymerization initiators, for example, α-carbonyl compounds (described in US Pat. No. 2,367, 66 and 2 3 6 7 6 70), indole ethers (described in US Pat. No. 2448828), and α-hydrocarbon-substituted aromatics Marriage compound (described in US Patent No. 2 722 5 1 2), polynuclear quinone compound (US Patent No. 3046 1 27, described in the same specification as No. 2 9 5 1 7 5 8), triarylimidazole dimer and ρ- Combinations of aminophenyl ketones (described in US Patent No. 3 5 49 3 67), acridine and phenoxine compounds (Japanese Patent Publication No. 6 0-1 0 5 6 6 7 and US Patent No. 42 3 9850 ) And oxadiazole compounds (described in US Patent No. 42 1 2970). The amount of the photopolymerization initiator used is preferably from 0.01 to 20% by mass of the solid content of the coating solution, and more preferably from 0.5 to 5% by mass. In order to irradiate the liquid crystal compound with light, ultraviolet rays are preferably used. The irradiation energy is preferably 20 m: T / cm2 to 50 J / cm2, and more preferably 100 to 800 mJ / cm2. In order to promote the photopolymerization reaction, light irradiation is performed under heating conditions. The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. [Optical properties of retardation plate] 200415373 The optical anisotropic layer formed by the above steps is preferably a retardation plate that achieves substantially π or π / 2 at a specific wavelength. When the phase difference π is reached at a specific wavelength (λ), the hysteresis 値 of the polarized photons measured at the specific wavelength (λ) can be adjusted to λ / 2, and when the phase difference π / 2 is reached at a specific wavelength (λ) , The hysteresis 値 of the polarized photons measured at a specific wavelength (λ) can be adjusted to λ / 4. However, at 550 nm, which is the middle wavelength of the visible light range, it is preferable that one of the phase difference reaches π and the other reaches π / 2. For example, when repeating steps (a) to (c) twice to form two optically anisotropic layers, the retardation chirp of one optically anisotropic layer (the first optically anisotropic layer) measured at a wavelength of 5 50 nm is 240. ~ 290nm is more preferred, and more preferably is 250 ~ 280nm. The other optically anisotropic layer (second optically anisotropic layer) is measured at a wavelength of 5500nm, and the hysteresis is preferably 110 ~ 145nm. It is 120 ~ 140nm. The hysteresis chirp is the in-plane hysteresis for light incident from the normal direction of the optically anisotropic layer. Specifically, it is 値 defined by the following formula. Hysteresis (Re) = (nx-ny) Xd where nx and ny are the in-plane principal refractive index of the optically anisotropic layer, and d is the thickness (n m) of the optically anisotropic layer. The thicknesses of the first and second optically anisotropic layers are determined arbitrarily within the range of the desired hysteresis. For example, when the same rod-shaped liquid crystalline compound is aligned horizontally and the first and second optically anisotropic layers are formed, the thickness of the optically anisotropic layer having a phase difference of π is an optically different direction having a phase difference of 7C / 2 The thickness of the thickness is better. The preferred range of the thickness of each optically anisotropic layer varies depending on the type of liquid crystal compound used. Generally, it is 0.1 to 10 μm, preferably 0.2 to 0.8 μm, and more preferably 0.5 to 5 μΐΏ. -27_ 200415373 [Configuration of retardation plate] Fig. 2 is a schematic diagram of a typical configuration of the retardation plate of the present invention when a rod-shaped liquid crystalline compound is used. The basic retardation plate in FIG. 2 includes a long transparent carrier (S) and a first optically anisotropic layer (A), and a second optically anisotropic layer (B). The phase difference of the first optically anisotropic layer (A) is π. The phase difference of the second optically anisotropic layer (B) is π / 2. The angle formed by the longitudinal direction of the transparent carrier (S) and the late phase axis (a) of the first optically anisotropic layer (A) was 30 °. The angle between the late phase axis (b) of the second optical anisotropic layer (B) and the late phase axis (a) of the first optical anisotropic layer (A). (Γ) is 60. . As shown in Fig. 2, each of the first optically anisotropic layer (A) and the second optically anisotropic layer (B) contains a rod-like liquid crystalline compound (c 1 and c 2). The rod-like liquid crystalline compounds c 1 and c 2 are aligned horizontally. The major axis direction of the rod-shaped liquid crystalline compound is the slow phase axis (a and b) of the optically anisotropic layer. In addition, in the second figure, when the cost is low, an optically anisotropic layer A (a phase difference plate is π) may be provided on the transparent carrier S, and an optically anisotropic layer B (a phase difference π) may be provided on the outer