JP5668738B2 - Pattern retardation film and method for producing the same - Google Patents

Description

  The present invention relates to a pattern retardation film and a method for producing the same.

  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. 8 is a schematic diagram illustrating an example of a passive three-dimensional display. As shown in FIG. 8, in this method, first, the pixels constituting the flat panel display are divided into a plurality of types of pixels, that is, a right-eye video display pixel and a left-eye video display pixel. 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 found that a polymerizable liquid crystal composition was formed on a substrate and then the polymerizable liquid crystal composition was dried. It has been found that the orientation direction can be controlled more strictly and the appearance defects due to charging can be improved by drying the polymerizable liquid crystal composition while removing the charge from the coated substrate on which the liquid crystal composition is applied. The invention has been completed. Specifically, the present invention provides the following.

(1) The present invention includes a substrate, a pattern alignment layer formed on the substrate and having an alignment pattern formed thereon, and a retardation formed on the pattern alignment layer and containing a polymerizable liquid crystal composition. A pattern retardation film including a layer, and a pattern position in which the number of specific optical axis deviations is less than 1 when a light sample is checked under crossed Nicols for a measurement sample cut into a sheet of 1 m ² It is a phase difference film.

  (2) Moreover, this invention forms the phase difference layer formation layer which consists of a process which provides an orientation pattern on a base material, and forms a pattern orientation layer, and this pattern orientation layer from a polymerizable liquid crystal composition. And a step of drying the polymerizable liquid crystal composition while neutralizing a coating substrate on which the polymerizable liquid crystal composition is applied, thereby aligning the polymerizable liquid crystal composition along the alignment pattern and causing a phase difference And a step of forming a layer.

  (3) Further, in the present invention, the static elimination is performed using a conductive fiber wire in which a conductive fiber is formed in a string shape or a thread shape, and the conductive fiber wire is a transport roller in a dryer for drying the polymerizable liquid crystal composition. It is a manufacturing method of the pattern phase difference film as described in (2) provided between each and a conveyance roller.

  (4) Further, in the present invention, the static elimination is performed by extending the conductive fiber wire linearly on an electrode support to form a static elimination electrode, to which an alternating high voltage is applied, and for the conductive fiber wire, The pattern phase difference film according to (3), wherein the pattern phase difference film is crossed in a non-contact manner, and the distance between the surface of the layer made of the polymerizable liquid crystal composition and the conductive fiber line is 20 mm or less. It is a manufacturing method.

(5) Further, in the present invention, the number of specific optical axis deviations is less than one when the light leakage is confirmed under crossed Nicols for a measurement sample cut into a sheet of 1 m ² from (2) to ( 4) The method for producing a patterned retardation film according to any one of 4).

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

It is the schematic of the pattern phase difference film 1 which concerns on this invention. It is the schematic which shows an example of the manufacturing method of the pattern phase difference film 1 of FIG. It is the figure which showed typically the method of forming an alignment pattern by a photo-alignment system. It is the schematic which shows the conveyance state of the pattern phase difference film in the inside of a dryer in a prior art. 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 pattern retardation film containing the base material 11 / pattern alignment layer 12 / layer 13 'for retardation layer formation. It is the schematic which shows the conveyance state of the pattern phase difference film 1 inside the dryer 38 in this invention. 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.

<Pattern retardation film 1>
FIG. 1 is a diagram showing a pattern retardation film 1 obtained by the manufacturing method of the present embodiment. 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. In this embodiment, the alignment pattern is formed by a photo-alignment method in which alignment is performed by light irradiation using a photo-alignment material that exhibits photo-alignment by polarized light irradiation.

[Phase difference layer 13]
The retardation layer 13 contains 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 retardation film 1 in the case of forming by a photo-alignment system is demonstrated, the retardation film 1 may be formed by the shaping UV system.

  FIG. 2 shows a method for producing the retardation film 1 by the photo-alignment 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 pattern alignment layer forming layer forming process is performed in which the composition is thermally cured by a dryer 33 to form a thin film pattern alignment layer forming layer 12 ′. Subsequently, (C) the ultraviolet irradiation process of irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays from the ultraviolet irradiation devices 34 and 35 is performed. The pattern alignment layer 12 is formed by the processes (A) to (C).

