JP5578166B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to a method for producing a laminate, and more particularly to a method for producing a pattern retardation film.

  In recent years, flat panel displays capable of three-dimensional display have begun to attract attention, and are also commercially available. In addition, it is expected that the future flat panel display is capable of three-dimensional display, and it is expected that the performance is naturally required, and a flat panel display capable of three-dimensional display is being studied in a wide range of fields.

  In order to perform three-dimensional display on a flat panel display, it is usually necessary to display a right-eye image and a left-eye image separately for the viewer in some way. As a method for separately displaying the right-eye video and the left-eye video, for example, a passive method is known. Such a passive three-dimensional display method will be described with reference to the drawings. FIG. 7 is a schematic view showing an example of a passive three-dimensional display. As shown in FIG. 7, in this method, first, the pixels constituting the flat panel display are divided into a plurality of types of pixels, a right-eye video display pixel and a left-eye video display pixel, in a pattern, and one group The pixel displays a right-eye image, and the other group of pixels displays a left-eye image. Also, using a linearly polarizing plate and a patterned retardation film on which a patterned retardation layer corresponding to the division pattern of the pixel is formed, a right-eye image and a left-eye image are orthogonal to each other. Convert to polarized light. In addition, the viewer wears circular polarizing glasses that employ circular polarizing lenses that are orthogonal to each other for the right-eye lens and the left-eye lens, so that the right-eye image passes only through the right-eye lens and the left-eye image is displayed. Pass only through the lens for the left eye. In this way, the passive method enables three-dimensional display by allowing the right-eye image to reach only the right eye and the left-eye image to reach only the left eye.

  Such a passive method has an advantage that three-dimensional display can be easily performed by using the pattern retardation film and the corresponding circular polarizing glasses.

By the way, as described above, in the passive method, it is essential to use a pattern retardation film. However, such a pattern retardation film has not been widely researched and developed, and can be used as a standard technique. There is nothing that has been established. As an example, a polymer film having optical anisotropy is formed by polymerizing a polymerizable liquid crystal composition containing a compound having —C (CF ₃ ) ₂ — or —SO ₂ —, and this polymer It has been proposed to use a film as a retardation plate (see Patent Document 1).

JP 2007-16213 A

  However, research and development of the retardation layer is in the process of development. In addition to the composition of the polymerizable liquid crystal composition constituting the retardation layer, from various viewpoints including the manufacturing method, more precise control of the orientation direction, by charging There is a need to improve various properties such as improvement of appearance defects.

  In order to solve the above-mentioned problems, the present inventor has made extensive studies, and after forming a layer made of a polymerizable liquid crystal composition on a substrate, an application substrate on which the polymerizable liquid crystal composition is applied is formed. It has been found that the orientation direction can be controlled more strictly and the appearance defect due to electrification can be improved by drying the polymerizable liquid crystal composition after removing the charge, and the present invention has been completed. Specifically, the present invention provides the following.

  (1) The present invention includes a step of forming a layer made of a polymerizable liquid crystal composition on a substrate, and a step of curing the layer made of the polymerizable liquid crystal composition by polymerizing the polymerizable liquid crystal composition. In the step of curing a layer comprising the polymerizable liquid crystal composition, the polymerizable liquid crystal composition is applied after the polymerizable liquid crystal composition is applied and before drying. It is a manufacturing method of a laminated body provided with the process of neutralizing the apply | coated application base material.

  (2) Moreover, this invention is a manufacturing method of the laminated body as described in (1) by which the said static elimination is performed from the application surface side.

  (3) The present invention is also described in (1) or (2), in which the charge removal is performed after applying the polymerizable liquid crystal composition and before passing through the first transport roller. It is a manufacturing method of this laminated body.

  (4) Further, according to the present invention, in the static elimination, a conductive fiber wire in which conductive fibers are string-like or thread-like is linearly stretched on an electrode support to form a static elimination electrode, and an AC high voltage is applied thereto. In addition, the conductive fiber is crossed in a non-contact manner with respect to the conductive fiber wire, and the distance between the surface of the layer made of the polymerizable liquid crystal composition and the conductive fiber wire is 20 mm or less. ) To (3).

  (5) Further, in the present invention, the laminate is a pattern retardation film, and the step of forming a layer composed of the polymerizable liquid crystal composition includes providing a pattern alignment layer by applying an alignment pattern on a substrate. After the forming step, the step of forming a retardation layer forming layer made of a polymerizable liquid crystal composition on the pattern alignment layer is performed, and the step of curing the layer made of the polymerizable liquid crystal composition is performed by the polymerization. It is a manufacturing method of the laminated body in any one of (1) to (4) performed by arranging a liquid crystalline composition along the said alignment pattern, and forming a phase difference layer.

  (6) Further, according to the present invention, an alignment deviation angle defined by an absolute value of an angle difference between an alignment axis set when forming the alignment pattern and an alignment axis of the retardation layer is within 2 degrees. (5) is a manufacturing method of the layered product.

  According to the present invention, by applying it to a pattern retardation film, it is possible to provide a laminate in which the orientation direction is more strictly controlled and the appearance defect due to charging is improved.

It is the schematic of the laminated body which concerns on this invention. It is the schematic which shows an example of the manufacturing method of the pattern phase difference film of FIG. It is the schematic which shows the conveyance state of a laminated body until it moves to the leveling apparatus 41 after static elimination of a laminated body. It is the schematic which shows the state of a polymerizable liquid crystal composition when a polymerizable liquid crystal composition is apply | coated to the pattern orientation layer. In prior art, it is the schematic which shows the state of the polymeric liquid crystal composition after conveying the laminated body containing the base material 11 / pattern alignment layer 12 / layer 13 for phase difference layer formation. FIG. 2 is a schematic view showing a static eliminator 40. It is a figure where it uses for description of the three-dimensional image display by a passive system.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Laminated body>
FIG. 1 is a view showing a laminate 1 obtained by the manufacturing method of the present embodiment. This laminate 1 is a pattern retardation film, and is hereinafter also referred to as “pattern retardation film 1”. In the following, “pattern phase difference” is abbreviated as “phase difference”, but “phase difference” is synonymous with “pattern phase difference” unless otherwise specified. The retardation film 1 is obtained by forming a pattern alignment layer 12 on a substrate 11 and forming a retardation layer 13 containing a polymerizable liquid crystal composition on the pattern alignment layer 12.