side thereof. / 2) The configuration of the retardation plate and the circular polarizer can change the positions of the optically anisotropic layer A and the optically anisotropic layer B to each other, so as to provide an optically anisotropic layer on a transparent carrier S. A (phase difference plate is π), and an optically anisotropic layer B (phase difference is π / 2) is preferably provided on the outside. The same applies to the third figure below. [Circular Polarizer] The retardation plate of the present invention can use λ / 4 used as a reflective liquid crystal display device, λ / 4 used in a pickup for optical disc recording, or λ / 4 used as an anti-reflection film -28- 200415373. Especially useful. The λ / 4 plate is generally a circular polarizer combined with a polarizing film. Therefore, when the structure of a circular polarizing plate that combines a retardation plate and a polarizing film is combined, it can be easily incorporated into a device such as a reflective liquid crystal display device. The polarizing film includes an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, or a polyolefin-based polarizing film. Iodine-based polarizing films and dye-based polarizing films are generally produced using polyvinyl alcohol-based films. [Configuration of Circular Polarizing Plate] FIG. 3 is a schematic diagram showing a typical configuration of a circular polarizing plate using the retardation plate (a retardation plate using a rod-shaped liquid crystal compound) of the present invention. The circular polarizing plate shown in FIG. 3 has a polarizing film in addition to the transparent carrier (S), the first optically anisotropic layer (A), and the second optically anisotropic layer (B) shown in FIG. (P). The polarization transmission axis (p) of the polarizing film is the angle formed by the length direction (s) of the transparent carrier (S) at 45 °, and the polarization transmission axis and the late phase axis (a) of the optically anisotropic layer (A). The angle is 15 °. As in Figure 2, the angle between the late phase axis (a) of the optically anisotropic layer (A) and the late phase axis (b) of the optically anisotropic layer (B) is 6 0 °. The first optically anisotropic layer (A) and the second optically anisotropic layer (B) shown in Fig. 3 include rod-like liquid crystalline compounds (c 1 and c 2). The rod-like liquid crystalline compounds (c 1 and c 2) are aligned horizontally. The length direction of the rod-like liquid crystalline compounds (c 1 and c2) corresponds to the late phases (a and b) in the plane of the optically anisotropic layers (A and B). The polarizing film combined with the retardation plate of the present invention is not particularly limited, and an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, or a polyolefin-based polarizing film can be used. Iodine-based polarizing films and dye-based polarizing films are generally manufactured using polyvinyl alcohol-based films. For the transparent carrier of the retardation plate of the present invention in the direction of -2 9-200415373 degrees, the transmission axis of the polarizing film is 45. Lamination is better. For the length direction, use is substantially 45. In the case of a polarizing film having a transmission axis of polarized light in the direction (the following _ is 45. A polarizing film) ', the circular polarizing plate of the present invention can be easily manufactured without adjusting the angle during lamination. Since the transmission axis' of the polarizing film formed of the stretched film is substantially the same as the stretched direction, the film is 4 to 5 in the longitudinal direction. Directional extension processing can be made 4 5. Polarizing film. So essentially towards 4 5. A polarizing film having a polarized light transmission axis in the direction (hereinafter referred to as 4 5. A polarizing film) can be produced by an oblique extension method described in JP-A-2002-865 54, and can be referred to Table 0 0 0 9 to 0 0 45 The conditions described in the 5th column, the structure of the device used, etc. The polymer film used as the polarizing film is not particularly limited, and a thermoplastic film made of a suitable polymer can be used. Polymers such as polyvinyl alcohol (PV A), polycarbonate, cellulose acetate, polymill and the like. The polymer is preferably PVA. PVA is generally a saponifier of polyvinyl acetate. For example, it may contain components copolymerizable with vinyl acetate such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ethers. Further, a modified PVA containing an ethylamidine group, a sulfonic acid group, a carboxyl group, an alkylene oxide group, or the like can be used. The degree of saponification of PVA is not particularly limited. In terms of solubility and the like, 80 to 100 mol% is preferable, and 90 to 100 mol% is more preferable. In addition, the degree of polymerization of PVA is not particularly limited, but is preferably 1,000 to 10,000, and more preferably 1,500 to 50,000.