  Subsequently, (D) a retardation layer forming coating solution 13 ′ is applied from a retardation layer forming coating solution supply device 36 containing a polymerizable liquid crystal composition for forming a retardation layer. A coating solution for forming a retardation layer for forming a layer forming layer is applied. Thereafter, (E) a leveling process is performed using the leveling device 37 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 forming temperature by using the dryer 38. 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. In the present embodiment, a static eliminator 39 is provided inside the dryer 38 to neutralize the coated substrate coated with the polymerizable liquid crystal composition. By providing the static eliminator 39, the orientation direction can be controlled more strictly, and appearance defects due to charging can be improved.

  Then, (G) Cooling process which cools the laminated body which consists of the base material 11 / pattern orientation layer 12 / retardation layer 13 is performed using the cooler 40, and (H) ultraviolet irradiation device 41 is used, and it is polymerizable. The rod-shaped compound is irradiated with ultraviolet rays. Then, (I) after the film is taken up on the take-up reel 42, a cutting process for cutting it 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, and the refractive index in the slow axis direction having the largest refractive index in the in-plane direction is Nx, 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 40 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 for pattern alignment layer]
When forming the pattern alignment layer 12 by a photo-alignment method, the pattern alignment layer 12 contains the composition for pattern alignment layers demonstrated below. This composition for pattern alignment layers contains the photo-alignment material which exhibits photo-alignment property by polarized light irradiation.

  The photo-alignment material refers to a material that can exhibit an alignment regulating force by irradiation with polarized ultraviolet rays. The alignment regulating force means that when an alignment layer containing a photo-alignment material is formed and a layer made of a rod-shaped compound (polymerizable liquid crystal composition for forming a retardation layer in the present invention) is formed on this alignment layer, the rod-shaped compound Is a function of arranging the in a predetermined direction.

  The photo-alignment material is not particularly limited as long as it exhibits the above-mentioned alignment regulating force by irradiating polarized light. Such photo-alignment materials include photoisomerization materials that reversibly change the alignment regulation force by changing only the molecular shape by cis-trans changes, and photoreaction materials that change the molecules themselves by irradiating polarized light. It can be divided roughly. In the present invention, any of the photoisomerization material and the photoreaction material can be preferably used, but the photoreaction material is more preferably used. Since the photoreactive material is one in which molecules react with each other when polarized light is irradiated to express the alignment regulating force, it is possible to irreversibly express the alignment regulating force. Therefore, the photoreactive material is superior in the temporal stability of the orientation regulating force.

  The photoreactive material can be further classified according to the type of reaction caused by polarized light irradiation. Specifically, a photodimerization type material that develops an alignment regulation force by causing a photodimerization reaction, a photodegradable material that produces an orientation regulation force by producing a photodecomposition reaction, an orientation regulation by producing a photobinding reaction It can be divided into a photocoupled material that develops force, and a photodecomposition-coupled material that develops alignment regulating force by causing a photodecomposition reaction and a photocoupled reaction. In the present invention, any of the above-mentioned photoreactive materials can be suitably used, but it is more preferable to use a photodimerization type material from the viewpoint of stability and reactivity (sensitivity).

  The photodimerization type material is not particularly limited as long as it is a material capable of expressing an alignment regulating force by causing a photodimerization reaction. It is preferable that it is within a range of 280 nm to 400 nm, and more preferably within a range of 300 nm to 380 nm.

  Examples of such a photodimerization type material include a polymer having cinnamate, coumarin, benzylidenephthalimidine, benzylideneacetophenone, diphenylacetylene, stilbazole, uracil, quinolinone, maleimide, or a cinnamylideneacetic acid derivative. Among them, a polymer having one or both of cinnamate and coumarin is preferably used in that the orientation regulating force is good. Specific examples of such a photodimerization type material include compounds described in, for example, JP-A-9-118717, JP-T-10-506420, JP-T2003-505561, and WO2010 / 150748. Can be mentioned.

As the cinnamate and coumarin, those represented by the following formulas Ia and Ib are preferably used.