[Substrate 11]
The base material 11 is a transparent film material, has a function of supporting the pattern alignment layer 12, and is formed in a long shape.

[Pattern orientation layer 12]
The pattern alignment layer 12 has two types of alignment patterns alternately. This alignment pattern may be formed by a molding UV method in which a concavo-convex shape is used to transfer the concavo-convex shape, or by light irradiation using a photo-alignment material that exhibits photo-alignment properties by polarized light irradiation. You may form by the photo-alignment system to orient. In the case where the pattern alignment layer 12 is formed by the shaping UV method, the pattern alignment layer 12 may be any material as long as it contains a widely used energy ray curable resin (such as an ultraviolet curable resin). Also good. On the other hand, when forming the pattern alignment layer 12 by a photo-alignment method, the pattern alignment layer 12 needs to contain the photo-alignment material which exhibits photo-alignment property by polarized light irradiation.

[Phase difference layer 13]
Returning to FIG. 1, the retardation layer 13 includes a rod-like compound that exhibits liquid crystallinity and has a polymerizable functional group in the molecule. Since the retardation layer 13 is formed along the alignment pattern, the retardation layer 13 includes a first retardation region 13A corresponding to the region for the right eye and a second retardation region 13B corresponding to the region for the left eye.

<Method for producing retardation film 1>
Below, although the manufacturing method of the phase difference film 1 in the case of forming by a shaping UV system is demonstrated, the phase difference film 1 may be formed by the photo-alignment method.

  FIG. 2 shows a method for producing the retardation film 1 by the shaped UV method. First, (A) The base material 11 is provided from the long film wound up by the roll 31, and the composition coating process which coats the composition 32 for pattern orientation layers on this base material 11 is performed. Subsequently, (B) a solvent removal treatment is performed in which the composition is dried with a dryer 33 to remove the solvent. Subsequently, (C) a molding process is performed to transfer the fine uneven shape formed on the surface of the transfer mold to the surface of the pattern alignment layer forming layer 12 '. The pattern alignment layer 12 is formed by the processes (A) to (C).

  Subsequently, (D) a retardation layer forming coating solution is applied from a retardation layer forming coating solution supply device 39 containing a polymerizable liquid crystal composition for forming a retardation layer to form a retardation layer. A coating solution for forming a retardation layer for forming a coating layer is applied. Thereafter, (E) using the static eliminator 40, a static elimination process for neutralizing the substrate 11 is performed. Thereafter, (F) a leveling process is performed by using the leveling device 41 to make the thickness of the retardation layer forming layer uniform. Then, the pattern alignment layer 12 has the above-mentioned pattern alignment layer 12 by heating the rod-shaped compound contained in the coating film of the retardation layer forming coating solution to a temperature higher than the liquid crystal phase formation temperature by using the dryer 42 (G). An alignment process is performed in which rod-shaped compounds are arranged along different alignment directions of the first alignment region 12A corresponding to the region of the second region and the second alignment region 12B corresponding to the region for the left eye. By this alignment treatment, the retardation layer forming layer becomes the retardation layer 13. Thereafter, (H) the cooling machine 43 is used to perform a cooling process for cooling the laminate composed of the substrate 11 / pattern alignment layer 12 / retardation layer 13, and (I) the ultraviolet irradiation device 44 is used for polymerization. A curing process for polymerizing and curing the rod-shaped compound is performed. Then, after the film (J) is taken up on the take-up reel 45, a cutting process of cutting out to a desired size is performed. The retardation film 1 is produced through the above steps.

[(A) Composition coating treatment]
First, the base material 11 is provided from the long film wound up by the roll 31, and the composition coating process which coats the composition 32 for pattern orientation layers on this base material 11 is performed.

[Base material 11]
The base material 11 is a transparent film material, has a function of supporting the pattern alignment layer 12, and is formed in a long shape.

  The substrate 11 preferably has a small retardation, and an in-plane retardation (in-plane retardation value, hereinafter also referred to as “Re value”) is preferably in the range of 0 nm to 10 nm, and 0 nm to 5 nm. More preferably, it is in the range of 0 nm to 3 nm. If the Re value exceeds 10 nm, the display quality of the flat panel display using the pattern alignment film may be deteriorated, which is not preferable.

Here, the Re value is an index indicating the degree of birefringence in the in-plane direction of the refractive index anisotropic body. When the refractive index in the fast axis direction orthogonal to the axial direction is Ny, and the thickness in the direction perpendicular to the in-plane direction of the refractive index anisotropic body is d,
Re [nm] = (Nx−Ny) × d [nm]
It is a value represented by. The Re value can be measured by, for example, a parallel Nicol rotation method using a phase difference measuring device KOBRA-WR (manufactured by Oji Scientific Instruments). Further, in this specification, unless otherwise specified, the Re value means a value at a wavelength of 589 nm.

  The transmittance of the substrate 11 in the visible light region is preferably 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a transparent film base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

  The substrate 11 is preferably a flexible material having flexibility that can be wound into a roll. Such flexible materials include cellulose derivatives, norbornene polymers, cycloolefin polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, polystyrene. And epoxy resins, polycarbonates, polyesters, and the like. Especially, it is preferable to use a cellulose derivative at the point which is excellent in optical isotropy and can manufacture the pattern orientation film excellent in the optical characteristic.

  Among the cellulose derivatives, cellulose esters are preferably used and cellulose acylates are more preferably used because they are widely used industrially and are easily available.

  As said cellulose acylates, C2-C4 lower fatty acid ester is preferable. The lower fatty acid ester may include only a single lower fatty acid ester such as cellulose acetate, and may include a plurality of fatty acid esters such as cellulose acetate butyrate and cellulose acetate propionate. There may be.