The polarizing film system prepared by dyeing PVA can be carried out by a dyeing step or gas-phase or liquid-phase adsorption. In the liquid phase, for example, when using iodine, the PVA film is immersed in an iodine-potassium iodide aqueous solution. Iodine is 0.1 to 20 g / L, potassium iodide is 1 to 100 g / L-30 to 200415373, and the weight ratio of iodine to potassium iodide is preferably 1 to 100. The dyeing time is preferably 30 to 5000 seconds, and the liquid temperature is preferably 5 to 50 ° C. The dyeing method may be any method such as dipping, coating or spraying with iodine or a dye solution. The dyeing step can be performed before and after the stretching step, because the film is properly expanded and stretched, and the liquid phase dyeing before the stretching step is better. Dyeing with dichroic pigments other than iodine is preferred. Specific examples of the dichroic pigment include azo-based pigments, 1,2-stilbene-based pigments, pyrazolin-5-one-based pigments, triphenylmethane-based pigments, quinoline-based pigments, and dioxin-based pigments. Pigment compounds such as thiophene-based pigments and awakening-based pigments. Those which are water-soluble are preferred, but are not limited thereby. Furthermore, it is preferable to introduce a hydrophilic substituent such as a sulfonic acid group, an amine group, or a hydroxyl group into these dichroic molecules. Specific examples of dichroic molecules are CI Direct. Yellowl2, CI Direct. Oraiige39, C. I. Direct. 〇range72, C. I. Direct. Red39, CI Direct. Red79, C. I. Direct. Red81, C. I Direct. Red83, C. I. Direct. Red89, CI Direct. Violet48, C. I. Direct. Blue67, C. I. Direct. Blue90, CI Direct. Gi: een59, C. I. Ac id. Red37, etc. In addition, Japanese Patent Application Laid-Open No. 1-161202, Japanese Patent Application Laid-Open No. 1-1 72906, Japanese Patent Application Laid-Open No. 1-1 72907, Japanese Patent Application Laid-Open No. 1-1 83602, Japanese Patent Application Laid-Open No. 1-2 48 1 0 5 Japanese Unexamined Patent Publication No. 1-2 6 5 2 0 5, Japanese Unexamined Patent Publication No. 7-2 6 1 0 24, and pigments described in each publication. As these dichroic molecules, free acids, or alkali metal salts, ammonium salts, and amine salts are used. These dichroic molecules can be used to produce two or more types of polarized photons having various hue. When the polarizing axis is orthogonally crossed as a polarizer or a polarizing plate, a compound (pigment) exhibiting black or various dichroic molecules exhibiting 200415373 black is used, and the single-plate transmittance and polarization ratio are both excellent. The process of extending PVA to produce a polarizing film is preferably using an additive crosslinked in PVA. Especially when the oblique stretching method of the present invention is used, when the PVA at the exit of the stretching step is not sufficiently hard, due to the pulling force of the step and the orientation direction of the PVA detached, the crosslinking agent solution is immersed in the pre-stretching step or the stretching step, or coated. Solutions and cross-linking agents are preferred. As the cross-linking agent, those described in U.S. Patent No. 23 2897 can be used, and boric acids are most preferred. In addition, PVA and polyvinyl chloride are formed by dehydration and dechlorination to form a polyene structure, and polarized light can be obtained by a conjugated double bond, that is, a polyvinylidene-based polarizing film is produced. It is preferable to use the stretching method of the present invention. The polarizing film manufactured by the above-mentioned oblique extension method can be directly used in this form as a polarizing plate for the retardation plate of the present invention, and a protective film can be attached to both sides or one side and used as a polarizing plate. The type of the protective film is not particularly limited, and cellulose esters such as cellulose acetate, cellulose acetate butyrate, cellulose propionate, polycarbonate, polyolefin, polystyrene, poly When the retardation 保护 of the protective film is equal to or more than 値, the polarizing axis is inclined away from the alignment axis of the protective film, and the linearly polarized light changes into elliptical polarized light, so it is not desirable. Therefore, the lower the hysteresis of the protective film is, the better. For example, the 63 2.8 nm is preferably 10 nm or less, and more preferably 5 nm or less. In order to obtain this low hysteresis, cellulose triacetate is more preferred as the polymer used as the protective film. In addition, polyolefins based on Jaynex (Transliteration), Jayne Rou (translated by Jayne), and ART0N () (SR) are preferred. Other examples are non-refractive optical resin materials described in JP-A No. 8-1 1 0 4 0 2 or JP 11--32- 200415373 2 9 3 Π 6. The adhesive of the polarizing film and the protective layer is not particularly limited, for example, PVA-based resins (including modified PVA such as ethenylacetamido, sulfonic acid, carboxyl, and ethylene oxide groups), or aqueous solutions of boron compounds, etc., among which PVA-based resin is preferred. After drying, the thickness of the adhesive layer is preferably from 0.01 to 10 μm, and more preferably from 0. 