TWI341928B - - Google Patents

Description

发明, invention description: The technical field to which the invention belongs; j The invention relates to a method for manufacturing a broadband twisted layer liquid crystal film. The wide-frequency twisted layer liquid crystal film of the present invention can be used as a circularly polarizing plate (reflective type polarizer). Further, the present invention relates to a linear polarizer using a s-circular polarizing plate, an illumination device, and a liquid crystal display device. C: Prior Art 3 In general, a liquid crystal display has a structure in which a liquid crystal is injected between glass plates forming a transparent electrode, and a polarizer is disposed in front of and behind the glass plate. The polarizer used in such a liquid crystal display is produced by absorbing iodine or a dichroic dye or the like on a polyvinyl alcohol film and extending it in a certain direction. The polarizer thus produced is itself a light that absorbs vibration in the side-side direction, and only causes light that vibrates in the other side direction to generate linearly polarized light. Therefore, the efficiency of the photon is theoretically impossible (4) 50%, which is the biggest cause of the decrease in the efficiency of the liquid crystal display. Moreover, since the absorption light —— causes the liquid crystal display device to increase to a certain extent when the output of the light source is increased to a certain extent, the polarizer is destroyed by the heat generated by the heat transfer of the absorbed light, and the liquid crystal is internal to the unit cell. The thermal effects of the layer can lead to poor display quality and other disadvantages. The twisted layer liquid crystal with off-state function is caused by the direction of rotation of the liquid crystal spiral and the direction of circular polarization, and has selective reflection characteristics of light that reflects only circularly polarized light having a wavelength of liquid crystal. This selective reflection characteristic is such that the mah bias of the predetermined wavelength band is excessively separated, and the residual wire reflection is utilized to thereby produce a "rate" polarizing film. At this time, the transmitted circle is converted by the ΛΜ wavelength plate into Straight light, and the direction of the direct light ^ 1341928 for the absorption direction of the absorption type polarizer of the liquid crystal display is uniform, thereby obtaining a high transmittance liquid crystal display device. That is, once the twisted layer liquid crystal film is When the λ /4 wavelength plate combination is used as a linear polarizer, there is theoretically no loss of light. Therefore, in comparison with a conventional absorption type polarizer that absorbs 50% of light alone, it is theoretically possible to obtain a brightness of 2 times. However, the selective reflection characteristics of the twisted layer liquid crystal are limited to a specific wavelength band, and it is difficult to cover the entire visible light line. The selective reflection wavelength domain width of the twisted layer liquid crystal λ λ is: Δ λ = 2 λ · ( ne-no ) /( ne+no ) 10 no : refractive index of twisted liquid crystal molecules to normal light ne : refractive index of twisted liquid crystal molecules to abnormal light λ : the center wavelength of selective reflection, depending on the molecular structure of the twisted layer liquid crystal. In the above formula, if ne-no is made larger, the width Δ of the reflection wavelength region is selected to be wider, and ne-no is usually 0.3 15 or less. If this value is made larger, it functions as other functions of liquid crystal (orientation characteristics, liquid crystal). Temperature, etc.) may become insufficient and practically difficult. Therefore, in reality, the width of the reflection wavelength region Δλ is also about 150 nm at the maximum. It can be practically used as a torsion layer liquid crystal with a maximum of 30 to 100 nm. λ is as follows: 20 λ — ( ne+no) P/2 P: The pitch of the twisted layer liquid crystal is required to be long. If the pitch is fixed, the average refractive index and pitch of the liquid crystal molecules are long. Therefore, it is necessary to cover visible light. In the whole field, it is possible to carry out a plurality of laminated layers having different selective reflection center wavelengths, or to continuously change the pitch in the thickness direction to form a distribution of selective reflection center wavelengths in the shape of 6 1341928. For example, the pitch length is continuously changed in the thickness direction. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the five-crystal composition of the torsion layer liquid is hardened, the exposure intensity difference between the exposure surface side and the emission surface side is given, and the polymerization rate difference is given, whereby the composition ratio of the liquid crystal composition having different reaction rates is provided in the thickness direction. The focus is on increasing the difference in exposure intensity between the side of the exposed surface and the side of the exit surface. Therefore, in many cases of the above-described embodiments, the ultraviolet absorber is mixed with the liquid crystal composition to make it thick. The method of absorbing the direction to increase the amount of exposure with the length of the optical path. However, in the method of continuously changing the pitch length in the Japanese Patent Publication No. 6-281814, the thickness of the liquid crystal layer required for the function to be exhibited must be 15 to 20 /zm, in addition to the precision coating problem of the liquid crystal layer, it requires a large amount of high-priced liquid crystal, so the cost increase of 15 is unavoidable. And the exposure time needs to be 1 to 60 minutes. If a line speed of 10 m/min is to be obtained, the length of the exposure line needs to be increased to a manufacturing line of 10 to 600 m. If the line speed is reduced, the production line length can be reduced, but the production speed is reduced but inevitable. This is disclosed in Japanese Laid-Open Patent Publication No. Hei 6-281814, which is formed by the difference in ultraviolet exposure intensity in the thickness direction and the difference in polymerization speed accompanying the change in the thickness direction of the screw 20 in the thickness direction. The composition ratio change, it is theoretically problematic to control the pitch of the torsion layer by the composition ratio change, so it is very difficult to form a rapid pitch change. In Japanese Laid-Open Patent Publication No. Hei 6-281814, the short pitch side and the long pitch side have a pitch difference of 100 nm, so the composition ratio must be changed to a large extent. To be true, it is necessary to have a liquid crystal thickness and a weak ultraviolet ray. Increased exposure time. In the publication of Japanese Laid-Open Patent Publication No. H11-248943, the material having a variable pitch is superior to the material used in the Japanese Patent Publication No. Hei 6-281814, so that the film can be formed in an exposure amount of 1 minute and 5 minutes. However, this situation still requires a thickness of 15Mm. In the special book No. 3272668, the conditions of the one-time exposure and the double-exposure are changed, and the time required for the composition ratio to change in the thickness direction is additionally placed in the dark, but if the true visible light region is covered by the method, The waiting time for the movement of the substance caused by this temperature change requires 12 (minutes). In the method of continuously changing the pitch length, the function of the liquid crystal layer required for the function is required to be 15 to 2 〇 ym, in addition to the precise coating problem of the liquid crystal layer, a large amount of high price is required. LCD, so the cost increase is inevitable. In the case of curing the torsion layer liquid crystal composition by ultraviolet light exposure from the substrate and the opposite side (air interface side), the exposure intensity of the exposure surface side and the emission surface side is imparted by the oxygen barrier 15 Poor, whereby the composition ratio change is varied in the thickness direction. However, in the fourth embodiment of the embodiment of the Japanese Patent Publication No. 2002-286935, although the selective reflection wavelength is widened, the inclination of the short-wavelength end side and the long-wavelength side of the transmittance curve is stable, substantially Not covered by the entire visible light range. Further, in Fig. 6 of the second embodiment of the publication, the inclination of the two wavelength ends is steep, and the frequency band is narrow. In particular, when such a polarizing element is used in a liquid crystal display device, it is necessary to sufficiently ensure a flat transmittance/reflectance characteristic for three wavelengths of 435 nm, 545 nm, and 615 nm of the light emission spectrum of the backlight source. The broadening range obtained by the method of Example 2, which is described in Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, 286, 935, each of which does not fully cover the gamma spectrum of 435 nm and 615 nm. In this case, it is difficult to obtain white color by the color of the light, and it cannot be used for a liquid crystal display device or the like.

C^ Ming content; J 5 for the above problem' The applicant applied for a special wish 200 339632. In the application, the substrate was coated with ultraviolet light from the liquid crystal group coated on the alignment layer. Thereby, the surface is polymerized from the surface of the liquid crystal layer, which is less susceptible to the influence of oxygen on the contact-oriented substrate, which is advantageous for the polymerization resistance, which facilitates the absorption of the molar extinction coefficient of the liquid crystal layer, and forms an ultraviolet irradiation intensity distribution in the thickness direction to reduce the air surface which is hindered by oxygen. The amount of effective radiation on the 10 side and the outside line is formed to form a slope larger than the conventional liquid crystal reaction speed and a composition concentration distribution slope. By giving the difference in the exposure intensity between the exposure surface side and the emission surface side as described above, it is possible to form a large change in the thickness direction of the twisted layer pitch length. In this application, the wavelength of the selected reflection wavelength can be up to 296 nm. The aforementioned application may cover a wavelength band of 400 to 700 nm. These wavelength bands cover the spectrum of the source. These provide good circularly polarized light reflection characteristics near normal incidence. On the other hand, when obliquely incident, a sufficient wavelength bandwidth cannot be said. Since the selected reflection wavelength at oblique incidence is again: In = npcos{sin·丨(sin0/n) } n==The average refractive index of the liquid crystal 20 P=The torsion layer pitch is longer than the incident angle. Once obliquely incident, the selection is made. The reflected wavelength will move to the shorter wavelength side than when it is incident normally. Therefore, to make the oblique incident light work effectively, it must be made to function in the long wave. The object of the present invention is to provide a method for fabricating a wide-band twisted layer liquid crystal germanium having a wide reflection band in a long wavelength region. Further, an object of the present invention is to provide a circular polarizing plate using a wide-band twisted-layer liquid crystal film produced by the manufacturing method, and to provide a linear polarizing element using the circular polarizing plate, an illumination device, and a liquid crystal display device. As a result of intensive studies in order to solve the above problems, the present inventors have found that a wide-band 杻 layer liquid crystal film which achieves the above object can be obtained by the following production method, and the present invention has been completed. That is, the present invention is as follows. A method for producing a wide-frequency twisted layer liquid crystal film comprising the steps of applying a liquid crystal mixture containing a polymerizable 10 liquid crystal original compound (A) and a polymerizable optical agent (B) to an oriented substrate, and performing the liquid crystal mixture a step of polymerizing and hardening by ultraviolet irradiation to produce a wide-band twisted-layer liquid crystal film having a reflection bandwidth of 2 〇〇 mn or more, wherein the ultraviolet ray polymerization step comprises: in a state where the liquid crystal mixture is brought into contact with an oxygen-containing gas, at 2 〇〇c above 15, at a temperature of 20 to 200 mW/cm 2 of ultraviolet ray irradiation, ultraviolet ray irradiation from the side of the oriented substrate is carried out for a period of 0·2 to 5 seconds (1); then 'the liquid crystal layer is brought into contact with In the state of the oxygen gas, at a temperature increase rate of 2 C/sec or more, the temperature is higher than the step (and the temperature reaches the temperature above 6 〇 art) and the ultraviolet ray irradiation intensity lower than the step (1), from the oriented substrate side 20 a step of irradiating ultraviolet rays for a second or more; (2); and then a step of performing ultraviolet irradiation in the absence of oxygen. 2. A method of manufacturing a broadband twisted layer liquid crystal film according to the above item The pitch length change of the wide-band twisted-layer liquid crystal film is continuously narrowed from the side of the oriented substrate. 3. The method for producing a wide-band twisted-layer liquid crystal film according to the above item 1 or 2, wherein 10 1341928 the polymerizable liquid crystal original compound (A) has one polymerizable functional group, and the polymerizable optically active agent (B) has two or more polymerizable functional groups. 4. The production of the wide-band twisted layer liquid crystal film according to any one of the above items 1 to 3 The method, wherein the molecular extinction coefficient of the polymerizable liquid crystal original compound (A) is: 0.1 to 500 (11113111〇1-|(^11-丨@36511111, 10~^ΟΟΟίΜιτ^ΓηοΓ1^!!-1®] The method for producing a broadband twisted layer liquid crystal film according to any one of the above items 1 to 4, wherein the polymerizable liquid crystal is used in the method of manufacturing a liquid crystal film of a wide frequency twisted layer liquid crystal according to any one of the above items 1 to 4, wherein: The original compound (A) is represented by the following general formula (1):