  Among the lower fatty acid esters, cellulose acetate can be particularly preferably used. As the cellulose acetate, it is most preferable to use TAC having an average degree of acetylation of 57.5% to 62.5% (substitution degree: 2.6 to 3.0). Here, the degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation can be determined by measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). In addition, the acetylation degree of TAC can be calculated | required by said method, after removing impurities, such as a plasticizer contained in a film.

  The thickness of the base material 11 is not particularly limited as long as it is within a range in which the necessary self-supporting property can be imparted to the retardation film, depending on the use of the retardation film produced using the pattern alignment film. Usually, it is preferably within the range of 25 μm to 125 μm, more preferably within the range of 40 μm to 100 μm, and even more preferably within the range of 60 μm to 80 μm. If it is less than 25 μm, the necessary self-supporting property may not be imparted to the retardation film, which is not preferable. When the retardation film is longer than 125 μm, when the retardation film is long, when the long retardation film is cut into a single-phase retardation film, the processing waste increases or the cutting blade is worn. May become faster, which is not preferable.

  The base material 11 is not restricted to the structure which consists of a single layer, You may have the structure by which the several layer was laminated | stacked. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked.

[Provision of Substrate 11]
In providing the base material 11, if a long film can be continuously conveyed, it will not specifically limit, The method using a general conveyance means can be used. Specific examples include a method using an unwinder that feeds a roll-shaped long film, a winder that winds the long film, and a method that uses a belt conveyor, a transport roll, and the like. Moreover, the method of using the floating-type conveyance stand which conveys in the state which floated the film for elongate alignment film formation by discharging and sucking | sucking air may be used.

  In addition, the presence or absence of tension applied to the long film at the time of conveyance is not particularly limited as long as it is a method capable of stably and continuously conveying the long film, but the film is conveyed with a predetermined tension applied. It is preferable. This is because continuous conveyance can be performed more stably.

  The color of the conveying means is preferably a color that does not reflect the ultraviolet light that has passed through the long film when it is disposed at a site where the long film is irradiated with ultraviolet light. Specifically, black is preferable. Examples of such a black method include a method of chromium treatment of the surface.

  The shape of the roll 31 is not particularly limited as long as it can stably convey a long film, but when it is arranged at a site where the long film is irradiated with ultraviolet rays, It is preferable that the distance between the surface of the long film and the ultraviolet irradiation device can be kept constant, and it is usually preferable to have a perfect circle shape.

[Composition 32 for pattern alignment layer]
When the pattern alignment layer 12 is formed by the shaping UV method, the pattern alignment layer 12 may be any energy ray curable resin (such as an ultraviolet curable resin) that is widely used in general, for example, UV curable polyol (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates.

  Examples of the polyfunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β-di (meth) acryloyloxypropionate , Trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) isocyanate di (meth) Acrylate, pentaerythritol di (meth) acrylate, 2,3-bis (meth) acryloyloxylethyloxymethyl "2,2,1" heptane, poly 1,2-butadiene di (meth) acrylate, 1,2-bis ( (Meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decandiol di (meth) acrylate, 3,8-bis (meth) acryloyloxymethyltricyclo "5" , 2,10 "decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane , Hydroxypivalin Acid ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate, and the like are exemplified, but not limited thereto.

  Further, if necessary, a monofunctional monomer may be used in combination with the polyfunctional monomer for copolymerization. Examples of the monofunctional monomer include (meth) acrylic acid esters such as N-vinylpyrrolidone, ethyl (meth) acrylate, and propyl (meth) acrylate, ethyl (meth) methacrylate, propyl (meth) acrylate, and isopropyl (meth). (Meth) acrylic acid esters such as acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, isooctyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenyl (meth) acrylate, etc. , Tetrafurfuryl (meth) acrylate. And derivatives thereof such as caprolactone-modified products thereof, styrene, α-methylstyrene, (meth) acrylic acid, and the like, and mixtures thereof.

[Coating of Composition 32 for Pattern Orientation Layer]
In applying the pattern alignment layer composition 32, in the present embodiment, the gravure coating method is applied to apply the pattern alignment layer composition 32. However, the present invention is not limited to this. Specifically, in addition to the gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip pulling method, curtain coating method A die coating method, a casting method, a bar coating method, an extrusion coating method, an E-type coating method, or the like can be used.

  The thickness of the pattern alignment layer forming layer 12 ′ is not particularly limited as long as the desired planarity can be achieved, but is preferably in the range of 0.5 μm to 10 μm, and preferably 1 μm to More preferably, it is in the range of 5 μm, and further preferably in the range of 1.5 μm to 3 μm.

[(B) Solvent removal treatment]
In the solvent removal treatment, the pattern alignment layer composition 32 is dried using a dryer 33 to remove the solvent. In this process, the substrate 11 is turned upside down by a reversing roller (not shown), and then guided to a dryer 33, where the solvent for removing the pattern alignment layer composition 32 is removed, and the next step is performed in a semi-dry state. Send it out.

  The drying temperature is preferably 60 ° C. or higher and 150 ° C. or lower. When the temperature is lower than 60 ° C., the solvent cannot be removed, which is not preferable in terms of causing deterioration in durability. If it exceeds 150 ° C., the substrate 11 and the thin film may shrink, which is not preferable.

  The drying time is preferably 0.5 minutes or more and less than 10 minutes. If it is less than 0.5 minutes, the solvent cannot be removed, which is not preferable in terms of causing deterioration in durability. Exceeding 10 minutes is not preferable because repelling or defects may occur and the base material 11 or the thin film may shrink.