In the above formula, A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furylene, 1,4- or 2,6-naphthylene, Unsubstituted, fluorine, chlorine or cyclic, linear or branched alkyl residues of 1 to 18 carbon atoms (unsubstituted or mono- or polysubstituted by fluorine, chlorine, 1 Represents phenylene which is mono- or polysubstituted by two or more non-adjacent —CH ₂ — groups which may be independently substituted by the group C.

  In the above formula, B represents a hydrogen atom or a group capable of reacting or interacting with a second substance, such as a polymer, oligomer, monomer, photoactive polymer, photoactive oligomer and / or photoactive monomer or surface. Represents.

In the above formula, C represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —. CO—O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and Si (CH 3) 2 — A group selected from O—Si (CH 3) 2 — (wherein R ₁ represents a hydrogen atom or lower alkyl).

In the above formula, D represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —. CO—O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and Si (CH 3) 2 — A group selected from O—Si (CH 3) 2 — (R ₁ represents a hydrogen atom or lower alkyl), an aromatic group or an alicyclic group.

In the above formula, S ₁ and S ₂ are independently of each other a single bond or a spacer unit, for example a linear or branched alkylene group having 1 to 40 carbon atoms (unsubstituted, fluorine or chlorine One or more substituted and one or more non-adjacent —CH ₂ — groups may be independently substituted by the group D, but the oxygen atoms are not directly bonded to each other).

In the above formula, Q represents an oxygen atom or NR ₁ — (R ₁ represents a hydrogen atom or lower alkyl).

In the above formula, X and Y are independently of each other hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 12 carbon atoms (optionally substituted by fluorine and optionally not one or more adjacent). alkyl -CH ₂ - groups are -O -, - CO-O - , - O-CO- and / or CH = CH- represents a) are replaced by.

  In addition, the photo-alignment material used for this invention may be only 1 type, and may use 2 or more types.

[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 0.1 μm to 10 μm. More preferably, it is in the range of 1 μm to 5 μm, and still more preferably in the range of 0.1 μm to 3 μm.

[(B) Layer formation processing for pattern alignment layer formation]
In the pattern alignment layer forming layer forming process, the pattern alignment layer composition is thermally cured using the dryer 33. In this process, the substrate 11 is turned upside down by a reversing roller (not shown), and then guided to the dryer 33, where the pattern alignment layer composition is thermally cured, and then the next step is performed in a semi-dry state. Send it out.

  The curing temperature of the pattern alignment layer composition is preferably 100 ° C. or higher and 130 ° C. or lower. When the temperature is lower than 100 ° C., the composition cannot be uniformly heat-cured, which is not preferable because the thin film may be non-uniform. If it exceeds 130 ° C., the substrate 11 and the thin film may shrink, which is not preferable.

  The curing time of the pattern alignment layer composition is preferably 1 minute or more and less than 10 minutes. If it is less than 1 minute, it cannot be thermally cured, and this is not preferable in that the thin film may become non-uniform. Exceeding 10 minutes is not preferable because repelling or defects may occur and the base material 11 or the thin film may shrink.

[(C) UV irradiation treatment]
Next, an ultraviolet irradiation process for irradiating the pattern alignment layer forming layer 12 'with ultraviolet rays will be described in detail with reference to FIG.
First, as shown in FIG. 3A, the first alignment preparation region 12′A corresponding to the region for the right eye is not shielded, and only the second alignment preparation region 12′B corresponding to the region for the left eye is used. By irradiating the pattern alignment layer forming layer 12 ′ with ultraviolet rays (polarized ultraviolet rays) by linearly polarized light through the mask 11 that is shielded from light, the first alignment preparation region 12′A that is not shielded from light is directed in a desired direction. Orient. Subsequently, as shown in FIG. 3B, ultraviolet rays are irradiated on the entire surface of the pattern alignment layer forming layer 12 ′ by linearly polarized light whose polarization direction is 90 degrees different from that of the first irradiation. The unexposed second alignment preparation region 12′B is aligned in a desired direction. Two types of alignment patterns are formed by these two UV irradiations.

  In the example of FIG. 3, the first alignment preparation region 12′A is first irradiated with polarized ultraviolet light, and then the second alignment preparation region 12′B is irradiated with polarized ultraviolet light. However, the order is not limited to this, First, the second alignment preparation region 12′B may be irradiated with polarized ultraviolet light, and then the first alignment preparation region 12′A may be irradiated with polarized ultraviolet light.