The compound represented (wherein Ri~Rl2 may be the same or different, representing -F, _H, -CH3, a C2H5 or an OCH3, Rl3 represents a Η or a CH3, and X represents a general formula (2): - ( CH2CH20) a—(CH2) b—(O) c—, x2 represents —CN or an F, except that a in general formula (2) is an integer from 0 to 3, and b is a positive number from 0 to 12 5 , c It is 0 or 1' and b=0, c=0 when a=1~3, b=1~12, C=Q~1) when a=0, 〇6·—a kind of circular polarizer, which is used as The wide-frequency twisted-layer liquid crystal film produced by the manufacturing method of any one of the above items. 7. The type of polarizing element system is disposed between at least two layers of reflected polarizers (a) in which the polarization bands of the polarized light selectively overlap each other, and the front phase difference (normal direction) is arranged to be almost zero and 3 inches in the normal direction. The oblique incident light 11 has a retardation layer (b) λ of λ/8 or more, wherein the reflective polarizer (a) is the circular polarizing plate of the sixth item. The polarizing element of the above item 7, wherein the selective reflection wavelength of the at least two reflective polarizers (1) overlaps each other in a wavelength range of 550 nm and 10 nm. 9. The polarizing element according to Item 7 or 8, wherein the phase difference layer (b) is a plane orientation for fixing a liquid crystal phase of a twisted layer having a selective reflection wavelength range outside the visible light region, for fixing the rod shape The vertical alignment state of the liquid crystal is used to fix the phase of the phase of the discotic liquid crystal or the orientation of the tube bundle phase, to orient the polymer 骐 2 axis, or to fix the inorganic lamellar compound having a negative one-axis property. , the normal direction of the face constitutes the optical axis. In the linear polarizing element of the above item 6, the λ/4 plate is laminated on the polarizing element of any of the above items 7 to 9 to obtain a linear polarized light. 11. The linear polarizing element according to item 10 above, wherein the twisted layer liquid crystal film of the laminated circular polarizing plate is formed on the Λ4 plate so that the pitch length is continuously narrowed. 12. The linear polarizing element according to Item 10 or 11, wherein the λ/4 plate is subjected to phase difference correction of the oblique incident light of the 2-axis extension to improve the phase difference plate of the viewing angle. 13. The linear polarizing element according to the above item 10 or 11, wherein the /4 plate is a liquid crystal polymer type retardation plate 0 1341928 obtained by coating and fixing a nematic liquid crystal or a matrix liquid crystal. 14. A linear polarizing element according to any one of the preceding claims, wherein the /4 plate has a principal refractive index of nx'ny in the plane, a main refractive index in the thickness direction is nz, and a formula (nx-nz) / ( Nx — ny) The defined Nz coefficient satisfies _〇5~·2 5 . - 15. - A linear polarizing element is attached to the λ/4 plate of the linear polarizing element of any one of the above items 1 to 14; 16. A linear polarizing element which aligns a transmission axis direction of an absorbing type polarizer with a transmission axis of a linear polarization element according to any one of the above items 10 to 15, and a linear polarization element; The absorption type polarizer. Φ 17. The illuminating device is a circular polarizing plate having the above-mentioned item 6 on the surface side of the surface light source having the reflective layer on the back side, and the polarizing element according to any one of the above items 7 to 9 or the above-mentioned 10th ~16 linear polarizing elements. A liquid crystal display device comprising a liquid crystal cell on a light-emitting side of the illumination device of the above item 17. 19. A viewing angle-enhancing liquid crystal display device according to the liquid crystal display device of item 8, wherein a viewing angle-enlarging film that diffuses light passing through a visual side of the liquid crystal cell is disposed on a visual side of the liquid crystal cell. . ® 20. The liquid crystal display device of the above-mentioned item 19 is expanded by using a diffusing plate which is substantially free of rear scattered and polarized light as a viewing angle widening film. ' (Effect of the Invention), as described above, in the present invention, in order to make the reflection bandwidth frequency, when the liquid crystal mixture is irradiated with ultraviolet rays from the side of the oriented substrate in contact with the oxygen-containing gas, the ultraviolet irradiation illuminance and the irradiation temperature are In the step (1) of the first exposure and the step (3) of the second exposure, conditions different from each other are used. Thereby, 13 1341928 can realize a more compact control of the reaction behavior of the polymerizable liquid crystal mixture, and a wide-band twisted layer liquid crystal film can be obtained by a high efficiency production speed as compared with the prior art.

That is, the ultraviolet irradiation conditions are the first irradiation intensity > the second irradiation intensity, and the first irradiation time < the second irradiation time. Further, a heating step (3) is provided between the first ultraviolet ray 5 irradiation and the second ultraviolet ray irradiation. The amount of radicals generated by the ultraviolet reaction of the photoreaction initiator in the liquid crystal composition per unit time varies greatly in the first ultraviolet irradiation and the second ultraviolet irradiation by the difference in irradiation intensity. In the first ultraviolet irradiation, a large amount of radicals are instantaneously formed in the monomer-rich condition at the initial stage of the reaction, and the absorption of the liquid crystal composition by the absorption of the liquid crystal composition causes the radicals to be distributed to form a large gradient in the thickness direction. A polymer/oligomer having an average molecular weight of about 10,000 to 500,000 is formed by this, and a concentration distribution is formed in the thickness direction. Further, at this time, since the reaction rate of the polymerizable liquid crystal original compound (A) in the liquid crystal mixture and the polymerizable optical agent (B) is different, the polymerization ratio is different in the thickness direction. Therefore, the polymerizable optical agent (B) 15 has a short pitch in the rich surface and a long surface in the opposite direction. Thereby, a twisted layer liquid crystal film having a wide reflection wavelength of a wide frequency can be obtained. The wide-frequency torsion layer liquid crystal film thus obtained can be used as a wide-band circularly polarizing reflector, and has the same optical properties as those of the above-mentioned Japanese Patent Publication No. Hei 6-281814, and the like, and the number of laminated sheets is reduced as compared with the conventional manufacturing method. The thickness can be reduced, 20 can be easily manufactured in a short time, and the cost can be reduced due to the increase in production speed. The wide-band torsion layer liquid crystal film obtained by the above-described manufacturing method of the present invention has a reflection bandwidth of a selective reflection wavelength of 200 nm or more and a wide-band reflection bandwidth. The reflection bandwidth is preferably 300 nm or more, more preferably 400 nm or more, and particularly preferably 450 nm or more. Further, the reflection bandwidth of 200 nm or more is preferably in the wavelength range of the visible light collar 14 1341928 domain, particularly 400 to 900 nm. The circularly polarizing reflector also has a broadband reflection band in the long wavelength region, which is an important problem for the liquid crystal display device in order to obtain a good viewing angle. In the practical range of view, in order to make the transmitted light not visible, the long wavelength end of the selective reflection must be 5 to 800 to 900 nm. According to the manufacturing method of the present invention, a wide-band twisted layer liquid crystal film having a reflection bandwidth at the long wavelength end can be obtained. The wide-frequency twisted-layer liquid crystal film is not only used as a polarizing element which is formed by a combination of other optical element groups such as a phase difference plate, but also when it is used as a reflective polarizer for obtaining high luminance. The oblique incident light has a stable optical characteristic. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view showing an enlarged liquid crystal display device using the viewing angles of the polarizing plate-integrated polarizing elements of Examples 1 and 3 and Comparative Examples 1 to 3. Fig. 2 is a conceptual view showing the expansion of the liquid crystal display device by the viewing angle of the polarizing plate-integrated polarizing element of the second embodiment. Fig. 3 is a view showing the axial angles of the respective layers in the polarizing plate-integrated polarizing element of the second embodiment. Fig. 4 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 1. Fig. 5 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 2. Fig. 6 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 3. 20 Fig. 7 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 4. Fig. 8 is a reflection spectrum of the twisted layer liquid crystal film produced in Comparative Example 1. Fig. 9 is a reflection spectrum of the twisted layer liquid crystal film produced in Comparative Example 2. Fig. 10 is a reflection spectrum of the twisted layer liquid crystal film produced in Comparative Example 3. [Embodiment 3 15 1341928] The wide-frequency twisted-layer liquid crystal film of the present invention is obtained by subjecting a liquid crystal mixture containing a polymerizable liquid crystal original compound (A) and a polymerizable optical agent (b) to ultraviolet polymerization. As the polymerizable liquid crystal original compound (A), those having at least one polymerizable functional group and having a liquid crystal starting group formed of a cyclic unit or the like are preferably used. The polymerizable functional group may, for example, be an acryl group, a mercapto propyl group, an epoxy group or an ethylene group, and particularly preferably an acrylonitrile group or a mercapto propylene group. Moreover, by using a polymerizable functional group having two or more, a crosslinked structure can be introduced to improve durability. Examples of the cyclic unit to be a liquid crystal priming unit include biphenyl, phenyl benzoate, 10 styrene cyclohexane, azobenzene, azomethine, azobenzene, and pyridyl pyrimidine. A system, a diphenylacetylene system, a biphenyl benzoate system, a dicyclohexane system, a cyclohexyl group, a hydrazine system, and the like. Further, the terminal '' of these cyclic units may have a substituent such as a cyano group, an alkyl group, an alkoxy group or a dentate group. The liquid crystal nucleus may also be bonded via a pitch plate portion that imparts flexibility. The pitch plate portion may be a polymethylene chain or a poly-15 hydroxymethylene chain. The number of the structural units forming the pitch plate portion can be appropriately determined by the chemical structure of the liquid crystal original portion, and the reversal unit of the polymethylene chain is preferably 0 to 20, and preferably 2 to 12, and the polyhydroxy hydrazine chain. The reversal unit is preferably 0 to 10, and preferably 1 to 3. The molar extinction coefficient of the polymerizable liquid crystal original compound (A) is preferably CU~500 20 , ΙΟ^βΟΟΟίΜη^ηιοΙ^ηΓ1®]]^!!!, and 100 O—lOOOOdn^moricnT'^SMnm. Those having the aforementioned moir extinction coefficient have ultraviolet absorbing energy. The Mohr extinction coefficient is also suitable for 〇UOdn^moricm-, @365nm, 5〇~Η)〇_ηΛη〇1-^ι@334ηηι, and ι〇〇〇〇~5〇〇〇〇dm ^ zhang is suitable for 0.1 ~ lOdn^mol icm 16 1341928 i@365nm, 1000~4000dm3mol-1cm1@334nm ' and 30000~40000d. If the molar extinction coefficient is less than 〇, ldm3mol-icm-i@3 65nm '10dm3m〇r, cm-, @334nm ' lOOOdm^or'cm'^SMnm · can not give sufficient polymerization speed difference, and it is difficult to widen. On the other hand, if 5 is larger than SOOdn^mor'cnr'^GSTim, SOOOOdn^mor'cm-^SS^m, 1 OOOOOdn^mol'm^SMnm, the polymerization may not be completed completely, and the hardening cannot be completed. Further, the molar extinction coefficient is a value obtained by measuring the spectrophotometry of each material from the extinction degrees of 365 nm, 334 nm, and 314 nm obtained. The polymerizable liquid crystal original compound (A) having one polymerizable functional group can be exemplified by the following general formula: (1)

