JP2013113939A - Method for manufacturing original plate for patterned alignment layer for three-dimensional display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an original plate which performs patterning a patterned retardation film for a three-dimensional display device with high accuracy, for a patterned alignment layer for a three-dimensional display.SOLUTION: The method aims to manufacture an original plate for a patterned alignment layer for a three-dimensional display, the original plate having a belt-like first rugged structure region where a minute linear rugged structure is formed in substantially a given direction, and a belt-like second rugged structure where a minute linear rugged structure is formed in a direction different from that of the first rugged structure, with the first region and the second region alternately formed. In forming a belt-like resist pattern to mask one rugged structure region, the method includes a drying step of controlling an amount of a residual solvent in the resist to 0.05 mass% or more and 1.0 mass% or less, after applying the resist and prior to exposing and developing.

Description

  The present invention relates to a method for producing an original plate for a 3D display pattern alignment film for producing a 3D display pattern alignment film capable of forming a 3D display pattern retardation film.

  In recent years, studies on flat panel displays capable of three-dimensional display have been promoted in a wide range of fields. In order to perform three-dimensional display, it is usually necessary to display the right-eye video and the left-eye video separately for the viewer in some way, and one of these methods is a passive method.

  FIG. 5 is a schematic diagram illustrating an example of a passive three-dimensional display. In this method, the pixels constituting the flat panel display are divided into a plurality of two types of pixels, a right-eye video display pixel and a left-eye video display pixel, and the right-eye video is displayed on one group of pixels. In the other group of pixels, the image for the left eye is displayed. In addition, the image for the right eye and the image for the left eye are converted into circularly polarized light by using a linearly polarizing plate and a pattern retardation film in which a patterned retardation layer corresponding to the division pattern of the pixel is formed. In addition, viewers can wear 3D display by wearing right-eye and left-eye circular polarizing glasses so that the right-eye video reaches only the right eye and the left-eye video only reaches the left eye. . Thus, in the passive method, a pattern retardation film is essential.

  As a prior art of this pattern retardation film, the following Patent Document 1 describes a liquid crystal that is aligned and polymerized along a groove extending direction on a substrate having a plurality of grooves extending in a specific direction on the surface. A retardation plate in which the material is present as a retardation layer is disclosed. The substrate includes a first groove region including a groove extending in a first direction and a second groove region including a groove extending in a second direction orthogonal to the first groove region. It is described that the first and second groove regions are obtained by transferring molds (plates) that are striped and alternately arranged, and that the grooves of this mold are formed by pulse laser, polishing, cutting by cutting tools, or the like. Has been.

JP 2010-152296 A Japanese Patent Laid-Open No. 10-239832 JP 2007-101738 A

  Thus, in the pattern retardation film, it is necessary to form different patterns alternately in a stripe shape. Such a strip-shaped first concavo-convex structure region in which a fine line-shaped concavo-convex structure is formed in a substantially constant direction, and a strip-shaped second concavo-convex structure in which a fine line-shaped concavo-convex structure is formed in a direction different from the first concavo-convex structure. As a method for manufacturing a master plate for a three-dimensional display pattern alignment film in which concavo-convex structure regions are alternately formed, for example, methods shown in FIGS. 1 to 2 are being studied.

  Specifically, this method includes a first polishing step of forming a first concavo-convex structure region as shown in FIG. 1B on the surface of the first layer made of the inorganic material shown in FIG. As shown in FIG. 1C, a step of patterning a strip-shaped resist portion on the surface of the first concavo-convex structure region of the first layer, and on the surface of the resist portion and the non-resist portion as shown in FIG. A second layer forming step of forming a second layer film made of an inorganic material; and a second concavo-convex structure region formed by polishing the surface of the second layer film in the different direction as shown in FIG. 2 polishing step and a resist peeling step for peeling the resist portion and the second layer film on the resist portion as shown in FIG. That is, by temporarily masking one concavo-convex structure region (which may be a region where a concavo-convex structure region will be formed in the future) by forming a strip-shaped resist portion, and then stripping the resist portion, a different concavo-convex structure region is formed into a strip shape. It is a method of arranging alternately.