  The pattern of the mask, that is, the pattern irradiation pattern, is stable in the first alignment region 12A (see FIG. 1) corresponding to the region for the right eye and the second alignment region 12B (the same) corresponding to the region for the left eye. If it can form in this, it will not specifically limit, For example, a strip | belt-shaped pattern, a mosaic pattern, a zigzag pattern, etc. can be mentioned. Among them, a belt-like pattern is preferable, and in particular, a belt-like pattern parallel to each other in the longitudinal direction of the long film, that is, pattern irradiation becomes a belt-like pattern parallel to each other in the longitudinal direction of the long film. It is preferable to irradiate polarized ultraviolet rays. It is because it can form easily by fixing the irradiation position of polarized ultraviolet rays and conveying a long film in a longitudinal direction. Moreover, it is because it can irradiate with pattern shape with sufficient precision. In the retardation layer 13, a pattern in which 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 are formed, and a color filter used in the display device This is because it is easy to make the correspondence with the pattern in which the pixels are formed.

  The pattern width of the mask, that is, the irradiation width and the irradiation interval (non-irradiation width) of polarized ultraviolet rays may be the same or different, but the width of the region corresponding to the region for the right eye and the left eye Preferably, the width of the region corresponding to the region for use is the same. The pattern in which the first phase difference region 13A and the second phase difference region 13B are formed in the phase difference layer 13 and the pattern in which the pixel portion is formed can be easily associated with each other. This is because a panel display can be easily manufactured. When aligning the position with the stripe line of the color filter, the pattern in which the region corresponding to the region for the right eye and the region corresponding to the region for the left eye are formed and the stripe pattern of the color filter have a corresponding relationship. It is preferable to irradiate with a width.

  In the case of a three-dimensional display application, the pattern width is preferably in the range of 50 μm to 1000 μm, and more preferably in the range of 100 μm to 800 μm. In addition, the pattern width here refers to the pattern width of the pattern orientation layer 12 in the base material 11 contained in the phase difference film 1 in a stable contraction state.

  The material constituting the mask is not particularly limited as long as a desired opening can be formed, and examples thereof include metals and quartz that are hardly deteriorated by ultraviolet rays. Specifically, a metal substrate such as SUS that has been patterned by etching, laser processing, or electroforming, and further subjected to surface treatment such as nickel plating as necessary can be used. Further, a light shielding film made of emulsion (silver salt) or chromium can be provided on a substrate made of soda lime glass or quartz.

  Among them, it is preferable that Cr is patterned on synthetic quartz. The pattern alignment layer forming layer 12 'made of a cured product of the pattern alignment layer composition is excellent in dimensional stability and ultraviolet transmittance with respect to changes in temperature and humidity, etc., and can be irradiated with ultraviolet rays with high accuracy, resulting in a highly accurate pattern. This is because the alignment layer 12 can be formed.

  The thickness of the synthetic quartz mask is not particularly limited as long as it can form a pattern with high dimensional accuracy, but it is preferably within a range of 1 mm to 20 mm, and within a range of 5 mm to 18 mm. Is more preferable, and it is still more preferable to be in the range of 9 mm to 16 mm. This is because when the thickness is within the above-mentioned range, the thickness can be reduced, the dimensional accuracy can be improved, and the photomask is not excessively heavy. .

  The polarization direction of the polarized ultraviolet light is not particularly limited as long as the polarization direction with respect to the region corresponding to the region for the right eye and the polarization direction with respect to the region corresponding to the region for the left eye are different. It is preferable that the difference is 90 °. Since the direction (slow axis direction) in which the refractive index is maximum between the first phase difference region 13A and the second phase difference region 13B can be orthogonal to each other, a display device capable of three-dimensional display It is because it can manufacture more suitably.

  The direction different by 90 ° is not particularly limited as long as it can perform three-dimensional display with high accuracy when a display device capable of three-dimensional display is formed using the retardation film 1. Usually, it is preferably within a range of 90 ° ± 3 °, more preferably within a range of about 90 ° ± 2 °, and further preferably within a range of about 90 ° ± 1 °. This is because a display device capable of high-performance three-dimensional display can be obtained.