The compound represented (wherein RcRu may be the same or different, and represents -F, -H, -CH3, -C2H5 or -〇CH3, and Ri3 represents -Η or -CH3, X, which represents the general formula (2): - ( CH2CH20) a- (CH2) b- (〇) c-, χ2 means ~(^ or -17. Only, 3 in the general formula (2) is an integer of 0 to 3, 1) is an integer of 0 to 1 2 , c is 0 or 1, and when a=l~3, b=0, c=0, when a=0, b=1~1 2 , c=〇~1) 聚合 is expressed by the general formula (1) Specific examples of the liquid crystal original compound (Α) are shown in Table 1. 17 1341928 Table 1 fri shows R, R4 Rs «6 R7 r4 Rs R ι〇Rn R.3 XI ί 匕 r a 2 abci Η Η Η Η Η Η F Η Η Η Η Η Η CN 1 0 0 2 Η 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Η Η Η Η 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 3 3 3 3 3 3 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 CN 0 Η Η 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Η z z Η Η Η Z Z Z Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η 1 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Η 2 3 3 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 CN 0 Η 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , , i , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 2 Η 2 2 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 2 2 2 2 2 F 0 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ^ 2 2 2 2 2 2 2 ^ 2 ^ ^ 2 ^ ^ 2 2 2 ^ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ^ ^ 2 F 0 30 2 30 30 FF FF 2 2 2 FF FF 2 2 2 2 2 2 F 2 0 0 40 F" ? Η Η Η Η Η Η Η Η 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2聚合 0 Η Η 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 A) is not limited to these exemplified compounds. Further, the polymerizable optical agent (B) is, for example, LC756 manufactured by BASF Corporation. The amount of the polymerizable optically active agent (B) is preferably from -20 parts by weight to 3 parts by weight based on the total amount of the polymerizable liquid crystal raw material 5 compound (A) and the polymerizable optically active agent (B). ί is better. The helical torsional force (ΗΤρ) can be controlled by the ratio of the polymerizable liquid crystal original compound (4) to the polymerizable optically active agent (Β). By making the aforementioned ratio within the foregoing range by 18 1341928, the reflection band can be selected so that the reflection spectrum of the obtained torsion layer liquid crystal film covers the long wavelength region. Further, the liquid crystal mixture usually contains a photopolymerization initiator (c). The photopolymerization initiator (c) can be used in various kinds without particular limitation. For example, it can be exemplified in the heart of the eight 5 Μ ... ... ... ... ... ... ... 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二The amount of the photopolymerization initiator to be mixed is preferably from 1 to 1 part by weight, based on 100 parts by weight of the total of the polymerizable liquid crystal original compound (Α) and the polymerizable optical agent (〇〇), and is 5 to 5 parts by weight. Better. 1〇 In the above mixture, in order to broaden the bandwidth of the obtained twisted layer liquid crystal film, an ultraviolet absorber may be mixed to increase the difference in ultraviolet exposure intensity in the thickness direction. Further, the same effect can be obtained by using a photoreaction initiator having a large molar extinction coefficient. The foregoing mixture can be used as a solution. The solvent used in the preparation of the solution 'usually can be used, three gas methane, two gas crater, two gas ethane, four gas ethane, three 15 gas ethylene, four gas ethylene, gas stupid and other functional hydrocarbons, stupid phenol And aromatic phenols such as phenol, benzene, hydrazine, xylene, methoxy stupid, 1,2-dimethoxy stupid, etc., other such as acetone, mercaptoethyl ketone, ethyl acetate Ester, tert-butanol, propylene glycol, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimercapto, acetoin, butyl quercetin, 2-pyrrole Pyridone, Ν-methyl-2-0 than bite 20 _, ° pyridine, triethylamine 'tetrahydrofuran, dimethyl carbamide 'dimethylamine, dimethyl hydrazine, acetonitrile, butyl Nitrile, carbon disulfide, cyclohexanone, cyclopentanone, and the like. The solvent to be used is not particularly limited, and methyl ethyl ketone, cyclohexanone, cyclohexanone or the like is preferred. The concentration of the solution may not be generalized due to the solubility of the thermonic liquid crystalline compound or the thickness of the twisted liquid crystal layer of the final purpose, and is usually preferably from 1 to 341,928 to 35% by weight. The production of the wide-frequency twisted-layer liquid crystal film of the present invention comprises the steps of applying the liquid crystal mixture to the oriented substrate, and subjecting the liquid crystal mixture to ultraviolet irradiation to cause polymerization hardening. 5 Oriented substrate can be known, for example, a film formed by forming a film formed of polyimide or polyvinyl alcohol on a substrate and rubbing it with rayon cloth or the like; An oblique vapor deposition film; a light-oriented film irradiated with a polarized ultraviolet ray on a polymer having a photocrosslinking group such as cinnamic acid or azobenzene; or a polyimide film; a stretched film or the like. In addition, it can be oriented by magnetic field, electric field orientation, and frictional stress operation 10. The type of the substrate is not particularly limited, and a method of irradiating the irradiation line (ultraviolet rays) from the substrate side is preferable to use a material having a high transmittance. For example, the substrate preferably has a transmittance of 10% or more, particularly 20% or more, in an ultraviolet region of 200 nm or more and 400 nm or less, particularly 300 nm or more and 400 nm or less. Specifically, a plastic film having a transmittance of ultraviolet rays having a wavelength of 15 365 nm of 10% or more and even 20% or more is preferable. Further, the transmittance is a value measured by a HITACHI U-4100 Spectrophotometer. Further, as the substrate, polyethylene terephthalate, triethyl hydrazine cellulose, normethazine resin, polyvinyl alcohol, polyimine, polyallyl ester, polycarbonate 20, polyfluorene or poly can be used. A film made of plastic such as ether oxime, a glass plate, or a quartz plate. For example, Fuji Photograph 7 彳 厶 厶 三 三 三 或 或 或 或 或 或 或 或 或 ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART ART Further, the polymer film described in JP-A-2001-343529 (WOO 1/37007) may, for example, contain a thermoplastic resin having a substituted and/or unsubstituted oxime 20 1341928 amine group in the side chain (A). And (B) a resin composition of a thermoplastic resin having a substituted and/or unsubstituted phenyl group and an eye group on the side chain. Specific examples thereof include a film comprising a cross-polymer of isobutylene and N-methyl cis-butanediamine and a resin composition of a propylene bromide copolymer. As the film, a film formed of a mixed product of a resin composition, or the like can be used. The substrate can be used in a state of being adhered to the liquid crystal layer of the twisted layer, or can be removed by peeling off. When used in a fitted state, a material having a very small phase difference in practical use is used. When it is used in combination with a substrate, it is preferable to use a substrate which does not decompose, deteriorate, or yellow even if it is irradiated with ultraviolet rays. For example, mixing a light stabilizer or the like in the aforementioned substrate can achieve the desired purpose. Light stabilizers can be used as appropriate. Less force / by company, only 匕,, > 12〇, 144, etc. When the wavelength is removed from the exposure light by 3 〇〇 nm or less, the coloring, deterioration, and yellowing can be reduced. The coating thickness of the liquid crystal mixture (in the case of a solution, the coating thickness after solvent drying) is preferably 1 to 2 Å/m. If the coating thickness is thinner than 丨^, the reflection bandwidth can be secured, but the degree of polarization tends to be inferior, which is not preferable. The coating thickness is preferably 2/zm or more, or even 3ym or more. On the other hand, if it is thicker than 2 〇 - ', the reflection bandwidth and the degree of polarization are not significantly improved, but the cost is increased, so it is not suitable. The coating thickness is preferably 15 or less, and more preferably 1 or less. 20 A method of applying the above-mentioned mixed solution to a substrate may be, for example, a roll coating method, a gravure coating method, a spin coating method, a wire coating method, or the like. After the coating of the mixed solution, the solvent is removed to form a liquid crystal layer on the substrate. The solvent removal conditions are not particularly limited as long as the solvent can be removed, and the liquid crystal layer does not flow or flow. Usually, the solvent is removed by drying at room temperature, drying in a drying oven, heating on a 21 1341928 hot plate, or the like. Next, the liquid crystal layer formed on the oriented substrate is in a liquid crystal state to orient the twist layer. For example, heat treatment is performed to make the liquid crystal layer a liquid crystal temperature range. The heat treatment method can be carried out in the same manner as the above drying method. The heat treatment temperature of 5 degrees varies with the type of liquid crystal material or oriented substrate, so it cannot be generalized, but is usually 60 to 300. (:, in the range of 70 to 200. (: The range is better. Also, the heat treatment time varies with the heat treatment temperature and the type of liquid crystal material or oriented substrate used), so it cannot be generalized, usually in 10 seconds~ It is preferable to select 'with a range of 20 seconds to 30 minutes in a range of 2 hours. 10 The step of applying the liquid crystal mixture to the oriented substrate and irradiating with ultraviolet rays comprises the above steps (1) to (3). Step (1) In the state in which the liquid crystal mixture is in contact with the oxygen-containing gas, the ultraviolet ray is irradiated with ultraviolet rays at a temperature of 2 Torr or more at a temperature of 20 to 200 mW/cm 2 for 0.2 to 5 seconds from the side of the oriented substrate. The mixture is polymerized, 15 forms a polymer/aggregate having an average molecular weight of about 5,000 to 500,000, and the difference in reaction rate due to oxygen inhibition and the amount of radical generation due to ultraviolet absorption of the liquid crystal composition A layer in which the amount of formation of the polymer/oligomer in the thickness direction is continuously distributed is generated in the thickness direction of the oriented substrate side and the opposite side (oxygen interface side). 2〇 In the step (1) When the liquid crystal mixture is polymerized and cured in a good orientation state, the temperature at the time of the first ultraviolet ray irradiation is 2 Å or more. In addition, the upper limit of the temperature is not particularly limited, but is 1 〇〇〇 c or less. Appropriate. If the temperature is lower than the loot: 'The radiation will cause diffusion and is difficult to manage. From these points, the above temperature is preferably 20 ° C ~ 50 eC. The first ultraviolet irradiation intensity is 2 〇 ~ 2 22 1341928 o 〇 Mw/cm ' is preferably 25~200mW/cm2, and 4〇~i5〇mw/cm2 is better. The ultraviolet irradiation intensity is purely 2Qmw/em2, which can not be completed in the direction of the thickness. When the ultraviolet irradiation intensity is higher than 200 mW/cm2, the polymerization reaction rate is higher than the diffusion rate, and it is not possible to complete the broadening, so it is not suitable. 4 Step (1) towel, the first ultraviolet irradiation time is 〇 2~5 seconds, preferably 〜3~3 seconds is better than 0.5~1.5 seconds. If it is shorter than 0 2 seconds, the polymerization of the monomer distribution in the thickness direction cannot be completed, and the frequency cannot be widened. After more than 5 seconds, the pitch of the twisted layer liquid crystal layer does not change. From the side of the oriented substrate to the side of the oxygen interface, it is a continuous change from ·10 to small, and it becomes discontinuous, so it is not suitable. If a discontinuous change is formed, the coloring becomes severe when viewed from an oblique direction. The exposure environment is carried out in a state where the liquid crystal mixture applied to the substrate is brought into contact with the oxygen-containing gas. The oxygen-containing gas preferably contains 5% or more of oxygen, and the environment can be used as long as it is resistant to oxygen polymerization. , generally, can be carried out in an atmospheric environment. In addition, the oxygen concentration can be increased or decreased according to the wavelength of the pitch control in the thickness direction and the speed required for the polymerization. Further, in the atmosphere, relative to the polymerization 100 parts by weight of the total of the liquid crystal original compound (A) and the polymerizable optically active agent (B), and the amount of the enthalpy is used in an amount of 1 to 5 parts by weight, the year 2 184 '彳 claw force, the year 2 y 907 (All of them are in the 〆 殳 · 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Further, when the weight average molecular weight of the formed polymer/oligomer is too small at the time of the first ultraviolet ray irradiation, the diffusion rate is too high. Therefore, care should be taken to minimize the concentration gradient of the polymer/oligomer due to uncontrolled diffusion rates. No 23 1341928 It is only necessary to form a large change in the thickness direction of the liquid crystal layer with a long twist pitch, and it must be able to maintain it. If the molecular weight of the polymer/aggregate is too low, the formed tilt cannot be maintained. The structure disappears due to molecular diffusion. In order for the diffusion rate to satisfy the conditions governed by industrial conditions, it is necessary to form a polymer/oligomer in a weight average molecular weight of 丨〇〇〇〇 to 500,000. The weight average molecular weight of the polymer/oligomer is preferably from 10,000 to 300,000. Further, the weight average molecular weight of the polymer/oligomer is a value measured by a GPC method. Further, the weight average molecular weight was calculated using a polyethylene oxide as a standard sample. Main body: HLC-8120GPC made by Dong V-, pipe column: East,) SuperAWM-H+SuperAWM-H+SuperAW3000 (6mm 10 4 X 15cm, 45cm each), pipe temperature · 40°C, Dissolution: 〖0 mM-LiBr / NMP, flow rate: 0.4 ml/min, inlet pressure: 8, 5 MPa, sample j degree: 〇·ι% NMP solution, detector: differential refractometer (RI). When the concentration distribution formed by the first ultraviolet ray irradiation in the step (1) is directly fixed, only the reflection wavelength band of the same level as that of JP-A-2002-286935 or the like can be obtained. Therefore, in the step (2), the liquid crystal layer is brought into contact with the oxygen-containing gas, and the liquid crystal layer is brought into contact with the oxygen-containing gas at a temperature increase rate of 2.匚 / sec or more, reaching the temperature higher than the step (1 ) and above 60 ° C, and lowering the ultraviolet ray intensity lower than the step (1), illuminating the purple 20 outer line from the side of the oriented substrate for more than 1 second . By the second ultraviolet irradiation in the step (2), the effective depth of the polymerization inhibition caused by the oxygen permeated from the oxygen interface side is deeper than the step (1), and further, since the polymer is obtained in the step (1) The oligomer is formed to be inclined at a concentration in the thickness direction, so that the concentration gradient of the formed unpolymerized monomer component can be made uniform. At the same time, the long pitch of the oriented substrate side can be further increased by merely performing the reaction of the long pitch field 24 1341928 on the oriented substrate side. The increase in the molecular weight of the liquid crystal composition layer and the diffusion rate are inferior, and the difference is large compared to the first ultraviolet irradiation in the step (1), so that the amount of radicals generated per unit time is reduced, and the polymerization progress rate is lowered. Can be more broadband. 