[(C) Molding process]
Subsequently, a molding process is performed to transfer the fine irregularities formed on the surface of the transfer mold to the surface of the pattern alignment layer forming layer 12 ′. In the forming process, a roll plate 34 having a cylindrical shape is a transfer mold, and a fine concavo-convex shape to be used for transfer is formed on the surface of the roll plate 34. Here, the fine concavo-convex shape of the transfer mold is formed by densely forming a streaky pattern on the surface of the master by a method such as rubbing, and the extension direction of the streaks is a region for the right eye and the left eye. A and B are formed so as to be different from each other by 90 degrees and inclined by 45 degrees with respect to the extending direction of each region. In addition, in the inclination with respect to the extension direction of each area | region, when the retardation of the base material 2 is so large that it cannot disregard, it is increased / decreased suitably according to the retardation value. In the forming process, the pattern alignment layer forming layer 12 ′ is pressed against the roll plate 20 using the pressing roller 35, and in this state, ultraviolet rays are irradiated from the substrate 11 side from the ultraviolet irradiation device 36, and the pattern alignment layer composition is formed. The object 32 is cured. Moreover, after peeling the base material 11 from the roll plate 20 with the peeling roller 37, ultraviolet rays are irradiated from the pattern alignment layer forming layer 12 ′ side from the ultraviolet irradiation device 38 to cure the uncured pattern alignment layer composition 32. .

  The wavelength of the ultraviolet light is appropriately set according to the composition of the pattern alignment layer composition 32 and the like. Specifically, the wavelength is 210 nm to 380 nm, preferably 230 nm to 380 nm, more preferably 250 nm to 380 nm. It is preferable to use irradiation light.

  Low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps) Etc. can be illustrated. Of these, a metal halide lamp, a xenon lamp, a high-pressure mercury lamp, and the like can be preferably used.

The irradiation amount of ultraviolet rays is not particularly limited as long as the composition 32 for pattern alignment layer can be cured. For example, when the wavelength is 310 nm, the range is 5 mJ / cm ^{2 to} 500 mJ / cm ² . preferably the inner ^is, more preferably in the range of ^{7mJ / cm 2 ~300mJ / cm 2} , and still more preferably in the range of ^{10mJ / cm 2 ~100mJ / cm 2} .

  The irradiation distance of the ultraviolet rays, that is, the distance in the transport direction of the long film that is irradiated with the ultraviolet rays is not particularly limited as long as it can be the above-mentioned irradiation amount in each exposure process, and the line speed It can set suitably according to etc. When the irradiation distance is short, it becomes easy to achieve high pattern accuracy, and when the irradiation distance is long, there is an advantage that it can be sufficiently cured even when the line speed is high. In addition, as a method of increasing the irradiation distance, a method of increasing the number of irradiation times of ultraviolet rays in each exposure process or increasing the irradiation area in the transport direction can be exemplified.

  When irradiating the thin film with ultraviolet rays, it is preferable to adjust the temperature so that the temperature of the thin film becomes constant. This is because the alignment region can be formed with high accuracy. The temperature of the thin film is preferably 15 ° C to 90 ° C, and more preferably 15 ° C to 60 ° C. Examples of the temperature control method include a method using a temperature control device such as a general heating / cooling device. Specifically, a method using a blower capable of blowing air at a predetermined temperature, a method using a temperature-adjustable as the conveying means, more specifically, a temperature-adjustable conveying roll, The method using a belt conveyor etc. can be mentioned.

  Although the thickness of the pattern orientation layer 12 will not be specifically limited if it is in the range which can form a desired pattern, It is preferable to exist in the range of 100 nm-1000 nm. If it is less than 100 nm, a desired pattern may not be formed. If it exceeds 1000 nm, the adhesion may be reduced, which is not preferable.

[(D) Retardation layer forming coating liquid coating treatment]
Returning to FIG. 2, the coating liquid coating process for forming the retardation layer will be described. In the present embodiment, the retardation layer forming coating solution is applied from the retardation layer forming coating solution supply device 39. A specific coating method is not particularly limited as long as it is a method capable of stably forming a coating film made of a retardation layer forming coating solution on the pattern alignment layer 12. The same thing as what was demonstrated by the material coating process can be illustrated.

[Phase difference layer forming coating solution]
The retardation layer forming coating solution contains one or more polymerizable liquid crystal compounds. This will be described in detail below.

(Polymerizable liquid crystal compound)
The polymerizable liquid crystal compound has a refractive index anisotropy, and has a function of imparting a desired retardation by arranging regularly along an alignment pattern expressed by a shaping treatment. Examples of the polymerizable liquid crystal compound include materials exhibiting a liquid crystal phase such as a nematic phase and a smectic phase, but nematic is preferable in that it can be regularly arranged as compared with liquid crystal compounds exhibiting other liquid crystal phases. It is more preferable to use a liquid crystal compound exhibiting a phase.

  As the liquid crystal compound exhibiting the nematic phase, a material having spacers at both ends of the mesogen is preferably used. Since the liquid crystal compound having spacers at both ends of the mesogen is excellent in flexibility, the use of such a liquid crystal compound can make the pattern retardation film excellent in transparency.

  The liquid crystal compound has a polymerizable functional group in the molecule. By having a polymerizable functional group, it is possible to polymerize and fix the liquid crystal compound, so that the alignment stability is excellent and the phase change is less likely to occur over time. The liquid crystal compound more preferably has a polymerizable functional group capable of three-dimensional crosslinking in the molecule. By having a polymerizable functional group that can be cross-linked three-dimensionally, the sequence stability can be further enhanced. Note that “three-dimensional crosslinking” means that liquid crystal molecules are polymerized three-dimensionally to form a network structure.

  Examples of the polymerizable functional group include polymerizable functional groups that are polymerized by the action of ionizing radiation such as ultraviolet rays and electron beams, or heat. Representative examples of these polymerizable functional groups include radically polymerizable functional groups or cationic polymerizable functional groups. Further, representative examples of the radical polymerizable functional group include a functional group having at least one addition-polymerizable ethylenically unsaturated double bond, and specific examples include a vinyl group having or not having a substituent, An acrylate group (generic name including an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group) and the like can be given. Moreover, an epoxy group etc. are mentioned as a specific example of the said cation polymerizable functional group. In addition, examples of the polymerizable functional group include an isocyanate group and an unsaturated triple bond. Among these, from the viewpoint of the process, a functional group having an ethylenically unsaturated double bond is preferably used.

  Furthermore, it is particularly preferable that the liquid crystal compound has the polymerizable functional group at the terminal. By using such a liquid crystal compound, for example, they can be polymerized three-dimensionally to form a network structure, so that they have column stability and excellent optical properties. This is because the above can be formed. In the present invention, even when a liquid crystal compound having a polymerizable functional group at one end is used, the alignment can be stabilized by crosslinking with other molecules.