  The polarized ultraviolet light may be collected or may not be collected. However, when the pattern irradiation is performed on the long film on the transport roll, that is, the polarized ultraviolet light. When there is a difference in the distance from the light source of polarized ultraviolet light within the region irradiated with, the light is preferably condensed with respect to the transport direction. This is because the influence of the distance from the light source can be reduced and the alignment region can be formed with high pattern accuracy.

  Examples of the condensing method include a generally used method, for example, a method using a condensing reflector or a condensing lens having a desired shape. In the present invention, it is preferable that the polarized ultraviolet light is parallel light with respect to the direction (width direction) orthogonal to the transport direction. As a parallelization method, a generally used method, for example, a desired shape is used. Examples thereof include a method using a condensing reflector or a condensing lens.

  The wavelength of the polarized ultraviolet light is appropriately set according to the photo-alignment material and the like, and can be a wavelength used when expressing the alignment regulating force in a general photo-alignment material. Specifically, It is preferable to use irradiation light having a wavelength of 210 nm to 380 nm, preferably 230 nm to 380 nm, more preferably 250 nm to 380 nm.

  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 method for generating polarized ultraviolet rays is not particularly limited as long as it is a method capable of stably irradiating polarized ultraviolet rays. it can.

  As such a polarizer, one that is generally used for generation of polarized light can be used. For example, a wire grid polarizer having a slit-shaped opening or a plurality of quartz plates are laminated. Examples thereof include a method of performing polarization separation using a Brewster angle, and a method of using a method of performing polarization separation using a Brewster angle of vapor-deposited multilayer films having different refractive indexes.

The irradiation amount of polarized ultraviolet rays is not particularly limited as long as an alignment region having a desired alignment regulating force can be formed. For example, when the wavelength is 310 nm, 5 mJ / cm ^{2 to} 500 mJ / cm. preferably ² is in the ^range, 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} . This is because an alignment region having a sufficient alignment regulating force can be formed.

  The irradiation distance of polarized ultraviolet rays, that is, the distance in the conveyance direction of the long film that receives irradiation of polarized ultraviolet rays is not particularly limited as long as it can be the above-mentioned irradiation amount in each exposure process, It can be set as appropriate according to the line speed or the like. When the irradiation distance is short, it becomes easy to achieve high pattern accuracy, and when the irradiation distance is long, the advantage is that an alignment region having a sufficient alignment regulating force can be obtained even when the line speed is high. There is. In addition, as a method of lengthening the irradiation distance, a method of increasing the number of irradiation times of polarized ultraviolet rays in each exposure process or increasing the irradiation area in the transport direction can be exemplified.

  When irradiating the thin film with polarized ultraviolet light, 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.

[(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).

  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) Leveling process]
Subsequently, the leveling device 37 is used to perform a leveling process for making the thickness of the retardation layer forming layer uniform. 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.

[(F) 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 by using a dryer 38. 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 115 nm to 135 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 the rod-shaped compound is heated to the liquid crystal phase formation temperature or higher using the dryer 38, 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.

  By the way, in this embodiment, the static elimination apparatus 39 which neutralizes the application | coating base material with which the polymeric liquid crystal composition was apply | coated is provided inside the dryer 38. FIG. By providing the static eliminator 39, the orientation direction can be controlled more strictly, and appearance defects due to charging can be improved.

  Conventionally, a pattern retardation film including a base material 11, a pattern alignment layer 12, and a retardation layer forming layer 13 ′ includes a plurality of drying guide rolls 50A, 50B, 50C,. In use, it is conveyed from the inlet of the dryer 38 toward the outlet. However, the polymerizable liquid crystal composition contained in the retardation layer forming layer 13 'has a dielectric anisotropy, and the orientation changes when a voltage is applied. Therefore, as shown in FIG. 5, 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. 4. As shown in FIG. 6, it is orientated along the electric field direction by static electricity caused by the friction between 11 and the plurality of drying guide rolls 50A, 50B, 50C,.