5 In the special book No. 3272668, change the number! The temperature conditions of the secondary ultraviolet irradiation and the second ultraviolet irradiation, and the time required for the composition ratio to vary in the thickness direction is additionally disposed in the dark, but if the whole visible light is covered by the method, the substance movement caused by the temperature change The waiting time takes 12 () minutes. On the other hand, in the manufacturing method of the present invention, dark places are not particularly required. And the steps can be completed in a short time within 10 minutes, so that a highly efficient and efficient production speed can be produced. In the step (2), the second and outer lines are irradiated while the temperature is raised to the predetermined reaching temperature. In the step (2), the starting temperature at the time of the second ultraviolet ray irradiation is the same as the temperature in the step (1). That is, at 2 (rc or more. If the starting temperature is lower than 15 CC', the diffusion rate of the polymerizable liquid crystal original compound (1) is very slow and takes a long time to be broadened. X, the reaching temperature is set higher than the step (1). In addition, when the temperature is lower than 6 (rc), the diffusion of the polymerizable liquid crystal original compound (a) is not sufficiently generated, and the frequency cannot be sufficiently broadened. The upper limit of the temperature is not particularly limited, but 14 (The following is better than rc. It is better to reach 20 °C to 120 °C when the temperature is 20 degrees. If the temperature is higher than M〇〇c, the diffusion speed is too fast and difficult to manage. From the end of the first ultraviolet irradiation, the temperature is rapidly increased to the reaching temperature at a temperature increase rate of 2 C/sec or more. If the temperature increase rate is less than 2 seconds, the diffusion of the polymerizable liquid crystal original compound (4) cannot be sufficiently produced. However, it is not possible to sufficiently widen the temperature. The temperature increase rate is preferably 2 to 2 〇t / sec. After reaching the arrival temperature of the pre-twist, 'normally, the second ultraviolet ray can be maintained while maintaining the temperature. In the range below 14〇t, it can also be When the temperature reaches a predetermined temperature, the temperature is gradually increased. The second ultraviolet ray is irradiated with an irradiation intensity lower than the ultraviolet ray intensity of the first ultraviolet ray. When the illuminance is lower than the first ray, the oxygen polymerization resistance depth is deeper than The oxygen resistance depth at the time of the th-th ultraviolet irradiation is such that the short-wavelength band formed on the air interface side hardly changes, and the long-wavelength bandwidth on the substrate side is frequency-divided. χ, the second ultraviolet ray irradiation intensity is lower than the first ultraviolet ray irradiation. The range of the intensity is preferably 1. The ultraviolet irradiation time varies depending on the illuminance, and is generally preferably in the case of leap seconds or more. The second ultraviolet irradiation time is the irradiation time and the reaching temperature at which the temperature is rapidly increased to reach the temperature. Further, the ultraviolet irradiation time is preferably 12 sec or less, more preferably 6 sec or more, from the viewpoint of the working time, and the widening is achieved by the step (7) as described above. After the realization of the wide frequency of the embodiment described in the fifth embodiment, the angle of view caused by the blue shift of the oblique eight-shot light causes coloring and discoloration to become very large, which can be significantly reduced. The coloring is caused by the angle of view. Next, in step (1), ultraviolet rays are irradiated in the absence of oxygen, and by the third ultraviolet irradiation, the torsion layer 2 〇 reflection band which is expanded in steps (1) and (7) can be made inferior and hardened. The pitch variation structure can be made inferior and fixed. In the absence of oxygen, for example, it can be in an inert gas atmosphere. The inert gas does not have any influence on the ultraviolet polymerization of the liquid crystal mixture. The inactive gas can be, for example, nitrogen H, nitrogen gas 氪 26 1341928, etc. Among them, II is most commonly used, and it is suitable, and the transparent substrate can be laminated on the twisted liquid crystal layer. In the step (3), the ultraviolet irradiation can be carried out from either the side of the oriented substrate or the side on which the liquid crystal mixture has been applied. 5 The external irradiation condition is not particularly limited as long as it is a condition that the liquid crystal mixture is hardened. Usually, the irradiation intensity of 40 to 30 〇 mW/cm 2 is preferably irradiated for 6 sec. The irradiation temperature is 20 toloot. Thereby, the crosslink density of the liquid crystal layer can be improved and the molecular weight can be improved. In the present invention, in the second step of the step (1), the ultraviolet ray irradiation and the second ultraviolet ray irradiation in the step (H) are irradiated with ultraviolet rays from the surface side of the oriented substrate in order to actively use oxygen. Therefore, a large gradient can be formed in the thickness direction in the reaction rate, but the problem is that the problem of insufficient hardness and strength of the film surface or insufficient long-term reliability may occur due to a low polymerization rate at the air interface side. Therefore, in the step (1), the third ultraviolet ray irradiation is performed in the absence of oxygen, and the residual monomer is polymerized 15 to complete the film quality enhancement. In this case, the reaction rate on the surface in an air environment (in the presence of oxygen) is not sufficiently increased, and the reaction rate is hardly increased to 9〇%. Therefore, in order to obtain sufficient reliability, it is preferred to perform ultraviolet irradiation in the absence of oxygen. The direction of irradiation is not particularly limited. It is preferred to irradiate from the liquid crystal layer side, but in the gas atmosphere, the surface reaction can be sufficiently performed even when irradiated from the substrate side. 20 The twisted-layer liquid crystal film thus obtained can be used without being peeled off from the substrate, or can be used after being peeled off from the substrate. The wide-band twisted layer liquid crystal film of the present invention can be used as a circularly polarizing plate. The circular polarizer can be laminated; the W4 plate acts as a linear polarizer. The circularly polarizing plate, that is, the twisted-layer liquid crystal film, is preferably laminated on the λ/4 plate in a state in which the pitch length is continuously narrowed. 27 1341928 λ/4 plate is not particularly limited, and may be suitably used such as polycarbonate, polyethylene, stearic acid, polystyrene, polyfluorene, polyvinyl alcohol, polymethyl methacrylate, etc. to extend the phase difference. A general-purpose transparent resin film or a normidine-based resin film such as an ARTON film manufactured by JSR Corporation. Further, it is preferable to use a phase difference plate that performs two-axis extension and compensates for a change in phase difference due to a 5-angle angle, thereby improving viewing angle characteristics. Further, in addition to exhibiting a phase difference by the resin extension, it is also possible to use a U4 plate obtained by fixing, for example, another layer obtained by orienting the liquid crystal; At this time, it can be greatly reduced; the thickness of 1/4 plate. The thickness of the /4 wavelength plate is usually preferably 〇5~2〇〇 /z m, particularly preferably 1~1 〇〇 μ m. (10) A phase difference plate that functions as a λ/4 wavelength plate in a wide wavelength range such as the visible light region, for example, a phase difference layer that functions as a λ /4 wavelength plate with pale light having a wavelength of 55 〇 nm. It is obtained by overlapping a phase difference layer which exhibits other phase difference characteristics, for example, a phase difference layer functioning as a Λ/2 wavelength plate. Therefore, the phase difference plate 15 disposed between the polarizing plate and the brightness enhancement film may be formed of a germanium layer or a retardation layer of two or more layers. The absorbing polarizer can be used by being aligned on the transmission axis in the direction of the transmission axis of the linear polarizer. The polarizer is not particularly limited and various types can be used. As a polarizer, for example, a hydrophilic polymer film such as a polyethylene glycol film, a partial methylation polyethylene film, or an ethylene/ethylene 20 acetic acid copolymer portion 4 film can be used. Broken or two-color f-raw wood, etc.—a single-strand stretcher of a coloring material, a dehydrated material of polyethylidene alcohol, or a degassing treatment of a gas-deficient sputum, and the like. This is preferable to a polarizer formed of a dichroic alcohol film and a dichroic substance such as ruthenium. The thickness of these polarizers is not particularly limited, and is generally 5 to m. The polarizer which is a single-stretched stretch of the polyephthyl alcohol film by moth dyeing can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of eucalyptus, and extending it to 7 times the original length. It may be immersed in an aqueous solution containing a sulphuric acid or a sulphuric acid such as zinc sulphate or the like as needed. It is also necessary to immerse the polyethylene glycol film in water for washing before the dyeing. By washing the polyethylene glycol film by water, it is possible to wash not only the dirt or the blocking preventive agent on the surface of the polyethylene film, but also the effect of swelling the polyvinyl alcohol film to prevent unevenness such as dyeing mottle. The extension can be carried out after dyeing, or by dyeing, or by iodine after stretching. It can also be extended in an aqueous solution such as boric acid or potassium iodide or in a water bath. 1〇 The polarizer is usually used as a polarizing plate provided with a transparent protective film on one side or both sides. The transparent protective film is excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and the like. The transparent protective film may, for example, be a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose polymer such as bisacetyl cellulose or triacetyl cellulose, or a poly A film formed of a transparent polymer such as a carbonate polymer or an acrylic polymer such as polymethacrylate. Further, a polystyrene, an acrylonitrile/styrene copolymer styrene styrene polymer, a polyolefin having a polyethylene, a polypropylene, a ring system or a deuterium structure, and an ethylene/propylene copolymerization may be mentioned. A film formed of a polyolefin polymer such as a polyolefin polymer, a gas-ethylene polymer, or a ruthenium-based polymer such as a donor or an aromatic polyamide. Further, an imine-based polymer, a fluorene-based polymer, a polyether fluorene-based polymer, a polyetheretherketone-based polymer, a poly-extension-based sulfide-based polymer, a glycol-based polymer, and a biased gas B A transparent polymer of a rare polymer, a polyglycol condensate polymer, an allyl ester polymer, a polyfurfural polymer, an epoxy polymer, or a blend of the foregoing polymers The film formed. In particular, it is better to use less optical refraction at 29. From the viewpoint of the protective film of the polarizing plate, it is suitable to use a polyethylene glycol, a polycarbonate, an acrylic polymer, a cycloolefin resin, a polyolefin having a norform structure, and the like. Further, the polymer film of the fifth embodiment described in JP-A-2001-343529 (WOO 1/37007) may, for example, contain a thermoplastic resin having a substituted and/or unsubstituted guanamine group in the side chain of (A), and (B) A resin composition of a thermoplastic resin having a substituted and/or unsubstituted base group and a nitrile group in a side chain. Specific examples thereof include a film comprising a cross-polymer of isobutylene and N-methylbutyleneimine and a resin composition of a propylene residual ethylene copolymer. As the film, a film formed of a mixture of 10 substances and the like can be used. A transparent protective film is preferably a triacetyl cellulose film which is saponified with a base or the like based on a polarizing property or durability. The thickness of the transparent protective film is appropriately determined, and it is generally 10 to 500 " m, especially 2 〇 to 3 〇〇 " m, from the viewpoints of workability such as strength and handleability, and thin layer properties. It is better to use 3〇~2〇〇"m 15. Further, the transparent protective film is preferably not colored as much as possible. Therefore, it is preferable to use: Rth=[ ( nx+ny ) /2-nz].d (only, nx, ny is the main refractive index in the film plane, nz is the refractive index in the film thickness direction, and d is the film thickness) The phase difference in the film thickness direction indicated is a protective film of -90 nm to +75 nm. By using the phase difference of the thickness direction of the thickness direction of -90 nm to +75 nm, the coloring (optical dyeing) of the polarizing plate caused by the protective film can be almost eliminated. The phase difference (Rth) in the thickness direction is preferably -80 nm to +60 nm, especially _7 〇 nm to +45 nm. The transparent protective film can be transparently protected by the same polymer material in the surface. The film may also be a transparent protective 30 1341928 film formed of a different polymer material or the like. The surface of the transparent protective film which is not followed by the polarizer may be subjected to a treatment for the purpose of a hard coat layer, reflection preventing treatment, adhesion prevention or diffusion, or even anti-glare. In order to prevent the loss of the surface of the polarizing plate, the hard mask treatment can be performed by using a suitable ultraviolet curable resin such as a polyacrylic acid-based polysulfide resin. The hardened film is formed by attaching it to the surface of the transparent protective film. The reflection preventing treatment is carried out for the purpose of preventing reflection of light outside the surface of the polarizing plate, and can be achieved by the formation of a conventional reflection preventing flaw or the like. Further, the adhesion prevention treatment is performed for the purpose of preventing adhesion to the adjacent layer. Further, the anti-glare treatment can be carried out for the purpose of preventing external light from being reflected on the surface of the polarizing plate and obstructing the visual observation of the light transmitted through the polarizing plate, and can be performed by, for example, a blasting method or an embossing method. A suitable method such as a surface-forming method or a method of blending transparent fine particles is applied to the surface of the transparent protective film to form a fine uneven structure. In the formation of the surface fine concavo-convex structure, as the fine particles contained therein, for example, ceria, alumina, titania, oxidized tin, tin oxide, indium oxide 氡 having an average particle diameter of 5 to 50 μm can be used. When the transparent fine particles such as organic fine particles formed by cadmium or cerium oxide and the organic fine particles formed by crosslinking or uncrosslinked polymer form a surface fine uneven structure 2, the use of fine particles The amount is preferably 2 to 5 Å by weight, and preferably 5 to 25 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure. The glare layer can also serve as a diffusion layer (expanding the viewing angle function, etc.), and the polarizing plate can be diffused by light to expand the viewing angle. Further, the anti-reflection layer, the adhesion preventing layer 'diffusion layer or the anti-glare layer 31 31341928 may be provided on the transparent protective film, or may be provided as a separate transparent layer from the transparent protective film.