  Specific examples of the liquid crystal compound used in the present invention include compounds represented by the following formulas (1) to (16).

  In addition, it is more preferable that the polymerizable liquid crystal compound is composed of only a lone electron pair-free compound that does not have an atom having a lone electron pair other than an oxygen atom. By doing in this way, it can contribute to exhibiting desired phase difference, and suppressing the appearance defect by charge. Moreover, it is preferable that a lone electron pair non-containing compound does not have an electron withdrawing group in a molecule | numerator. Specifically, the lone pair-free compound preferably does not have a cyano group or a halogen group in the molecule, preferably does not have a cyano group or a halogen group at the molecular end, and has a phenyl group in the para position. It is preferred not to have a p-substituted phenyl group substituted with a cyano group or a halogen group at the molecular end.

  The amount of the polymerizable liquid crystal compound is not particularly limited as long as the viscosity of the coating liquid for forming the retardation layer can be set to a desired value depending on the coating method applied on the pattern alignment layer 12, but the above coating is not limited. In the liquid, it is preferably in the range of 5 to 40 parts by mass, and more preferably in the range of 10 to 30 parts by mass. If the amount is less than 5 parts by mass, the amount of the polymerizable liquid crystal compound is too small, and therefore, there is a possibility that the incident light to the retardation layer 13 may not be properly aligned. If the amount exceeds 30 parts by mass, the viscosity of the retardation layer forming coating solution becomes too high, and the workability is inferior.

  As the polymerizable liquid crystal compound, only one kind may be used, or two or more kinds may be mixed and used. For example, as a polymerizable liquid crystal compound, a mixture of a liquid crystal compound having one or more polymerizable functional groups at both ends and a liquid crystal compound having one or more polymerizable functional groups at one end is used. It is preferable because the polymerization density (crosslinking density) and the optical characteristics can be arbitrarily adjusted by adjusting. Further, from the viewpoint of ensuring reliability, a liquid crystal compound having one or more polymerizable functional groups at both ends is preferable, but from the viewpoint of liquid crystal alignment, it is preferable that one polymerizable functional group at both ends is provided.

(solvent)
The above polymerizable liquid crystal compound is usually dissolved in a solvent. The solvent is not particularly limited as long as the polymerizable liquid crystal compound can be uniformly dispersed. For example, hydrocarbon solvents such as benzene and hexane, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone (hereinafter referred to as “CHN”). ) And other ketone solvents, tetrahydrofuran, 1,2-dimethoxyethane, ether solvents such as propylene glycol monoethyl ether (PGME), halogenated alkyl solvents such as chloroform and dichloromethane, methyl acetate, ethyl acetate, butyl acetate, Ester solvents such as propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, anone solvents such as cyclohexane, methanol, ethanol, isopropyl It can be exemplified an alcohol solvent such as alcohol (hereinafter referred to as "IPA".), But is not limited thereto. Moreover, one type of solvent may be sufficient and the mixed solvent of two or more types of solvents may be sufficient.

  The amount of the solvent is preferably 66 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. If it is less than 66 parts by mass, the polymerizable liquid crystal compound may not be uniformly coated and dissolved, which is not preferable. If it exceeds 900 parts by mass, a part of the solvent remains, which is not preferable in that reliability may be lowered and coating may not be performed uniformly.

(Other compounds)
The polymerizable liquid crystal composition may contain other compounds as necessary. The other compound is not particularly limited as long as it does not impair the arrangement order of the polymerizable liquid crystal compound described above, and examples thereof include a polymerization initiator, a polymerization inhibitor, a plasticizer, a surfactant, and a silane coupling agent. Can be mentioned.

(Polymerization initiator)
Examples of the polymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Hiller ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride , Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, N1717 manufactured by Adeka, carbon tetrabromide, tribromophenyl Examples include a combination of a photoreductive dye such as sulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid or triethanolamine. In this embodiment, these photoinitiators can be used 1 type or in combination of 2 or more types.

  The photopolymerization initiator needs to be added within a range that does not significantly impair the alignment of the liquid crystal, and is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. It is more preferably ˜12 parts by mass, further preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 10 parts by mass.

  In addition to the polymerization initiator, a polymerization initiation assistant may be used in combination. Examples of polymerization initiation aids include tertiary amines such as triethanolamine and methyldiethanolamine, and benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylamidebenzoate. It is not limited.

(Polymerization inhibitor)
The polymerization inhibitor is used to increase the storage stability of the polymerizable liquid crystal composition. As a polymerization inhibitor, for example, reaction of diphenylpicrylhydrazide, tri-p-nitrophenylmethyl, p-benzoquinone, p-tert-butylcatechol, picric acid, copper chloride, methylhydroquinone, methoquinone, tert-butylhydroquinone, etc. Although a polymerization inhibitor can be used, a hydroquinone polymerization inhibitor is preferable from the viewpoint of storage stability, and methylhydroquinone is particularly preferable.

(Surfactant)
The surfactant is used to adjust the dynamic surface tension of the polymerizable liquid crystal composition and suppress lateral stripe unevenness in the retardation layer.

  An example of the surfactant is a fluorine-based surfactant. As the fluorosurfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at at least one of the terminal, main chain, and side chain is preferable, and specific examples thereof include 1,1,2,2-tetra Fluorooctyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycol di (1,1,1, 2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2) -Tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-penty ) Ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, par Anionic surfactants such as sodium fluoro-n-dodecyl sulfonate, sodium fluoroalkylbenzene sulfonate, sodium fluoroalkyl phosphonate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxy Ethylene ether), perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylates, nonionic surfactants such as fluoroalkyl esters, cationic surfactants such as fluoroalkylammonium iodide, fluoroalkylbetaines, etc. It may be mentioned amphoteric surfactants. Among these, nonionic surfactants are particularly preferably used from the viewpoint that the voltage holding ratio when the retardation layer is used in a liquid crystal display element can be maintained satisfactorily.