0 to 5 μm. There is no particular limitation on the thickness of the film before stretching, so as to maintain the stability and uniformity of the film. In terms of properties, 1 μm to 1 mm is preferred, and more preferably 20 to 200 μm. Figure 4 shows a perforation example of a conventional polarizing plate, and Figure 5 shows a perforation example of a polarizing plate of the present invention. As for the conventional polarizing plate, as shown in FIG. 4, the absorption axis 7 1 of polarized light, that is, the extension axis and the length direction 7 2-to the extent that the polarizing plate of the present invention is the absorption axis 8 1 of polarized light as shown in FIG. 5. That is, the extension axis is inclined 45 ° with respect to the length direction 82. This angle is consistent with the angle formed by the absorption axis of the polarization axis of the LCD cell and the vertical and horizontal directions of the liquid crystal cell itself, so it is perforated. No oblique perforation is required in the step. Further, as shown in Fig. 5, it can be seen that the polarizing plate of the present invention is cut into a straight line along the longitudinal direction and is manufactured by forming a gap along the longitudinal direction without perforation, so the productivity is more excellent. The preferred polarizing film of the present invention is better in terms of improving the contrast of the liquid crystal display device, and the one having the higher transmittance is preferable, and the one having the higher polarization is better. The transmittance is preferably 30% or more at 550 nm, and more preferably 40% or more. The degree of polarization is preferably 95.0% or more at 550nm, more preferably 99% or more, and 99.9% or more. Polarizing films generally have protective films on both sides, but the phase difference of the present invention can be used as a protective film on one side of the polarizing film. When a 45 ° polarizing film is used as the polarizing plate, right and left circular polarizing plates can be easily manufactured by changing the overlap. [Configuration of Circular Polarizer] Fig. 6 is a schematic view showing the configuration of a circular polarizer using the retardation plate of the present invention. The circular polarizing plate shown in FIG. 6 is formed by laminating a 45 ° polarizing film P and a protective film G on the retardation plate of the present invention. The retardation plate is made of optically anisotropic layers A and B (only one layer is shown in the figure) and a transparent carrier S. The retardation plate is a polarizing film P laminated on the transparent carrier S without the optically anisotropic layers A and B on its side facing 45 °. In this configuration, the retardation plate has a function as a protective film of a 45 ° polarizing film P. Fig. 6 shows the relationship between the length direction s of the transparent carrier S, the retardation axes a and b of the optically anisotropic layers A and B, and the transmission axis P of the 45 ° polarizing film P. When the circular polarizing plate of FIG. 6 is incorporated in a display device, the protective film P side is the display surface side (the direction shown by the arrow in the figure is the direction of view). The circularly polarizing plate obtained from Fig. 6 is right circularly polarized. The light incident in the direction of the arrow in Fig. 6 passes through the polarizing film P, the optically anisotropic layers A and B in order to form a right circularly polarized light. The other structure of the circularly polarizing plate using the retardation plate of the present invention is shown in FIG. The circular polarizing plate shown in FIG. 7 is a structure that replaces the positions of the protective film G and the retardation plate of the circular polarizing plate shown in FIG. 6. In FIG. 7, the protective film G, 45 ° polarizing film P, and The configuration of the transparent carrier s and the optically anisotropic layers A and B. The circularly polarizing plate of this structure can obtain left circularly polarized light. In this way, when the protective layer and the retardation plate are bonded on the 4th and 5th polarities, only right-to-left polarized light and left-to-circular polarized light can be manufactured by