  The present invention has found that adjustment of the residual solvent amount of the resist is effective in order to improve the patterning accuracy of the resist, and has completed the present invention.

  For example, Patent Document 2 and Patent Document 3 exist as conventional techniques for examining the residual solvent in the resist. Patent Document 2 relates to a photosensitive lithographic printing plate, and Patent Document 3 describes lithography of a silicon wafer. These are related to a resist layer having a film thickness of 500 nm, which is used for different applications and purposes.

  The present invention has been made in view of such a situation, and a pattern alignment film capable of forming a pattern retardation film for three-dimensional display can be produced with high accuracy. A method for producing an original film is provided. Specifically, the present invention provides the following.

(1) A strip-shaped first concavo-convex structure region in which a fine line-shaped concavo-convex structure is formed in a substantially constant direction, and a strip-shaped second concavo-convex structure in which a fine line-shaped concavo-convex structure is formed in a direction different from the first concavo-convex structure. A method for producing an original plate for a three-dimensional display pattern alignment film in which structure regions are alternately formed,
A step of patterning a resist portion for temporary masking on one band-shaped concavo-convex structure region or on a region where the concavo-convex structure is formed later,
In the pattern formation of the resist portion, a three-dimensional display use comprising a drying step in which the residual solvent of the resist is 0.05% by mass or more and 1.0% by mass or less after application of the resist and before exposure. A method for producing an original plate for a pattern alignment film.

(2) The method for producing an original plate for a three-dimensional display pattern alignment film according to (1), wherein a residual solvent of the resist in the drying step is 0.05% by mass or more and 0.8% by mass or less.

(3) The method for producing an original plate for a three-dimensional display pattern alignment film according to (1) or (2), wherein the residual solvent of the resist includes a solvent having an evaporation rate of 1 or less when butyl acetate is 1.

(4) Any of (1) to (4), wherein the residual solvent of the resist includes one or more selected from a polyhydric alcohol having a hydroxyl group, a polyhydric alcohol ether having a hydroxyl group, and a polyhydric alcohol ester having a hydroxyl group A method for producing an original plate for a three-dimensional display pattern alignment film according to claim 1.

(5) The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of (1) to (5), which contains propylene glycol monomethyl ether as a residual solvent for the resist.

(6) The method for producing an original plate for a three-dimensional display pattern alignment film according to (6), wherein a residual amount of the propylene glycol monomethyl ether in the drying step is 0.4% by mass or less.

(7) The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of (1) to (7), wherein the resist portion has a thickness of 1 μm to 10 μm.

(8) The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of (1) to (8), wherein the resist contains a styrene-maleic acid resin.

(9) The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of (1) to (9), wherein the drying step is performed at 10 ° C. to 30 ° C. for 10 hours or more.

  ADVANTAGE OF THE INVENTION According to this invention, the original plate for 3D display pattern orientation films which can produce the pattern orientation film which can form the pattern retardation film for 3D displays with high precision can be provided.

It is process drawing which shows an example of the manufacturing method of the pattern alignment film original plate for three-dimensional displays of this invention, and is a figure which shows process (a) to (c). FIG. 2 is a diagram illustrating steps (d) to (f) following FIG. 1. It is a perspective view of the pattern orientation film for three-dimensional display shape-transferred using the plate obtained by the manufacturing method of the present invention. FIG. 4 is a perspective view of a pattern retardation film in which a liquid crystal layer is aligned on the three-dimensional display pattern alignment film of FIG. 3. It is the schematic which shows the example of the liquid crystal display device which can display a three-dimensional image | video with a passive system. It is a graph which shows the relationship between the drying time and residual solvent amount in an Example. It is a graph which shows the relationship between the drying time in another Example, and the amount of residual solvents. It is a graph which shows the relationship between the drying time in another Example, and the amount of residual solvents. It is a graph which shows the relationship between the drying time in another Example, and the amount of residual solvents.