  Examples of commercially available fluorosurfactants include BM-1000, -1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F183, F178, and the like. F191, F444, F471, F475, F476, F477, F477, F553, F554 (manufactured by DIC), Fluorard FC-170C, FC-171, FC-430, FC-431 ( Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC -103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (hereinafter Manufactured by Shin-Akita Kasei Co., Ltd.), FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (manufactured by Neos) and the like.

  The fluorine-based surfactant is preferably added in a range that does not significantly impair the alignment of the liquid crystal, and is preferably added in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. By adding an amount of 0.01 parts by mass or more, sufficient coating properties can be imparted to the liquid crystal composition, and a good effect of preventing horizontal stripe unevenness can be exhibited. Moreover, it can suppress that the orientation defect arises in the liquid crystal in a phase difference layer, and the electrical reliability of a phase difference layer falls by making addition amount into 5 mass parts or less.

[Thickness of layer for forming retardation layer]
The retardation layer 13 contains a rod-shaped compound, so that the retardation is developed. The degree of the retardation depends on the type of the rod-shaped compound and the thickness of the retardation layer 13. It is to be decided. Therefore, the thickness of the retardation layer forming layer is not particularly limited as long as it is within a range in which a predetermined retardation can be achieved, and is appropriately determined according to the use of the retardation film 1 and the like. Is.

[(E) Static elimination treatment]
Subsequently, using the static eliminator 40, a static elimination process for neutralizing the base material 11 is performed. Conventionally, a laminate including a base material 11, a pattern alignment layer 12, and a retardation layer forming layer 13 ′ is a leveling device using a plurality of rubber rollers 50A, 50B, 50C,... As shown in FIG. 41. However, the polymerizable liquid crystal composition contained in the retardation layer forming layer 13 ′ has a dielectric anisotropy, and its orientation changes when a voltage is applied. Therefore, as shown in FIG. 4, the polymerizable liquid crystal composition 14 in the retardation layer forming layer 13 ′ aligned along the alignment direction defined by the pattern alignment layer 12 is converted into the base material shown in FIG. 3. 11 and the plurality of rubber rollers 50 </ b> A, 50 </ b> B, 50 </ b> C,...

  In the present invention, after the formation of the retardation layer forming layer 13 ′, the base material 11 is neutralized prior to moving to the next step, so that the base material 11 has a plurality of rubber rollers 50A, 50B, 50C,. Even if it contacts, it can suppress that static electricity generate | occur | produces by friction with the base material 11 and several rubber roller 50A, 50B, 50C, ..., As a result, the polymerizable liquid crystal composition 14 before superposition | polymerization It is possible to prevent the orientation from being disturbed.

  The neutralization may be performed after the phase difference layer forming layer 13 ′ is formed and before the layer thickness of the phase difference layer forming layer 13 ′ is made uniform, but the base 11 is made of the rubber rollers 50A, 50B, It is more preferable to carry out until the contact with 50C,.

  FIG. 6 shows a schematic diagram of the static eliminator 40. The static eliminator 40 includes a conductive wire 37a and two supports 37b that are provided so as to sandwich the substrate 11 in the width direction and support the conductive wire 37a, and one of the two supports 37b. The book is connected to an alternating high voltage HV.

  The conductive wire 37a may be a metal wire such as tungsten or stainless steel, or may be a conductive fiber wire in which conductive fibers are string-like or thread-like. However, the conductive wire 37a is conductive in that it has an excellent ability to remove static electricity uniformly. It is preferable to use a fiber wire. Conventionally used conductive fiber wires may be used. For example, blended yarns in which conductive materials containing copper sulfide are mixed with acrylic fibers, and blended yarns of stainless fibers and polyester fibers are known. Yes. Moreover, as a commercial item of a conductive fiber wire, self-discharge type static elimination string Bequistat (manufactured by Bekaert Toami Metal Fiber Co., Ltd.), TSJO4100 (manufactured by Tosco Corporation), static elimination string (trade name: SPS305-B71S B-100, Yazaki Kako Co., Ltd.) Manufactured), explosion-proof static elimination bar (manufactured by Hugle Electronics), static elimination bar (trade name: N10-1600-1800, diameter: 20 mm, manufactured by Fuji Kiko Co., Ltd.), and the like.

  The thickness of the conductive wire 37a is preferably 1 mm or more and 100 mm or less. If it is less than 1 mm, it is not preferable in that it may be cut. If it exceeds 100 mm, it is not preferable in that handling becomes difficult.

  In the static elimination using the static eliminator 40, the conductive wire 37a was stretched linearly on the two supports 37b. The conductive line 37a is crossed in a non-contact manner with a laminate including the substrate 11, the pattern alignment layer 12, and the retardation layer forming layer 13 '. At this time, the distance between the surface of the retardation layer forming layer 13 ′ and the conductive wire 37 a is preferably 20 mm or less, and more preferably 10 mm or less. If it exceeds 20 mm, the static elimination performance is inferior, and the orientation of the polymerizable liquid crystal composition 14 may be disturbed, which is not preferable.

[(F) Leveling process]
Subsequently, a leveling process for making the thickness of the retardation layer forming layer uniform is performed using the leveling device 41. The thickness of the retardation layer forming layer made of the retardation layer forming coating liquid is in a range such that the in-plane retardation of the retardation layer 13 formed thereafter corresponds to λ / 4 minutes. It is preferable to apply to. As a result, the linearly polarized light passing through the first retardation region 13A and the second retardation region 13B can be made into circularly polarized light that is orthogonal to each other, and as a result, a three-dimensional image can be displayed with higher accuracy. is there.

  When the thickness of the retardation layer 13 is set to a distance within a range in which the in-plane retardation of the retardation layer 13 corresponds to λ / 4 minutes, the specific distance is determined by the rod-shaped compound. It will be determined appropriately depending on the type. When a general rod-shaped compound is used, the distance is in the range of 0.5 μm to 2 μm, but is not limited thereto. Note that λ is a wavelength of 500 nm. As a result, the linearly polarized light passing through the retardation layer 13 can be made into circularly polarized light orthogonal to each other, so that a three-dimensional image can be displayed with higher accuracy.