An adhesive layer for attaching to other members such as a liquid crystal cell may be disposed on the linear polarizer. The adhesive for forming the adhesive layer is not particularly limited. For example, an acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine atom or a rubber may be appropriately selected. The polymer is used as a matrix polymer. In particular, an acrylic pressure-sensitive adhesive is excellent in optical transparency, exhibits moderate wettability, cohesiveness and adhesion property, and is excellent in weather resistance and heat resistance, and is particularly preferably used. 10 In addition to the above, it is based on the prevention of foaming or peeling due to moisture absorption, prevention of deterioration of optical properties due to thermal expansion, or warpage of liquid crystal cells, and high quality and excellent durability. In order to form the liquid crystal display device, it is preferable to use an adhesive layer having a low moisture absorption rate and excellent heat resistance.

The adhesive layer may contain, for example, a resin of a natural product or a composition, particularly, for example, an adhesive property-imparting resin, a glass fiber, a glass bead, a metal powder, a filler formed of other inorganic powder or the like, a pigment, a colorant or an antioxidant. An additive that can be added to the adhesive layer. Further, it may be an adhesive layer containing fine particles and exhibiting light diffusibility. The attachment of the adhesive layer can be carried out in an appropriate manner. For example, it can be prepared by dissolving or dispersing a matrix polymer or a composition thereof in a solvent formed by a single substance or a mixture of a suitable solvent such as toluene or ethyl acetate to form an adhesive of about 10 to 40% by weight. The solution solution is directly attached to the polarizing plate or the optical film by a suitable expansion method such as a flow-through method or a coating method, or an adhesive layer is formed on the release film according to the above, and then moved to The manner of 32 on the polarizing plate or on the optical film. The adhesive layer may be provided on one or both sides of the polarizing plate or the optical film as an overlapping layer of different compositions or types. Further, in the case of double-sided, an adhesive layer of a different composition, type, thickness or the like may be formed in the surface of the polarizing plate or the optical iridium. The thickness of the adhesive layer can be appropriately determined depending on the purpose of use or adhesion, etc., generally 1 to 500/zm, and preferably 5 to 200 " m, especially 1 〇 to 1 〇〇 " m is preferred. Before the application for practical use, the release film is temporarily attached to the exposed surface of the adhesive layer for the purpose of preventing contamination thereof. Thereby, the handling of the money can prevent contact with the adhesive layer. In addition to the above-mentioned thickness conditions, the release film may be, for example, a suitable sheet of a plastic film, a rubber sheet, a paper, a cloth, a non-woven fabric, a mesh, a foamed sheet or a metal thin layer, a laminate of these sheets, etc., if necessary (4) Suitable stripping such as oxygen-based, long-chain pit system, fluorine element or sulphide, etc., is suitable according to the conventional application of the coating agent. Further, in each layer such as an adhesive layer, for example, an ultraviolet absorber such as a salicylic acid vinegar compound or a benzene sulfonate compound, a diazonium salt compound, a cyanoacrylic acid compound, or a morphological salt compound can be used. The method of treatment, etc., such that it has ultraviolet absorption energy and the like. The linear polarizer of the present invention can be suitably used for formation of various devices such as a liquid crystal display device. The formation of the liquid crystal display device can be conventionally carried out as a reference. In other words, the liquid crystal display device is generally formed by appropriately combining a liquid crystal cell, an adhesive optical film, and a component such as an illumination system as needed, into a driving circuit, etc., in addition to the use of the present invention. The formation of the polarizing plate before the film is not particularly limited, and can be carried out according to a conventional method. As the liquid crystal cell, any type such as TN type, STN type or π type can also be used. It can be made into a suitable liquid crystal display device such as a polarizer or an optical film on the one side 4 of the liquid crystal cell, or a backlight or a reflector for use in an illumination system. At this time, the polarizing plate or the optical film formed by the present invention may be disposed on one side or both sides of the liquid crystal cell. When a polarizing plate or an optical film is provided on both sides, the same may be the same or different. Further, in the case where the liquid crystal display device is formed, suitable components such as a diffusion plate, an anti-glare layer, a reflection preventing cymbal, a protective plate, a ruthenium array, a lens array film, a light diffusing plate, and a backlight can be disposed at appropriate positions. 1 or more layers. Further, a circularly polarizing plate (reflecting polarizer) using the twisted-layer liquid crystal film is used for the polarizing element system 1 described below, that is, at least two layers of reflective polarizers (a) which are mutually overlapped in a wavelength band of selective reflection of polarized light. Between them, the front phase difference (normal direction) is arranged to be almost zero and is 3 相对 with respect to the normal direction. The incident light obliquely incident above has a retardation layer (b) of λ/8 or more. Further, the twisted layer liquid crystal film may have a spiral pitch twisted molecular structure on either side of the maximum pitch and the minimum pitch as the phase difference layer (b) side, but from the viewpoint of a viewing angle (good viewing angle and small coloration), 15 right will reflect The polarizer (a) is expressed by (maximum pitch/minimum pitch), and is preferably configured to have a maximum pitch/minimum pitch/phase difference layer (b) / maximum pitch / minimum pitch. Further, as shown in Fig. 6, when the λ/4 plate is combined, it is preferable that the minimum pitch side of the reflected polarizer (a) is set to be /4 plate side. The polarizing element system, that is, a layered liquid 20-layer laminate having a wide-band selective reflection function, has a circular polarization reflection/transmission function in the front direction, and can be used as a wide-frequency circular polarizing plate for a liquid crystal display device. In this case, it can be used as a circularly polarizing plate by a liquid crystal cell arranged in a circularly polarized type; for example, a light source side of a multi-domain transmissive VA type liquid crystal cell. The phase difference layer (b) has a phase difference of almost zero in the front direction and a phase difference of λ/8 or more with respect to incident light at an angle of 30 from the line direction of the method 34 1341928. The purpose of the front phase difference is to maintain the polarization of the normal incidence, so it is preferably below λ/10. The incident light from the oblique direction can be appropriately determined in accordance with the angle at which the polarized light can be efficiently converted and totally reflected. For example, to make a total total reflection at an angle of 5 60 ° from the normal, the phase difference at 60 ° is λ /2.

Just fine. However, since the transmitted light is reflected by the reflected photon (a), the polarization state changes depending on the birefringence of the C-plate property of the reflected polarizer itself, so that the phase difference of the normally inserted C plate at the angle is determined. Less than λ /2. Since the phase difference of the C plate is more monotonous when the incident light is inclined, the incident light having an angle of 10 degrees with respect to 30° has λ/8 or more as an effect at an angle of 30° or more. The standard of reflection can be.