  The present invention will be specifically described with reference to the drawings. 1 and 2 are process charts showing an example of a method for producing an original plate for a three-dimensional display pattern alignment film according to the present invention. This manufacturing process includes steps (a) to (f). Specifically, a first polishing step of forming a first concavo-convex structure region as shown in FIG. 1B on the surface of the first layer made of the inorganic material shown in FIG. ) And a step of patterning a strip-shaped resist portion on the surface of the first concavo-convex structure region of the first layer, and the surface of the resist portion and the non-resist portion is made of an inorganic material as shown in FIG. A second layer forming step for forming the second layer film, and a second polishing step for polishing the surface of the second layer film in the different direction as shown in FIG. 2F, and a resist stripping step for stripping the resist portion and the second layer film on the resist portion. Hereinafter, each step will be described in detail.

<First polishing step>
As shown in FIGS. 1A and 1B, the surface of the first layer 10 is polished to form a first concavo-convex structure region 12 that is a fine line-shaped concavo-convex structure on substantially the entire surface thereof.

The first layer 10 is an inorganic material layer that exists as the outermost layer of the substrate. The inorganic material is not particularly limited as long as the second layer to be described later can be laminated so as to be peeled and removed. Metal materials such as nickel, copper, aluminum, tin, chromium, stainless steel, and iron; SiO ₂ , _{SiO x, Al 2 O 3,} GeO 2, TiO 2, Cr 2 O 3, ZrO 3, Ta 2 O 5, inorganic oxides such as _{Nb 2 O 3; Si 3 N} 4, an inorganic nitride such as AlN; SiO inorganic oxynitride of _x N _y or the like; inorganic carbides such as SiC; can be mentioned DLC (diamond-like carbon) or the like, among others, from the viewpoint of stacking the second layer and the third layer to be described later peeling removably , Metal material, DLC, and the like are preferable, and titanium, nickel, chromium, and DLC are more preferable.

  The first uneven structure region 12 is randomly formed on the surface of the first layer 10 in a substantially constant direction. Here, the fine line-shaped uneven structure formed randomly in a substantially constant direction is, for example, a line-shaped uneven structure such as a fine scratch formed when the surface is rubbed. It is formed in a substantially constant direction. The fine line-shaped uneven structure is not particularly limited as long as it can be a pattern retardation film that can be three-dimensionally displayed by the pattern alignment film formed using the original plate of the present invention.

  The cross-sectional shape of the fine line-shaped concavo-convex structure is not particularly limited as long as it has a concavo-convex structure and the liquid crystal compound can be arranged in a predetermined direction, and is substantially rectangular, substantially triangular, substantially trapezoidal, etc. can do. Moreover, it may not be a fixed shape. The height, width, and period of the minute line-shaped concavo-convex structure are not particularly limited as long as the liquid crystal compounds can be arranged. In the present invention, the width of the fine line-shaped uneven structure is preferably in the range of 1 nm to 1000 nm, more preferably in the range of 1 nm to 500 nm, and particularly in the range of 1 nm to 100 nm. More preferably. The height of the fine line-shaped uneven structure is preferably in the range of 1 nm to 500 nm, more preferably in the range of 1 nm to 100 nm, and particularly in the range of 1 nm to 50 nm. Preferably there is. Furthermore, the period of the fine line-shaped uneven structure is not necessarily constant, but is preferably in the range of about 1 nm to 1000 nm, and more preferably in the range of 1 nm to 100 nm. This is because the liquid crystal compound can be stably arranged when the minute line-shaped uneven structure has the above-described size.

  Polishing methods include grinding stones, paper polishing, tape polishing, buffing, sand blasting, shot blasting, grit blasting, blasting methods such as glass bead blasting, nylon, polypropylene, vinyl chloride resin, rayon, cotton, etc. Uses brush materials such as synthetic resin bristles, non-woven fabrics, animal hairs, steel wires, etc. made of synthetic fibers, brush graining method including rubbing method, wire graining method by scratching with metal wire, supplying slurry liquid containing abrasive Examples thereof include a brush polishing method (brush graining method), a ball grain method, a buffing method such as a liquid honing method, and a shot peening method.