[(G) Orientation treatment]
Subsequently, the rod-shaped compound contained in the coating film of the retardation layer forming coating solution is converted into a rod-shaped compound along different alignment directions of the first alignment region 12A and the second alignment region 12B included in the pattern alignment layer 12. Array. The method for arranging the rod-shaped compounds is not particularly limited as long as the rod-shaped compounds can be arranged in a desired direction. For example, the rod-shaped compounds are heated to a temperature higher than the liquid crystal phase formation temperature using the dryer 42. Can be mentioned.

  The pattern of the retardation layer 13 formed by this process is the same as the pattern of the pattern alignment layer 12, and the first position corresponding to the right eye region is present on the first alignment region 12 A corresponding to the right eye region. A phase difference region 13A is formed, and a second phase difference region 13B corresponding to the region for the left eye is formed on the second alignment region 12B corresponding to the region for the left eye.

  Whether or not the first retardation region 13A and the second retardation region 13B are formed in the retardation layer 13 is determined, for example, when a sample is put in a polarizing plate crossed Nicol and the sample is rotated. It can be evaluated by confirming that the dark line is reversed. At this time, when the pattern composed of the area A for the right eye and the area B for the left eye is fine, it may be observed with a polarizing microscope. Alternatively, the direction (angle) of the slow axis in each pattern may be measured using an AxoScan manufactured by AXOMETRICS (USA).

  The in-plane retardation of the retardation layer 13 is preferably in the range of 100 nm to 160 nm, more preferably in the range of 110 nm to 150 nm, and still more preferably in the range of 120 nm to 130 nm. In the retardation layer 13, the in-plane retardations indicated by the first retardation region 13A and the second retardation region 13B are substantially the same except that the direction of the slow axis is different.

  By the way, when heating the rod-shaped compound to the liquid crystal phase formation temperature or higher using the dryer 42, the rod-shaped compound is not only arranged in a desired direction, but also the coating film of the retardation layer forming coating liquid is dried. The The drying of the coating film may be appropriately adjusted according to the amount of solvent remaining, but the wind speed of the drying air applied to the coating film is preferably 3 m / second or less, particularly 0.5 m / second or less. It is preferable.

  The temperature condition depends on the liquid crystal → isotropic phase transition temperature of the liquid crystal used, but is preferably in the range of 40 ° C. to 150 ° C., more preferably in the range of 50 ° C. to 120 ° C. In particular, it is more preferably in the range of 55 ° C to 110 ° C. The drying time is preferably in the range of 0.2 to 30 minutes, more preferably in the range of 0.5 to 20 minutes, and particularly in the range of 1 to 10 minutes. More preferably it is. This is because the solvent can be removed stably under these conditions.

[(H) Cooling treatment]
Then, the cooling process which cools the laminated body which consists of the base material 11 / pattern orientation layer 12 / retardation layer 13 using the cooler 43 is performed. The cooling process may be performed until the stack reaches room temperature.

[(I) Curing treatment]
Subsequently, a curing treatment for polymerizing and curing the polymerizable rod-shaped compound is performed. The method for polymerizing the polymerizable rod-shaped compound may be arbitrarily determined according to the type of the polymerizable functional group possessed by the polymerizable rod-shaped compound. However, an appropriate amount of a polymerization initiator is added and cured by irradiation with actinic radiation. The method is preferred. The actinic radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable rod-like compound, but it is usually preferable to use ultraviolet light or visible light from the viewpoint of the ease of the apparatus. Specifically, it can be the same as the ultraviolet rays used when forming the pattern alignment layer 12. By undergoing such a curing treatment, they can be polymerized to form a network structure, so that the retardation layer 13 having column stability and excellent optical properties can be obtained. Can be formed.

  The orientation deviation angle defined by the absolute value of the angle difference between the orientation axis set when forming the orientation pattern and the orientation axis of the retardation layer 13 is preferably within 3 degrees, preferably within 2 degrees. It is more preferable. If it exceeds 3 degrees, there is a possibility that uniform orientation cannot be obtained.

<Flat panel display>
The retardation film 1 is preferably used for a flat panel display for three-dimensional display, and has an exceptional effect that it has excellent photo-alignment properties when used for a flat panel display for three-dimensional display.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Examples and Comparative Examples>

<Manufacture of retardation film>
The retardation film which concerns on an Example and a comparative example was obtained through the manufacturing process demonstrated in FIG. In that case, the base material used was a TAC base material (trade name: TD60UL-P, thickness: 60 μm, manufactured by Fuji Film Co., Ltd.) whose surface was antiglare-treated, and the conveyance speed was 12 m / min.

  First, 100 parts by mass of urethane acrylate (trade name: UV1700B, solid content: 100%, manufactured by Nippon Synthetic Chemical Co., Ltd.) and pentaerythritol triacrylate (trade name: light acrylate PE-3A, solid content: 100%, manufactured by Kyoei Chemical Co., Ltd.) ) 100 parts by mass and 8 parts by mass of a photopolymerization initiator (trade name: Lucillin TPO, manufactured by BASF) are dissolved in a diluent so as to have a solid content of 45% and a viscosity of 2500 mPa · s. A composition was obtained. As a diluent, a mixed solution of 80 parts by mass of methyl ethyl ketone and 20 parts by mass of methyl isobutyl ketone was used.

  Then, the said composition for pattern orientation layers was apply | coated to the back surface of the said TAC base material by the gravure coating method so that the film thickness after hardening might be set to 5 micrometers. And it was made to flow for 1 minute in the dryer adjusted to 100 degreeC, and the solvent was evaporated. As a result, a thin film having a thickness of 5 μm was formed.

The thin film was pressed against a roll plate having a fine concavo-convex shape formed on the surface using a pressing roller, and ultraviolet rays were irradiated from the substrate side in this state. At this time, “H bulb” (manufactured by Fusion) was used as the ultraviolet irradiation device. The wavelength of the ultraviolet light was 350 nm, and the integrated light amount was 350 mJ / cm ² . The integrated light quantity was measured using an ultraviolet light quantity meter “UV-351” (manufactured by Oak Manufacturing Co., Ltd.).