The material of the retardation layer (b) is not particularly limited as long as it has the optical characteristics as described above. For example, it is possible to fix the direction of the plane of the twisted layer liquid crystal having a selective reflection wavelength other than the visible light region (380 nm to 780 nm) or the vertical alignment state of the fixed rod-shaped liquid crystal, and to orient the tube bundle phase using the discotic liquid crystal. Or a phase-aligned person, a negative one-axis crystal orientation in the plane, a biaxially oriented polymer film, or the like. In the present invention, a C-plate having a plane-oriented state of a twisted-layer liquid crystal having a selective reflection wavelength, which is fixed in the visible light region (380 nm to 780 nm), is preferably used as a selective reflection wavelength of the twisted-layer liquid crystal in the visible light field. . Therefore, the choice of reflected light must not be in the visible light field. The selective reflection is determined by a single meaning of the optical pitch of the twisted layer liquid crystal and the refractive index of the liquid crystal. The value of the center wavelength of the selective reflection may be in the infrared field, but it may be slightly complicated due to the influence of the optical rotation, so that the ultraviolet portion of 350 nm or less is more preferable. About the twisted layer 35 1341928 The formation of the liquid crystal layer can be performed simultaneously with the formation of the twisted layer of the reflective polarizer. In the present invention, the c-plate in the fixed vertical orientation state uses a liquid crystal thermoplastic resin or a liquid crystal monomer which exhibits nematic liquid crystal at a high temperature by irradiation with ionizing radiation such as electron beam or ultraviolet rays, or by heat. The alignment aid is a combination of a polymeric liquid crystal, or a mixture thereof. The liquid crystal property may be liquid or thermal, but it is preferably a thermal liquid crystal from the viewpoint of ease of control or ease of formation of a single sound. The vertical alignment system is obtained by, for example, coating the above-mentioned birefringent material on a film on which a vertically oriented film (long-hole pit base, etc.) is formed, exhibiting a liquid crystal state and being fixed. 10 As a C-plate using discotic liquid crystal, a discotic liquid crystal material having a negative axis such as a phthalocyanine or a biphenyl compound having a molecular enlargement in a plane, exhibiting a nematic phase or tube The column phase is fixed and used as a liquid crystal material. The negative 1-axis inorganic layered compound can be found, for example, in JP-A-6-82777. By using a biaxially oriented C plate of a polymer film, a method of pressurizing a thermoplastic resin with a polymer film having a positive refractive index anisotropy in a well-balanced two-axis manner can be parallelized. A method of directional crystal cutting and the like is obtained. The laminate of the respective layers may be placed only in an overlapping manner, and it is preferable to laminate the layers by using an adhesive or an adhesive from the viewpoint of workability and light use efficiency. In this case, the adhesive or the adhesive is transparent. 'There is no absorption in the visible light region, and the refractive index based on the surface reflection of the substrate is preferably as close as possible to the refractive index of each layer. From this viewpoint, for example, an acrylic adhesive or the like can be suitably used. Each layer may be formed into a single domain by using a different orientation film or the like, and then sequentially stacked by a method such as transcribing a light-transmissive substrate, or an adhesive layer may be formed to form an orientation film or the like for orientation. The layers are directly formed in order. 36 Each layer and (adhesive) layer may be added as necessary for the degree of diffusion adjustment, to impart isotropic properties, or to appropriately add a UV absorber, an antioxidant, and an interface activity for the purpose of imparting adjustability to the crucible. Agents, etc. The polarizing element (twist layer liquid crystal layered body) of the present invention has a circularly polarized light reflecting/transmitting machine, and can be used as a straight green polarized photo which converts transmitted light into linearly polarized light by combining λ /4. The same as the above can be exemplified as the λ/4 plate. If the λ / 4 plate is a single layer formed of a single material, it has a good function only for a specific wavelength, and for other wavelengths, there is a problem that the wavelength dispersion characteristic is inferior as λ/4. Therefore, if the λ/2 plate is laminated with the shaft angle, it is practically unobstructed, and it functions as a wide-band λ/4 plate in the entire visible light range. In this case, each of the λ/4 plates and the λ/2 plates may be the same material, or may be produced by a combination of another material obtained by the same method as the above λ/4 plate. For example, 'in a wide-band circular polarizer layer; 1/4 plate (Ι4〇ηη〇, with an angle of 11 into 5 degrees with respect to the sleeve angle and 2 plates (270ηπ〇. In this case, the transmission polarization axis is relative to λ/4) The axis of the plate is 1 degree. The bonding angle varies by the phase difference of each phase difference plate, and is not limited to the above-mentioned bonding angle. The absorption type polarizer is aligned with the transmission axis of the linear polarizer. The direction is applied to the transmission shaft. (Distribution of the diffuse reflector) The diffuser reflector should be disposed on the lower side of the light guide plate (opposite side of the liquid crystal cell arrangement surface). The light reflected by the parallel actin film The component is an oblique incident component, and the parallel actinic film is reflected back to the backlight direction. When the specular reflection of the reflector on the back side is high, the reflection angle is maintained and the front direction cannot be emitted. Therefore, in order to prevent the scattered reflection component from expanding toward the front direction without maintaining the angle of reflection 1341928 reflected back, it is preferable to dispose the diffuse reflection plate. (Distribution of Dispersion Plate) Parallel actin film and backlight in the present invention Between the light sources, it is advisable to set a suitable diffusion plate. Because the light reflected by oblique incidence is scattered near the backlight light guide, and a part of it is scattered in the vertical incident direction, the light reuse efficiency can be improved. The diffusing plate used may be obtained by embedding a fine particle having a different refractive index in a resin, etc. The diffusing plate may be sandwiched between the parallel actinic film and the backlight, or may be bonded to the parallel light. When the liquid crystal cell to which the parallel actinic film is attached is disposed close to the backlight, a Newton ring may be generated between the surface of the film and the gap of the backlight, and the side surface of the light guide plate of the light parallelizing film in the present invention is configured to have The diffusing plate having the surface unevenness can suppress the occurrence of the Newton's ring. Further, a layer having both the uneven structure and the light diffusing structure may be formed on the surface of the parallel actinic film of the present invention. 15 (Arrangement of the viewing angle widening film) The present invention The viewing angle expansion in the liquid crystal display device is such that the backlight combined with the parallelized light is combined, and the light obtained from the vicinity of the front surface of the liquid crystal display device and having good display characteristics is diffused. The line is diffused to obtain uniform and good display characteristics in the entire viewing angle. 20 The viewing angle-expanding film used herein uses a diffusing plate which is substantially free from the rear. The diffusing plate can be provided as a diffusion adhesive. For the visual side of the liquid crystal display device, any one of the polarizing plate can be used. However, in order to prevent the contrast caused by the infiltration of the pixels or the slightest residual, the polarizing plate to the liquid crystal cell For example, it is preferable to set it as close as possible to the layer 38 close to the unit cell. Further, it is preferable to use a film which does not substantially depolarize the light at this time. For example, JP-A-2000-347006 and JP-A-2000-347007 can be suitably used. The microparticle dispersion type diffusion plate disclosed in the publication. When the viewing angle expansion film is located outside the polarizing plate, the liquid crystal layer-to the polarizing plate is transmitted through the collimated light, so if it is a TN liquid crystal cell, it is not necessary to specifically Use the viewing angle to compensate the phase difference plate. In the case of an STN liquid crystal cell, it is only necessary to use a retardation film which can be well compensated only with the front side characteristics. In this case, the viewing angle widening film has an air surface, so that the type of refraction effect by the surface shape can also be employed. On the other hand, when the viewing angle widening film is inserted between the polarizing plate and the liquid crystal layer, it diffuses light at the stage of passing through the polarizing plate. In the case of TN liquid crystal, the viewing angle characteristics of the polarizer itself need to be compensated. In this case, it is necessary to insert a phase difference plate for compensating for the viewing angle characteristic of the polarizer between the polarizer and the viewing angle widening film. In the case of the STN liquid crystal, in addition to the front phase difference compensation of the STN liquid crystal, it is necessary to insert a phase difference plate which compensates for the viewing angle characteristic of the polarizer. 15 ^ If the microlens array film or the holographic film-like film having a regular structure as in the past has a viewing angle expansion film, it will be parallel to the black matrix of the liquid crystal display device or the conventional backlight. Fine structures such as microlens arrays/稜鏡 arrays/louver/micro-mirror arrays of the system interfere with each other to easily generate moiré. However, the parallel actinic film of the present invention does not have a regular structure in the plane, and the emitted light does not have a regular tone change, so that it is not necessary to consider the degree of matching or arrangement with the viewing angle expanding film. Therefore, the viewing angle widening film is not particularly limited as long as it does not interfere with the pixel black matrix of the liquid a display device, and the selection is wide. In the present invention, the viewing angle widening film can be used as it is, and the optical scattering plate described in Japanese Laid-Open Patent Publication No. 2000-347006, No. 2000-347007, and the like. %~90%. Others, all-image sheets, micro-turn matrices, microlens arrays, etc., even if they have a regular internal structure, can be used as long as they do not form a pixel black matrix interference/moire with the liquid crystal display device. Further, the liquid crystal display device can be produced by appropriately using various optical layers or the like according to a usual method. EXAMPLES Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited by these Examples. Example 1 Photopolymerizable liquid crystal original compound (using a polymerizable nematic liquid crystal monomer, the compound 20 of the above Table 1 'More extinction coefficient was 2100 (^311101^01'@33411111, ΒόΟίΚΜη^πιοίΛιη-^βΜηηι. Purity 15 > 99%) 94.8 parts by weight of a polymerizable optically active agent (LC756 manufactured by BASF Corporation) 5.2 parts by weight and a solvent (cyclopentanone) 'mixed and mixed into a solution having a reflection center wavelength of 55 〇 nm, in which the solution 3% by weight of a photopolymerization initiator was added to the solid content (manufactured by X シ亇 亍 亍 力 力 7 7 7 7 7 7 7 7 7 7 , , , , , , , , , , , , , , , , , , , 调制 调制 调制 调制 ( %). The 20 coating liquid is applied to the extended polyethylene p-triconic acid δ| film (oriented substrate) by using a wire ingot, so that the thickness after drying is 7/zm, so that the solvent is in i〇〇°c. After drying for 2 minutes, the first ultraviolet ray was irradiated for 1.2 seconds from the oriented substrate side at 4 〇mW/cm 2 on the obtained crucible. Then, one side was 3»c/sec. The heating rate is increased to reach the temperature of 9 (rc (maintained at 9 到达 after arrival), while The second ultraviolet ray was irradiated for 60 seconds at 4 mW/cm 2 in an air atmosphere of 40 1341 928. Then, the third ultraviolet ray was irradiated for 10 seconds at 60 mW/cm 2 from the oriented substrate side in a nitrogen atmosphere at 50 ° C to obtain a selected wavelength. Wide-band torsion layer liquid crystal film of 425 to 900 nm. The reflection spectrum of the wide-band torsion layer liquid crystal film is shown in Fig. 4. 5 Using a light-transmitting adhesive, the upper portion of the obtained wide-band 杻 layer liquid crystal film (circular polarized reflection plate) is obtained. Copying a negative two-axis phase difference plate. The negative two-axis phase difference plate is obtained by the following method, that is, the photopolymerizable nematic liquid crystal monomer ("LC242" manufactured by BASF Corporation). The optically active agent (LC756, manufactured by BASF Corporation) was added with cyclopentanone as a solvent in 7 parts by weight, and the solution was made up to 30% by weight, and the concentration of the reflection center was 350 nm, and the solid content was adjusted with respect to the solid content. Adding 5% by weight of a photopolymerization initiator, reducing the force, and aging 907, preparing a coating liquid, using a wire ingot to apply the above solution to an extended polyethylene terephthalate substrate, so that the thickness after drying is 4/zm, dry the solvent at 100 ° C for 2 minutes Then, 'the temperature is once raised to the isotropic transfer temperature 15 of the liquid crystal monomer, and then slowly cooled to form a layer having a uniform orientation state. The obtained layer is irradiated with ultraviolet rays of 50 mW/cm 2 for 5 seconds. The phase difference plate was obtained in a fixed orientation state, and the phase difference of the negative two-axis phase difference plate was measured, and the light with respect to the wavelength of 550 nm was 2 nm in the front direction, and tilted by 30. The phase difference value during the measurement was The measurement of the phase difference of 120 nm ° and 'phase difference' was carried out by K0BRA-2IADH manufactured by JJ Scentific Instruments 20 Corporation. Further, in the upper portion, a light-transmitting adhesive was used in the same manner, and a circular polarizing reflector was laminated in the same manner as described above to obtain a polarizing element. On the obtained polarizing element, a further 4 sheets (front surface retardation i4 〇 nm) obtained by stretching a polycarbonate film on one axis were obtained to obtain a linear polarizing element. A polarizing plate (TEG1465DU manufactured by Tosoh Corporation 41 1341928) was attached to the linear polarizing element so that the direction of the transmission axis was uniform, and a polarizing plate-integrated polarizing element was obtained. Example 2

The coating liquid prepared in Example 1 was applied to the extended polyethylene terephthalate film (oriented substrate) by a wire ingot to have a thickness of 7#m after drying, and the solvent was 100. Dry at °C for 2 minutes. On the obtained film, the first ultraviolet ray was irradiated for 120 seconds from the oriented substrate side at 40 mW/cm 2 in an air atmosphere of 40 ° C, and then the temperature was raised to a temperature increase rate of 10 ° C / sec. After 90 ° C (maintained at 90 ° C after arrival), the second ultraviolet light 10 was irradiated for 60 seconds at 4 mW/cm 2 in an air atmosphere. Subsequently, ultraviolet irradiation was carried out at 60 mW/cm 2 for 10 seconds from the oriented substrate side under a nitrogen atmosphere of 50 ° C to obtain a wide-band twisted layer liquid crystal film having a selected wavelength of 430 to 900 nm. The reflection spectrum of the wide-band twisted layer liquid crystal film is shown in Fig. 5. A negative two-axis phase difference plate similar to that of Example 1 was produced by using a light-transmitting adhesive to the upper portion of the obtained wide-band twisted layer liquid crystal film (circularly polarized light-reflecting plate).