up-and-down bonding with -34-200415373 transformation. When a protective film is additionally used for the transparent support, a cellulose ester film having high optical isotropy as a protective film is used, and a triethylfluorene-based cellulose film is particularly preferred. Using the retardation plate of the present invention and the above-mentioned polarizing plate to obtain a wide range of λ / 4, specifically means that the hysteresis 値 / wavelength 测定 measured at the wavelengths of 450 nm, 5 50 nm, and 6 50 nm are all 0.2 ~ 0 · 3 range. The hysteresis chirp / wavelength chirp is preferably 0.21 to 0.29, more preferably 0.22 to 0.28, even more preferably 0.23 to 0.27, and most preferably 0.24 to 0.26. [Examples] The present invention will be described more specifically with examples and the like in the following. The materials, reagents, substance amounts, ratios, operations, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the following specific examples. [Example 1] An optically isotropic triethylfluorinated cellulose film (having an acetic acid degree of 60.9 ± 0.2%, a hysteresis of 6. Onm) having a thickness of 80 μm, a width of 680 mm, and a length of 500 m was used as a transparent carrier. After saponifying both sides of the transparent carrier, an alignment film coating solution A (with NH40H adjusted to pH 4 to 4 to 5) was continuously applied to one side of the transparent carrier, and dried to form an alignment having a thickness of 1 μm. membrane. Then, the rubbing treatment is continuously performed on the alignment film in the direction of 30 ° with respect to the length direction of the transparent carrier. Composition of alignment film coating solution A 200415373 4% by mass 7 2. 6% by mass 2 3.3% by mass 0.2% by mass The following modified polyvinyl alcohol water methanol glutaraldehyde [Chemical 8]

A coating solution with the following composition was continuously applied on the alignment film using a rod coater, dried and heated (alignment maturation), and irradiated with ultraviolet rays to form an optically anisotropic layer (A) having a thickness of 2.1 μm. The optically anisotropic layer has a slow phase axis in the 30 ° direction with respect to the longitudinal direction of the transparent carrier. The hysteresis (R e 5 5 0) of 5 5 0 nm is 2 5 9 n m. The coating solution for the optically anisotropic layer (A) has a composition of 38.1% by mass, 0.38% by mass, 1.4% by mass, 0.19% by mass, 0.4% by mass, and 6.0% by mass, and this specification Medium rod-shaped liquid crystalline compound (exemplified compound I-2) The following sensitizer A The following photopolymerization initiator B The compound (PX-9) exemplified in the present specification glutaraldehyde methyl ethyl ketone 200415373 sensitizer A [Chemical formula 9] Ο

Photopolymerization initiator B [Chem 1]

For the late phase axis of the optically anisotropic layer (A) produced as described above, −60. And for the length direction of the optically anisotropic layer (A)-30. Then, after the optical anisotropic layer (A) is coated, a rubbing treatment is continuously performed on the optical anisotropic layer (a) without being unrolled. The rubbing-treated optically anisotropic layer (A) was rubbed with a coating liquid having the following composition using a rod coater, and then continuously coated, dried, and heated without being unrolled (oriented maturation), and ultraviolet ray was irradiated. A phase difference plate (λ / 4 plate) was formed by forming a pre-existing anisotropic layer (B) ′ having a thickness of 1.0 μμη. The average hysteresis (Re550) at 550 n Hi is 136 nm. The angle of the length direction of the transparent carrier and the retardation axis of the optically anisotropic layer (B) is shown in Table 1. Composition of coating liquid for optically anisotropic layer (B) The rod-like liquid crystalline compound (Exemplary Compound I-2) of the present invention 38.4% by mass Sensitizer A 0 · 3 8% by mass 1. 1.5% by mass

Photopolymerization initiator B -37-200415373 〇 .〇 6% by mass 6 〇 .0% by mass Alignment control agent c Methyl ethyl ketone Alignment control agent C [Chem. 11]

[Comparative Example 1]