Then, after peeling a base material from a roll plate using a peeling roller, ultraviolet rays were again irradiated from the thin film side. The wavelength of the ultraviolet light was 300 nm, and the integrated light quantity was 300 mJ / cm ² .

  Subsequently, a mixture obtained by mixing two kinds of polymerizable liquid crystal compositions shown in Table 1 at 50 parts by mass: 50 parts by mass was applied onto the pattern alignment layer of the pattern alignment film by a die coating method. Then, about the Example, static elimination was performed until the laminated body containing a base material, a pattern orientation layer, and a phase difference layer forming layer passes the conveyance roller which conveys this laminated body. About the comparative example, static elimination was not performed.

  The charge removal was performed as follows. A self-discharge type static eliminator string (trade name: Bequistat, manufactured by Bekarto Toami Metal Fiber Co., Ltd.) was stretched in a straight line on the supports on both sides as shown in FIG. The length of the static elimination cord was 1500 mm, and the distance between the surface of the phase difference layer forming layer and the conductive wire was as shown in Table 1.

After neutralization, leveling was performed so that the final layer thickness of the retardation layer forming layer was 1 μm. Then, it flows for 1 minute in the first dryer adjusted to 60 ° C., 0.5 minute in the second dryer adjusted to 95 ° C., and 0.5 minute in the third dryer adjusted to 105 ° C., and is cooled to near room temperature. After that, ultraviolet rays having a wavelength of 260 nm were irradiated using the same type of ultraviolet irradiation apparatus as the above-described ultraviolet irradiation apparatus until the integrated light amount reached 300 mJ / cm ² . The retardation film which concerns on an Example and a comparative example was obtained through said process.

<Evaluation of charging on the web>
First, the amount of charge on the web was measured for the laminate immediately after neutralization. The charge amount was measured using a digital electrostatic potential measuring device MODEL KSD-2000 (Kasuga Denki Co., Ltd.) according to the instructions in the attached instruction manual. The results are shown in Table 2.

<Appearance evaluation>
Moreover, the external appearance of the retardation film was evaluated. Appearance evaluation is carried out by attaching polarizing plates (trade name: HCL2-5618HCS, manufactured by Sanlitz) on both sides of the retardation film so as to be in a crossed Nicol arrangement, and placing the bonded members on a liquid crystal backlight. The degree of cloudiness on the front was visually observed in a dark room. “O” indicates that there is almost no cloudiness and no alignment failure is observed, and “Δ” indicates that there is a little cloudiness but is not so high that alignment failure is observed. The degree of cloudiness is high and alignment failure is recognized. The case was set to “x”. The results are shown in Table 2.

  After forming the phase difference layer forming layer, if the coating substrate coated with the polymerizable liquid crystal composition is neutralized and then dried, the coated substrate is in a desired orientation state compared to the case where it is not neutralized, It was confirmed that the pattern phase difference film which is excellent also in an external appearance can be provided (Examples 1-6). Especially, it was confirmed that the distance between the surface of the phase difference layer forming layer and the neutralization string is preferably 20 mm or less (Examples 1 to 6), and more preferably 10 mm or less ( Examples 1, 2, 4, 5). This is probably because the charge on the web changed at a low value in the entire manufacturing process of the retardation film as a result of the charge removal.

  Moreover, the polymeric liquid crystal composition containing the 1 type, or 2 or more types of polymeric liquid crystal compound comprised only with the lone electron pair non-containing compound which does not have an atom which has a lone electron pair other than an oxygen atom was used. It was confirmed that the charge on the web of the pattern retardation film transitioned at a lower value (Examples 4 to 6).

  On the other hand, when not passing through the static elimination process, it was confirmed that the external appearance was inferior compared with the Example (Comparative Example 1). This is considered to be due to the fact that the charge on the web is higher than in the examples, and the charge amount on the web also changes in the subsequent steps.

DESCRIPTION OF SYMBOLS 1 Pattern retardation film 11 Base material 12 Pattern orientation layer 13 Phase difference layer

Claims (4)

Forming a layer comprising a polymerizable liquid crystal composition on a substrate;
A step of curing the layer made of the polymerizable liquid crystal composition by polymerizing the polymerizable liquid crystal composition,
In the step of curing the layer composed of the polymerizable liquid crystal composition, after applying the polymerizable liquid crystal composition and before drying, removing the coating substrate on which the polymerizable liquid crystal composition is applied Prepared,
The static elimination is performed from the coating surface side and after the application of the polymerizable liquid crystal composition and before passing through the first transport roller,
In the step of forming a layer made of the polymerizable liquid crystal composition, a phase difference layer forming layer made of the polymerizable liquid crystal composition is formed on the alignment layer after the step of forming the alignment layer on the substrate. Made by
The method for producing a laminate, wherein the layer made of the polymerizable liquid crystal composition cured by the step of curing the layer made of the polymerizable liquid crystal composition is a retardation layer that imparts a retardation to transmitted light. The laminate is a pattern retardation film,
The step of forming a layer composed of the polymerizable liquid crystal composition includes providing an alignment pattern on a substrate and creating the alignment layer with a pattern alignment layer,
The process of hardening the layer which consists of the said polymeric liquid crystal composition is performed by arranging the said polymeric liquid crystal composition along the said alignment pattern, and forming a phase difference layer. The laminated body of Claim 1 characterized by the above-mentioned. Production method. And the orientation axis is set at the time of forming the alignment pattern, the orientation deviation angle defined by the absolute value of the angular difference between the orientation axis of the phase difference layer is Ru der within 2 degrees, according to 請 Motomeko 2 A manufacturing method of a layered product. The static elimination is a static elimination electrode by stretching a conductive fiber wire in the form of a string or a string of conductive fibers on an electrode support, and applying an alternating high voltage to this, and for this conductive fiber wire, Performed by crossing the laminate without contact;
The manufacturing method of the laminated body in any one of Claim 1 to 3 whose distance of the surface of the layer which consists of the said polymeric liquid crystal composition, and the said conductive fiber wire is 20 mm or less.

Images