Further, in the upper portion, a light-transmitting adhesive was used in the same manner, and a circularly polarizing reflector similar to the above was laminated, and a polarizing element was obtained. The obtained polarizing element was obtained by extending a polycarbonate film on one axis, and a quarter plate (front surface difference of 140 nm) was obtained to obtain a linear polarizing element. Further, on the λ/4 plate, a λ/2 plate (front surface retardation of 270 nm) obtained by stretching the polycarbonate film by 20 was obtained to obtain a linear polarizing element. A polarizing plate (TEG1465DU, manufactured by Nitto Denko Corporation) was bonded to the linear polarizing element, and the direction of the transmission axis was aligned to obtain a polarizing plate-integrated polarizing element. The layers are formed by the angle of the extension axis (phase retardation axis) of the 1/4 plate, the 1/2 plate, and the extension axis (absorption axis) of the polarizing plate as shown in Fig. 3. In Fig. 3, PL is 42 1341928 absorption type polarizing plate, Cl is; W4 board (front surface difference MOnm), and C2 is Λ/2 plate (front surface difference 270 nm). The arrow of PL indicates the extension axis (longitudinal direction), and 0 1 is 17_5. , 02 is 80°. Example 3 5 Photopolymerizable liquid crystal original compound (using a polymerizable nematic liquid crystal monomer,

The compound 20 of Table 1 has a molar extinction coefficient of 2100 dm 3 mol km 丨@33411111, 36000 (31113111〇1 "<:111-1@31411111. purity> 99%), 94.8 parts by weight, a polymeric optically active agent ( LC756) manufactured by BASF Co., Ltd. 5.2 parts by weight and a solvent (cyclopentanone) were mixed and mixed into a solution having a selective reflection center wavelength of 550 nm 10 , and 0.3% by weight of a photopolymerization initiator was added to the solid content in the solution.亍彳夂S 力 乂 乂 乂 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , a benzoic acid ester film (oriented substrate), the thickness after drying was m, and the solvent was dried at 100 ° C for 2 minutes. On the obtained film of 15 at 40 ° C in an air environment, from the orientation group On the material side, the first ultraviolet ray was irradiated at 40 mW/cm 2 for 2 seconds, and then the temperature was raised to 90 ° C at a temperature increase rate of 3 ° C / sec (maintained at 90 ° C after arrival) while being in an air atmosphere. The second ultraviolet ray was irradiated at 4 mW/cm 2 for 30 seconds, and then under a nitrogen atmosphere of 50 ° C, from the side of the oriented substrate to 6 mW/cm2 is subjected to the third ultraviolet irradiation for 10 seconds, 20 to obtain a wide-band twisted-layer liquid crystal film having a wavelength of 420 to 925 nm. The reflection spectrum of the wide-band twisted-layer liquid crystal film is shown in Fig. 6. Using a light-transmitting adhesive, On the upper portion of the obtained wide-frequency twisted-layer liquid crystal film (circular polarizing reflector), a negative two-axis phase difference plate similar to that of Example 1 was reproduced. Further, a translucent adhesive was used in the upper portion, and the copy laminate was the same as described above. 43 1341928 circular polarizing reflector, obtaining a polarizing element. On the obtained polarizing element, a λ/4 plate obtained by biaxially stretching a polycarbonate film (front phase difference 125 nm, Nz coefficient - L0) is obtained to obtain a linear polarizing element. A polarizing plate (TEG1465DU, manufactured by Nitto Denko Corporation) was bonded to the linear polarizing element so that the transmission axis direction was uniform, and a polarizing plate-integrated polarizing element was obtained.

A photopolymerizable liquid crystal original compound (using a polymerizable nematic liquid crystal monomer, the compound 3 of the above Table 1, a molar extinction coefficient of 2200 dm3m〇rlcm'1@334 nm '37000dm3m〇r1cm'1@314nm) 94.8 10 parts by weight, Polymeric optical rotator (LC756, manufactured by BASF Corporation) 5.2 parts by weight and a solvent (cyclopentanone) were mixed and mixed into a solution having a selective reflection center wavelength of 550 nm, and 3% by weight of photopolymerization was added to the solid content in the solution. The agent (Yu パスパシ亇 / レテ &; 夂殳 乂 乂 乂 彳 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Applying the coating liquid to the 15 extended polyethylene p-phthalate film (oriented substrate) by using a wire ingot, so that the thickness after drying is 7

The solvent was dried at 1 ° C for 2 minutes. On the obtained film, the first ultraviolet ray was irradiated for 2.2 seconds from the oriented substrate side at 50 mW/cm 2 in an air atmosphere of 4 Torr. Subsequently, the temperature was raised to 9 ° C (at 90 ° C after arrival) at a temperature elevation rate of 3 ° C / sec, and the ultraviolet ray was irradiated for 20 seconds at 4 mW/cm 2 in an air atmosphere. Subsequently, the third ultraviolet ray was irradiated from the oriented substrate side at 60 mW/cm 2 for 10 seconds in a nitrogen atmosphere at 50 ° C to obtain a wide-band twisted layer liquid crystal film having a selected wavelength of 455 to 930 nm. The reflection spectrum of the wide-band 杻 liquid crystal film is shown in Fig. 7. Comparative Example 1 44 1341928 The coating liquid prepared in Example 1 was applied to an extended polyethylene p-phthalate film (oriented substrate) by a wire ingot to have a thickness of 5 m after drying. The solvent was dried at 1 ° C for 2 minutes on the obtained film, and under the air environment of Tc, 'the first ultraviolet irradiation was performed at 50 mW/cm 2 from the oriented substrate side for 1 sec 5 seconds'. Then, at 50 Under the nitrogen environment of °c, the external irradiation of rabbits was carried out at 60 mW/cm2 for 10 seconds from the side of the oriented substrate to obtain a wide-band twisted-layer liquid crystal film with a selected wavelength of 435 to 835 nm. The reflection spectrum of the wide-band twisted-layer liquid crystal film was shown in the eighth. In the upper portion of the obtained wide-band twisted-layer liquid crystal film (circular polarized light-reflecting sheet), a negative two-axis phase difference plate similar to that of Example 复印 was used, and the same was applied to the upper portion thereof. The polarizing element was laminated on the same circular polarizing reflector as described above to obtain a polarizing element. The obtained polarizing element was then subjected to a λ/4 plate obtained by stretching the polycarbonate film in the axial direction (the front phase difference was 14 〇). Nm), a linear polarizing element is obtained. The linear polarizing element The polarizing plate ("TEG1465DU" manufactured by Nitto Denko Corporation" was bonded to the direction of the axis to obtain a polarizing plate-integrated type 15 polarizing element. Comparative Example 2 The coating liquid prepared in the first embodiment was coated with a wire ingot. Extending the polyethylene to the benzoic acid lysate (orienting substrate) so that the thickness after drying is 7/zm, and the granules are dried at 100 C2 minutes. On the obtained film, under the air ring of the peach, The first ultraviolet ray was irradiated to the substrate 铡 at 4 〇 mW/cm 2 for 1.2 seconds. Then, the temperature was raised to 9 〇 ° C at a temperature of 3 C / sec. After reaching 90 c, it was at 90 c in an air atmosphere. The treatment was carried out for 2 sec. Next, ultraviolet irradiation was carried out at 60 mW/cm 2 from the side of the oriented substrate under the nitrogen gas of C, and a wide-band twisted-layer liquid crystal film having a selected attack length of still (10) was applied. 1341928 The reflection spectrum of the frequency twisted layer liquid crystal film is shown in Fig. 9. Using the light-transmitting adhesive, the upper part of the wide-band twisted-layer liquid crystal film (circular polarized reflection plate) obtained is copied in the same manner as in the first embodiment. Axial phase difference plate. Also in the upper part of the same, using a light-transmitting adhesive, A 5-polar polarizing reflector was laminated to obtain a polarizing element, and a λ/4 plate (front surface retardation of 140 nm) obtained by stretching a polycarbonate film on one axis was obtained on the obtained polarizing element to obtain a linear polarizing element. A polarizing plate (TEG1465DU, manufactured by Nitto Denko Corporation) was bonded to the linear polarizing element to obtain a polarizing plate-integrated polarizing element. The comparative example 3 used the coating liquid prepared in the first embodiment. The ingot was coated on an extended polyethylene terephthalate film (oriented substrate) so that the thickness after drying was 7/zm, and the solvent was dried at 100 ° C for 2 minutes. On the obtained film, at 40 ° C In the air environment, the first ultraviolet ray was irradiated for 120 seconds at a temperature of 40 mW/cm 2 for 15 seconds from the direction of the oriented substrate, and then the temperature was raised to 90 ° C at a temperature increase rate of 3 ° C / sec (maintained at 90 ° C after arrival). The second ultraviolet ray was irradiated for 60 seconds at 4 mW/cm 2 in an air atmosphere to obtain a wide-band twisted layer liquid crystal film having a selected wavelength of 425 to 900 nm. The reflection spectrum of the wide-band twisted layer liquid crystal film is shown in Fig. 10. A negative two-axis phase difference plate similar to that of Example 1 was produced by using a light-transmitting adhesive to the upper portion of the obtained wide-band twisted-layer liquid crystal film (circularly polarized light-reflecting plate). Further, in the upper portion, a light-transmitting adhesive was used in the same manner, and a circularly polarizing reflector similar to the above was laminated, and a polarizing element was obtained. On the obtained polarizing element, a λ/4 plate (front surface retardation of 140 nm) obtained by stretching a polycarbonate film on one axis was used to obtain a linear polarizing element. A polarizing plate ("TEG1465DU" manufactured by Nitto Denko 46 1341928) was attached to the linear polarizing element, and the polarizing plate-integrated polarizing element was obtained by matching the axial direction. (Liquid crystal display device) The polarizing plate-integrated polarizing element obtained in each of the above examples was used as a 5 TFT-LCD lower plate, and the acrylic-based adhesive material (thickness 25 "m, refractive index 1.47) was used. ) A light-scattering adhesive (20% by weight) of spherical cerium oxide particles (refractive index 144, diameter m,) is embedded in the upper plate side as a laminated polarizing plate (manufactured by Nitto Denko Corporation) , TEG1465DU). Further, a cold cathode tube having a diameter of about 3 mm was placed on the side surface of the light guide body having a fine 稜鏡 10 structure, and was covered with a light source holder formed of a silver-deposited polyethylene terephthalate film. A silver vapor-deposited polyethylene terephthalate film reflector is disposed under the light guide plate, and a polyethylene terephthalate film having a disordered layer formed of stupid ethylene bubbles is formed on the surface of the light guide plate. This is disposed as a light source on the lower side of the polarizing plate-integrated polarizing element. In the case of the polarizing plate-integrated polarizing element of the first and third embodiments and the comparative examples 1 to 3, the case of the polarizing plate-integrated polarizing element of the second embodiment is shown in Fig. 2 . In Fig. 1 and Fig. 2, PL is an absorbing polarizing plate, D is a viewing angle widening film (diffusion bonding material), LC is a liquid crystal cell, C1 is a λ/4 plate, C2 is a /2 plate, and Α is a reflection. Polarized photon (a): circular polarizing plate, Β is a phase difference plate (b): 20 C plate, S is a side light type light guide plate, and R is a diffuse reflection plate. Further, X is a polarizing element, Y is a linear polarizing element, and Z is a polarizing-integrated linear polarizing element. Further, in the fourth embodiment, only the reflection wavelength band, the bandwidth (??), and the pitch variation were selected for evaluation. <Evaluation method> 47 The following evaluation was performed on the wide-band torsion layer liquid crystal film (circularly polarized light-reflecting sheet) and the polarizing plate-body type polarizing element obtained above. The results are shown in Table 2. Further, the respective step conditions of the examples and comparative examples are also shown in Table 2. (Selecting the reflection wavelength band and the bandwidth (△ long)) The spectrophotometric 4 (manufactured by Dayuan Electronics Co., Ltd., the instantaneous multi-photometry system MCPD2_ measures the reflection spectrum of the wide-band torsion layer liquid crystal film, and obtains the selected reflection wavelength band and the half-value bandwidth. Δλ. The half-valued bandwidth Δλ is used as the reflection bandwidth of the semi-reflectivity at one of the maximum reflectances. (Pitch change) The wide-band torsion layer liquid crystal film is measured near the ultraviolet ray irradiation surface by the surface ΤΕΜ photograph (1/zm from the ultraviolet ray irradiation surface) The lower layer is longer than the pitch near the air interface (the lower layer from the air interface) and the middle thereof. (Reliability) The wide-band 杻 layer liquid crystal film is put into 8〇, and 6〇<>>9〇%RH Reliable I1 students "Test 500 hours" to evaluate whether the surface of the powder can be seen. The 〇: no precipitates. x: There are precipitates. (Front brightness) Place the polarizing plate-integrated polarizing element on the dots. In the printed backlight, the polarizing plate was placed on the side of the polarizing plate, and it was evaluated by a luminance meter (manufactured by TOPCON, BM-7). (Twisting change in color tone) The liquid crystal was evaluated by ELDIM's viewing angle measuring device EZ-CONTRAST with the following criteria. Display The color change of the tilt of the device. △xy= ((Χ〇,χ丨)2+ (y〇—y丨)2) 0.5 1341928 Front color (x〇, y〇), chromaticity from tilt ± 60° (Xi, y!) Good: the color change Axy at a viewing angle of 60° is less than 〇.〇4. Poor: the hue change Axy at a viewing angle of 60° is 0.04 or more. Table 2 Example 1 Example 2 Example 3 Example 4 Comparative Example Comparative Example 2 Comparative Example 3 Step (1) Ultraviolet illuminance (mW/cm2) 40 40 40 50 50 40 40 Temperature (°c) 40 40 40 40 60 40 40 Time (seconds) 1.2 1.2 1.2 2.2 10 1.2 1.2 Environment Oxygen Oxygen Oxygen Oxygen Oxide Step (2) Ultraviolet Illumination (mW/cm2) 4 4 4 4 - - 4 Heating Temperature (°c / sec) 3 10 3 3 - 3 3 Arrival Temperature (°C) 90 90 90 90 - 90 90 Time (seconds) 60 60 30 60 - 20 60 Ambient Oxygen Oxygen - Oxygen Oxygen Step (3) Ultraviolet Illumination (mW/cm2) 60 60 60 60 60 60 Heat Temperature rc) 50 50 50 50 50 50 - Time (seconds) 10 10 10 10 10 10 - Environment 龀 Nitro nitrogen, Nitrogen, Nitrogen • __ 1 Equivalent reflection band (nm) 425-900 430-900 420-925 450-930 435-835 415-710 425- 900 Selecting the reflection bandwidth (half-value bandwidth Δλ : nm) 475 470 505 480 400 295 475 Pitch change substrate side - air interface side large - * > small - small - small - small - large - small - > Small - small substrate 恻 (nm) 0.54 0.54 0.56 0.56 0.38 0.42 0.54 Intermediate (nm) 0.40 0.40 0.41 0.41 0.50 0.33 0.40 Air interface side (nm) 0.26 0.26 0.26 0.27 0.27 0.25 0.26 Reliability 〇〇〇 - 〇 〇X Front brightness (cd/cm2) 138 140 142 • 135 110 138 The color tone of the tilt changes well and is good - bad and bad