  In the present invention, as shown in FIG. 7, conductive fiber wires 39A, 39B, 39C,... In which conductive fibers are string-like or thread-like are provided between the drying guide rolls 50A, 50B, 50C,. Since the base material 11 is neutralized using these conductive fiber wires 39A, 39B, 39C,..., Even if the base material 11 comes into contact with the plurality of drying guide rolls 50A, 50B, 50C,. In addition, it is possible to suppress the generation of static electricity due to friction between the substrate 11 and the plurality of drying guide rolls 50A, 50B, 50C,..., And as a result, the orientation of the polymerizable liquid crystal composition 14 before polymerization is It can be prevented from being disturbed.

  The static eliminator 39 is provided so as to sandwich the conductive fiber wire and the substrate 11 in the width direction, and one of the two supports that support the conductive fiber wire is connected to the AC high voltage HV. Yes.

  The conductive fiber wire may be a metal wire such as tungsten or stainless steel, or may be a conductive fiber wire in which the conductive fiber is formed in a string shape or a thread shape. However, the conductive fiber wire 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 fiber line 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.

  The static elimination using the static eliminator 39 includes a conductive fiber wire stretched linearly on two supports, and includes a base material 11, a pattern alignment layer 12, and a retardation layer forming layer 13 'with respect to the conductive wire. The pattern retardation film 1 is crossed in a non-contact manner. At this time, the charge removal using the charge removal device 39 is preferably performed such that the maximum charged voltage of the base material 11 between adjacent drying guide rolls is ± 5.0 kV or less, and is ± 1.0 kV or less. More preferably. At that time, the distance between the surface of the retardation layer forming layer 13 ′ and the conductive fiber line 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.

[(G) 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 40 is performed. The cooling process may be performed until the stack reaches room temperature.

[(H) 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.

<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>

<Example>
The retardation film which concerns on an Example and a comparative example was obtained through the manufacturing process demonstrated in FIG. At that time, a TAC base material (trade name: TD60UL-P, thickness: 60 μm, manufactured by Fuji Film Co., Ltd.) whose surface was subjected to an antiglare treatment was used as the base material, and the conveyance speed was 10 m / min.

  First, 100 parts by mass of a photo-alignment material (trade name: ROP-103, manufactured by Rorick) having both a photodimerization site and a thermal crosslinking site was dissolved in 900 parts by mass of PGME to obtain a composition for a pattern alignment layer. .

  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 200 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 200 μm was formed.

Synthetic quartz with a stripe pattern of width 500μm in the direction parallel to the transport direction of the original fabric with polarized ultraviolet rays (polarization axis is 45 ° with respect to the transport direction of the film) passed through the wire grid. Irradiation was through the mask formed above. Subsequently, polarized ultraviolet rays (with a polarization axis of −45 ° with respect to the film transport direction) that passed through a wire grid without passing through a mask were irradiated. At this time, “H bulb” (manufactured by Fusion) was used as the ultraviolet irradiation device. The wavelength of polarized ultraviolet light was 313 nm, and the integrated light quantity was 40 mJ / cm ² . The integrated light quantity was measured using an ultraviolet light quantity meter “UV-351” (manufactured by Oak Manufacturing Co., Ltd.). A patterned alignment film was obtained through the above steps.

  Subsequently, a liquid crystal material dissolved in propylene glycol monomethyl ether acetate (PEGMEA) on the pattern alignment layer of the pattern alignment film (trade name: licrive (registered trademark) RMS03-013C, Merck) was applied by a die coating method. Then, 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. did.

  In the 1st-3rd dryer, static elimination was performed so that the maximum charged voltage between adjacent drying guide rolls might be -5 kV. The charged voltage 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 charge removal was performed as follows. As shown in FIG. 7, a self-discharge type static eliminator (trade name: Bequistat, manufactured by Bekarto Tome Metal Fiber Co., Ltd.) was stretched linearly at each location between the drying guide rolls. The distance between the surface of the retardation layer forming layer and the conductive wire is 50 mm.

After drying and cooling the laminate, ultraviolet rays having a wavelength of 260 nm were irradiated using an ultraviolet irradiation device of the same type as the above-described ultraviolet irradiation device until the integrated light amount reached 300 mJ / cm ² . The pattern retardation film which concerns on an Example was obtained through said process.