After the optically anisotropic layer (a) was formed in Example 1, the carrier was directly wound up, and it was placed in a rolled-up roll state under the atmosphere shown in Table 1 at a temperature of 25 ° C and a relative humidity of 60% RH. . Then, the surface of the optically anisotropic layer (A) was subjected to a rubbing treatment in the same manner as in Example 1, and an optically anisotropic layer (B) was applied to prepare a retardation plate, each of which is Comparative Examples 1 to 3. For each sample, the angle between the length direction of the transparent support and the retardation axis of the optically anisotropic layer (B) is shown in Table 1. -38- 200415373 Table 1 Elapsed time after coiling The angle between the length direction of the transparent carrier and the retardation axis of the optically anisotropic layer (B) Example 10 hours (without coiling) -30. (Soil 1.) Comparative Example 1 1 hour -25 to 30 ° (in-plane irregularities) Comparative Example 2 6 hours -20 to 30 ° (mostly in-plane irregularities) Comparative Example 3 24 hours -20 to 30 ° (there are many cases of in-plane irregularities) Ideal 値 -30. As can be seen from the table above, after the optically anisotropic layer (A) is formed, if it is not placed in the rolled state over time, the length of the transparent carrier in the plane and the late phase of the optically anisotropic layer (B) are The angular irregularity is small, and the liquid crystal compound is uniform and aligned with an ideal 値. Therefore, the effect of the present invention is known. After the optically anisotropic layer (A) was applied, the alignment film coating solution A was applied at a thickness of 1 μηη after drying, and then the optically anisotropic layer was applied in the same manner as in Comparative Examples 1 to 3. (B), as shown in Table 1, the angle between the length direction of the transparent carrier in the plane and the late phase axis of the optical anisotropic layer (B) will not cause the phenomenon of feminine inhomogeneity after rolling, and implementation Example 1 has the same result. From this, it can be known that Table 1 is called the female heterogeneity due to the time angle after winding. Since the alignment film is not coated on the optically anisotropic layer (A), many problems will occur. When the alignment film is not coated, The present invention is extremely effective. [Example 2] A PVA film was immersed in an aqueous solution of 2.0 g / L of iodine and 4.0 g / L of potassium iodide at 25 ° C for 240 seconds, and in an aqueous solution of boric acid 10 g / L at 25 After being immersed at 60 ° C for 60 seconds, it was introduced into the tenter stretcher of the shape shown in Fig. 2 of JP-A No. 2002-8 6 5 5 4 to extend it by 5.3 times. Extending-3 9-200415373 In the direction shown in Fig. 2 of Japanese Unexamined Patent Publication No. 2 0 0 2-8 6 5 54, the width is kept constant, the shrinkage is performed, and after drying in an atmosphere of 80 ° C, Disengaged from the tenter. The moisture content of the PVA film before stretching started was 31%, and the moisture content after drying was 1.5%. The difference in conveying speed between the left and right tenter clips is less than 0.05%, and the angle formed by the center line of the introduced film and the center line of the conveyed film in the subsequent steps is 46. . Here, the relationship between | L1-L2 | is 0.7m, W is 0.7m, and | L1-L2 | = W. The direction of substantially extending Ax-Cx of the tenter exit is inclined 45 with respect to the centerline 22 of the film sent to the subsequent steps. . The tenter exit is free of wrinkles and film deformation. In addition, a 3% aqueous solution of PVA (PVA-117H manufactured by Kuraray) was used as a binder, and saponified Fuji photographic film (Fujita) manufactured by Fujitako (transliteration) (cellulose triacetate, Hysteresis (3. Onm), followed by drying at 80 ° C to obtain a polarizing plate with an effective width of 6 50 ηπι. The direction of the absorption axis of the obtained polarizing plate was inclined by 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance of 43.7% and a polarization degree of 99.97% at 550 nm. In addition, when the dimensions are 3 1 0 X 2 3 3 mm as shown in Fig. 5, a polarizing plate having an area efficiency of 91.5% and an inclined absorption axis of 45 ° to the side can be manufactured. Then, as shown in FIG. 8, the retardation plate 96 produced in Example 1 was laminated on one surface of the iodine-based polarizing film 91 produced as described above, and the saponified anti-glare anti-reflection film 97 was laminated on the other surface to produce circularly polarized light. Plate 9 2. Except that the retardation plates 96 were each replaced with Comparative Examples 1 to 3, circular polarizing plates 93 to 95 were produced in the same manner. In making any polarizing plate, the polarizing film and the retardation plate are adhered in the same length direction to make a circular polarizing plate. 