In the embodiment, a twisted layer liquid crystal film having a selective reflection wavelength in a wide frequency band including a long wavelength region can be obtained. The twisted layer liquid crystal film is highly reliable, and the polarizing element used as a circular polarizing plate is also excellent in brightness enhancement characteristics. In addition, the liquid crystal display device using the S-transparent element separates the display information of the field of the unpolarized inversion in the oblique direction by light diffusion, so that it is difficult to generate a hue change or a harmonic inversion from the oblique direction, and a wide viewing angle can be obtained. Liquid crystal display device. INDUSTRIAL APPLICABILITY A wide-frequency twisted-layer liquid crystal film obtained by the production method of the present invention can be used as a circularly polarizing five-light plate (reflective polarizer), which can be used for a linear polarizing element, an illumination device, a liquid crystal display device, or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view showing an enlarged liquid crystal display device using the viewing angles of the polarizing plate-integrated polarizing elements of Examples 1 and 3 and Comparative Examples 1 to 3. Fig. 2 is a conceptual view showing an enlarged liquid crystal display device by the viewing angle of the polarizing plate-integrated polarizing element of the second embodiment. Fig. 3 is a view showing the axial angles of the respective layers in the polarizing plate-integrated polarizing element of the second embodiment. Fig. 4 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 1. 15 Fig. 5 is a reflection spectrum of a twisted layer liquid crystal film produced in Example 2. Fig. 6 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 3. Fig. 7 is a reflection spectrum of the twisted layer liquid crystal film produced in Example 4. Fig. 8 is a reflection spectrum of a bismuth liquid crystal film produced in Comparative Example 1. Fig. 9 is a reflection spectrum of the twisted layer liquid crystal film produced in Comparative Example 2. 20 Fig. 10 is a reflection spectrum of the twisted layer liquid crystal film produced in Comparative Example 3. [The main components of the diagram represent the symbol table] PL... Absorptive polarizing plate C1...λ/4 plate D...Viewing angle expansion film (diffusion bonding material) C2"a/2 plate LC...liquid crystal cell A...reflecting polarizer (a ): circular polarizing plate 50 1341928 B···phase difference plate (b) : C plate Y... linear polarizing element S··· side light type light guide plate 偏...polarizing integrated linear polarizing element R···diffusion reflector X ...polarizing element 51

Claims (1)

1341928 Patent Application No. 93107989 Patent Application Revision This revision period: January 28, 100, the patent application scope: 1. A method for manufacturing a wide-band twisted-layer liquid crystal film, comprising a polymerizable liquid crystal original compound ( A) a step of applying a liquid crystal mixture of the polymerizable optical agent (B) to the oriented substrate, and irradiating the liquid crystal mixture with ultraviolet rays to cure the polymerization of 5 to produce a broadband twist layer having a reflection bandwidth of 200 nm or more. In the liquid crystal film, the ultraviolet polymerization step includes: irradiating the ultraviolet ray at a temperature of 20 ° C or higher with a UV irradiation intensity of 20 to 200 mW/cm 2 in a state where the liquid crystal mixture is brought into contact with the oxygen-containing gas, from the side of the oriented substrate Step (1) of ultraviolet irradiation for 0.2 to 5 seconds; 10 Next, in a state where the liquid crystal layer is brought into contact with the oxygen-containing gas, the temperature increase rate is 2 ° C / sec or more, and is higher than the step (1 ) and at 60 ° C a step (2) of irradiating the ultraviolet ray for 10 seconds or more from the side of the oriented substrate at a temperature lower than the reaching temperature of the step (1); and then In the absence of oxygen, step (3) of UV irradiation. The method of producing a wide-band twisted-layer liquid crystal film according to the first aspect of the invention, wherein the pitch length change of the wide-band 杻 liquid crystal film is continuously narrowed from the side of the oriented substrate. 3. The method for producing a wide-band twisted-layer liquid crystal film according to the first aspect of the invention, wherein the polymerizable liquid crystal original compound (A) has one polymerizable functional group, and the 20 polymerizable optically active agent (B) has two The above polymerizable functional group. 4. The method for producing a wide-band twisted-layer liquid crystal film according to claim 1, wherein the molecular extinction coefficient of the polymerizable liquid crystal original compound (A) is: Ol-SOOdn^mol-icnr^SGSnm, 10~, and 52 1341928 j_^31〇7989 Patent Application Revision Patent Revision Amendment Date: October 20th, summer 10th, lOOOO-lOOOOOdn^mol-'ciTr^SMnm. 5. The method for producing a wide-band twisted layer liquid crystal film according to claim 1, wherein the polymerizable liquid crystal original compound (A) is represented by the following general formula (1): The compound represented (wherein, |^~12 can be the same or different, representing _F, Η, CH3, C2H5 or 〇CH3, Rl3 represents a Η or ~CH3, X, represents the general formula (2 ): — (CH2CH20) a—(CH2) b—(〇) c—, X2 represents a CN or an F′ 'only'. In the general formula (2), a is an integer from 0 to 3, and b is 0 to 12. Integer, c is 〇 or 1, and when a=i~3, 1>=0, c=〇, a=〇10, b=l~12, c=0~1) 〇6· _ kinds of polarizing elements Between the at least two reflective polarizers (a) in which the wavelength bands of the selective reflection of the polarized light overlap each other, the front phase difference (normal direction) is almost zero and is approximately 3 相对 with respect to the normal direction. The obliquely incident incident light has a phase difference layer (b) of a phase difference of 1/8 or more, wherein 15 ^ , the reflective polarizer (a) is a circular polarizing plate, which is used for the patent application range 1 The wide-band 杻 liquid crystal 制 obtained by the method of manufacture. 7. The polarizing element according to claim 6, wherein the selective reflection wavelengths of the at least two layers of the reflective polarizers (a) overlap each other in a wavelength range of 5 SOnm ± i 〇 nm. 20 8 The polarizing element of the sixth application of the patent scope, wherein the phase difference layer (b) is: μ 53 1341928. The revised period: January 28, 100, special shot, please use the full-length correction to fix it. A plane orientation of a liquid crystal phase of a twisted layer having a selective reflection wavelength range outside the visible light region, for fixing the vertical alignment state of the rod-shaped liquid crystal, for fixing the phase of the phase of the discotic liquid crystal or the orientation state of the tube bundle phase, 5 The orientation of the polymer film 2 is oriented or the inorganic layered compound having a negative one-axis property is oriented and fixed, so that the normal direction of the surface constitutes light extraction. 9. A linear polarizing element which is laminated on a polarizing element of the scope of the patent application of the λ/4 plate to obtain a linear polarizer. In the linear polarizing element of claim 9, the twisted layer liquid crystal film of the laminated circular polarizing plate is formed on the Λ/4 plate so that the pitch length is continuously narrowed. 11. The linear polarizing element of claim 9, wherein the λ/4 plate is phase-corrected by a 2-axis extended oblique incident light to improve the phase difference plate of the viewing angle. 15 12' The linear polarizing element of claim 9, wherein the λ/4 plate is a liquid crystal polymer type retardation plate obtained by coating and fixing a nematic liquid crystal or a matrix liquid crystal. a linear linear polarizing element of 9th, wherein the λ/4 plate is expressed by the formula (nx - nz) / ( η χ - ny) when the principal refractive index in the in-plane is nx and the main refractive index in the thickness direction is η , The coefficient of definition is equal to -0.5~-2·5. A linear polarizing element which is laminated on a λ/4 plate of a linear polarizing element of claim 9 of the patent application. 15· A linear polarizing element that aligns the transmission axis direction of the absorbing polarizer with the transmission axis of the linear polarizing element of claim 9 and the patent range revision of the correction range of the linear deviation 54 丄~~~~ : On January 28, 100, the λ/4 plate side of the illuminating element is laminated with the absorbing type photon. The illumination S S is a linear polarizing element of claim 9 in the surface side of the surface light source having the reflective layer on the inner side. A liquid crystal display device having a liquid crystal cell on the light emitting side of the illumination device 5 of claim 16 of the patent application. 18. The viewing angle-enhancing liquid crystal display device is provided on a liquid crystal display device of the seventh aspect of the patent application, wherein a viewing angle expansion film that diffuses light passing through a visual side of the liquid crystal cell is disposed on a visual side of the liquid crystal cell. Founder. 19. The liquid crystal display device is expanded from the viewpoint of the application of the ninth aspect of the patent application, and the diffusion plate having substantially no rear scattered and polarized light is used as the viewing angle expansion film. 55