<Comparative Example 1>
A pattern retardation film according to Comparative Example 1 was obtained in the same manner as in the Examples except that the static elimination was not performed. In Comparative Example 1, since static elimination was not performed, the maximum voltage between adjacent drying guide rolls was −10 kV.

<Comparative example 2>
Although the above neutralization was not performed, a patterned retardation film according to Comparative Example 2 was obtained by the same method as in the Example, except that the neutralization was performed until just before the coating of the liquid crystal layer. In Comparative Example 2, since the static elimination was not performed during the drying process of the polymerizable liquid crystal composition, the maximum charged voltage between adjacent drying guide rolls during the drying process was −10 kV, but before the coating of the liquid crystal layer. Since the static elimination was performed, the maximum charged voltage of the original fabric before coating was -5 kv.

<Appearance evaluation>
First, the 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 light leakage on the front was visually observed in a dark room. A case where there was almost no specific light leakage and no optical axis deviation was observed was indicated by “◯”, and a case where even a part of the optical axis deviation was observed was indicated by “X”. The results are shown in Table 2.

  Moreover, the haze value was measured by a method based on JIS K-7361 using a haze meter HM-150 (manufactured by Murakami Color Research Laboratory). The results are shown in Table 2.

<Evaluation of adhesion>
Moreover, adhesiveness was evaluated. Using a cross-cut guide (Cortech), scratches the liquid crystal surface in a grid pattern with a cutter equipped with a new blade, and then, using a cellophane tape, peel test based on JIS K5600 (new) five times at the same place It was carried out and the percentage remaining in 100 squares was measured. The results are shown in Table 2.

<Evaluation of in-plane retardation and optical axis>
The in-plane phase difference / optical axis is measured using a phase difference / optical axis measuring device Axostep (manufactured by Axometrics), and the in-plane phase difference at a wavelength of 550 nm is applied to a 1 m ² sheet-cut sample consisting of a 1 m square. (Re value)-The measurement was performed by limiting the position where the optical axis deviation occurred with respect to the optical axis. Table 2 shows the in-plane retardation (Re value), the average value of the optical axis, and the standard deviation.

  After forming the phase difference layer forming layer, the polymerizable liquid crystal composition is dried along the alignment pattern by drying the polymerizable liquid crystal composition while neutralizing the coating substrate on which the polymerizable liquid crystal composition is applied. In the case where the retardation layer is formed, it is confirmed that a pattern retardation film having a desired orientation state and excellent appearance can be provided as compared with the case where static elimination is not performed (Example). This is presumably because, as a result of charge removal, the charge on the web changed at a low value in the entire manufacturing process of the retardation film.

  On the other hand, if the charge is not eliminated in the drying step after the polymerizable liquid crystal composition is applied to the substrate, it cannot be said that the orientation direction can be controlled as strictly as in the examples, and it is confirmed that appearance defects due to charging can occur. (Comparative Examples 1 and 2). 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 phase difference film 11 Base material 12 Pattern orientation layer 13 Phase difference layer 36 Polymerizable liquid crystal composition 38 Dryer 39 Static elimination apparatus 39A, 39B, 39C ... Conductive fiber wire 40A, 40B, 40C ... Conveyance roller

Claims (2)

Providing an alignment pattern on the substrate to form a pattern alignment layer;
Forming a retardation layer forming layer comprising a polymerizable liquid crystal composition on the pattern alignment layer;
The polymerizable liquid crystal composition is dried while discharging the coating substrate coated with the polymerizable liquid crystal composition, thereby forming the retardation layer by aligning the polymerizable liquid crystal composition along the alignment pattern. Including the steps of:
The static elimination is performed using a conductive fiber wire in which a conductive fiber is in a string shape or a thread shape,
The said conductive fiber wire is a manufacturing method of the pattern phase difference film each provided between the conveyance roller in the dryer which dries the said polymeric liquid crystal composition, and a conveyance roller, respectively. In the static elimination, the conductive fiber wire is stretched linearly on an electrode support to form a static elimination electrode, and an alternating high voltage is applied to the conductive fiber wire, and the pattern retardation film is intersected with the conductive fiber wire in a non-contact manner. Done by letting
The distance of the polymerizable liquid crystal comprising the composition layer surface of said conductive fibers line is 20mm or less, the production method of the patterned retardation film according to claim 1.

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