1 4 0- 200415373 In the obtained circular polarizing plates 9 2 to 95, light was irradiated from the anti-glare anti-reflection film 97 (the measurement wavelengths were 45 0ηι, 5 5 0 11 1Ώ, and 6 50 nm), and the phase of the light passing therethrough was adjusted. The difference is arbitrarily selected at 20 points with a width of 650 nm and a length of 100 mm. The maximum and minimum 値 are used to indicate unevenness. The results are shown in Table 2. Table 2 Circular polarizer retardation plate Re Re Re No. Type (450nm) (550nm) (650nm) 92 Example 1 109 ~ 11lnm 133 ~ 137nm 150 ~ 155nm 93 Comparative Example 1 108 ~ 112nm 133 ~ 141nm 150 ~ 160nm 94 Comparative Example 2 108 to 116 nm 133 to 149 nm 150 to 167 nm 95 Comparative Example 3 108 to 118 nm 133 to 153 nm 150 to 171 nm Ideal 値 112.5 nm 137.5 nm 157.5 nm As shown in Table 2 'Re-in-plane can be produced by the production method of the present invention Circular polarizer with few irregularities. [Example 3] (Production of a reflective liquid crystal display device) A circularly polarizing plate 92 was used in place of a commercially available reflective liquid crystal display device (color Larus (transliteration) Mbu 3 1 0, sha 1. p (stock)) ), The polarizing plate and the retardation plate are peeled off, and the circular polarizing plate 92 produced in Example 2 is wound up. When the produced reflective liquid crystal display device was visually evaluated, it was found that the white display, the black display, and the halftone had no color tone, and a neutral gray was displayed. Secondly, a measuring machine (EZ c ο nt 1 · ast 1 6 0D, E (1 dim Corporation) The contrast of the reflection brightness was measured. The comparison from the front is 10, which is a comparison of practical charge -41- 200415373 points. [Effects of the Invention] According to the present invention, a phase difference plate with high accuracy of liquid crystal alignment and few alignment defects can be easily and inexpensively manufactured. (V) Brief Description of Drawings FIG. 1 is a schematic flow chart of a manufacturing example of the phase difference plate of the present invention. Fig. 2 is a schematic diagram of an example of a retardation plate according to the present invention. Fig. 3 is a schematic diagram of an example of a circularly polarizing plate using a retardation plate of the present invention. Fig. 4 is a schematic plan view of perforating a conventional polarizing plate. Fig. 5 is a schematic plan view of perforating a 45 ° polarizing plate used in the present invention. Fig. 6 is a schematic plan view of the layer constitution of a circular polarizing plate using the retardation plate of the present invention. Fig. 7 is a schematic plan view of another example of the layer constitution of the circular polarizer using the retardation plate of the present invention. Fig. 8 is a schematic plan view of the layer structure of the circular polarizing plate prepared in Example 2. [Symbol description] 1 Transparent carrier 2 Alignment film 3 Friction roller 4, 5 Optical anisotropic layer-42-200415373 s Transparent carrier A First optical anisotropic layer B Second optical anisotropic layer s Length direction of the transparent carrier a Late phase axis of the first optical anisotropic layer b Late phase axis of the second optical anisotropic layer cl rod-shaped liquid crystalline compound c 2 rod-shaped liquid crystalline compound 71 absorption axis (extension axis) 72 length direction 81 absorption axis (Extended axis) 82 Length direction 91 Polarizing film produced in Example 2 92 Circular polarizing plate using retardation plate of Example 96 Phase difference plate produced in Example 1 97 Anti-glare anti-reflection film

Claims (1)

200415373 Scope of patent application: 1. A method for manufacturing a retardation plate having a long roll-shaped transparent carrier and an optically anisotropic layer made of two or more liquid crystal compounds on one side thereof The method includes: coating an alignment film on a continuously moving carrier, (a) rubbing the surface of the carrier on which the alignment film is formed, and (b) coating the rubbed surface with a composition containing a liquid crystal compound, (c) hardening the composition applied in step (b) to form an optically anisotropic layer, (d) repeating steps (a) to (c) at least once without taking off the carrier, and (e) Steps of taking up the carrier. 2 · The method according to item 1 of the scope of patent application, wherein when steps (a) to (c) are repeated, the surface of the optically anisotropic layer is rubbed at least once in step (a), and the optically anisotropic layer It contains modified polyvinyl alcohol having a hydrocarbon group having 9 or less carbon atoms. 3. The method of claim 1 or 2, wherein the liquid crystal compound used in step (b) at least once is a rod-shaped liquid crystal compound having a polymerizable group. 4. The method of claim 1 or 2, wherein the liquid crystal compound used in step (b) at least once is a discotic liquid crystal compound having a polymerizable group. 5 · A retardation plate 'is manufactured by a method according to any one of claims 1 to 4 of the scope of patent application. One 44-