  When the first layer 10 is a hard substrate surface such as DLC, tape polishing or paper polishing is preferred. In the present invention, the first layer 10 is a metal material such as chromium or nickel. In this case, the Rabink method is also preferably used.

<Second layer forming step>
First, as shown in FIG. 1C, a strip-shaped first resist portion 31 and a non-resist portion 32 are pattern-formed on the surface of the first layer 10 on which the first concavo-convex structure region 12 is formed.

  As a method for forming a resist in parallel strips, a resist film (not shown) is formed by applying a resist material, and then exposed to a parallel strip, and then developed, whereby the first resist portion 31 is formed. And the non-resist portion 32 can be patterned.

  As the resist material used in this step, either a positive resist material (one that dissolves the light-irradiated portion) or a negative resist material (one that hardens the light-irradiated portion) can be used. Examples of the positive resist material include a chemically amplified resist using a novolac resin as a base resin. Examples of the negative resist material include a chemically amplified resist based on a crosslinked resin, specifically, a chemically amplified resist obtained by adding a crosslinking agent to polyvinylphenol and further adding an acid generator. Especially, it is preferable that it is a positive resist material from a viewpoint of the ease of resist peeling in a resist peeling process, the ease of melt | dissolution, and pot time (pot life).

  As the resist material, either a chemically amplified resist or a non-chemically amplified resist can be used, but a resist that does not contain a hydrophilic material as much as possible is preferable because of the relationship with a residual solvent described later. Positive resists include base resins such as styrene-maleic acid resin, polyvinyl acetal, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl phenol resin, and novolac resin, which contain hydrogen atoms such as phenol groups and carboxyl groups. A resin substituted with a group capable of dissociating by the action of an acid can be exemplified. Examples of the negative resist include a resin obtained by substituting a hydrogen atom such as a phenol group or a carboxyl group with a group capable of polymerizing with an acid or light in the above base resin.

  As a positive resist containing a styrene-maleic acid resin, for example, a polymer having at least one carboxyl group in the molecule, such as a styrene / maleic acid copolymer described in WO2005 / 001576 International Publication. Examples thereof include a positive photosensitive composition containing a substance and a photothermal conversion substance (infrared absorbing dye) that absorbs infrared rays from an exposure light source and converts them into heat. Here, the styrene / maleic acid copolymer is a styrene / maleic anhydride copolymer that is a copolymer of a styrene monomer and maleic anhydride, and a compound having a hydroxyl group such as hydroalcohol. It can be obtained by partial esterification by reaction. This styrene / maleic acid copolymer is known, and for example, trade name SMA1140 manufactured by SARTOMER can be used.

  The resist material is a composition containing a solvent, and the resist composition can be usually prepared by dissolving the above components in a solvent and filtering the solution as necessary. Examples of the solvent used here include ketone solvents such as cyclohexanone, acetone, ethyl methyl ketone (MEK), and methyl isobutyl ketone; cellosolv solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; Ester solvents such as ethyl, butyl acetate, isoamyl acetate, γ-butyrolactone, methyl 3-methoxypropionate; glycol solvents such as propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate; dimethyl sulfoxide, hexamethylphosphoric Nitrogen-containing solvents such as triamide dimethylformamide and N-methylpyrrolidone, and dimethyl sulfoxide, di- Chill formaldehyde, a mixed solvent obtained by adding N- methylpyrrolidinone and the like can be used. In addition, propionic acid derivatives such as methyl methyl propionate, lactic acid esters such as ethyl lactate, PGMEA (propylene glycol monoethyl acetate), and the like have low toxicity and can be preferably used. In addition, it contains aliphatic alcohols such as isopropyl alcohol (IPA), ethyl alcohol, methyl alcohol (MeOH), n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, and isobutyl alcohol, and aromatic solvents such as toluene and xylene. It does not matter. In the present invention, such solvents can be used alone or in admixture of two or more.

  The solvent used in the resist material of the present invention preferably contains a solvent having an evaporation rate of 1 or less when butyl acetate is 1. When water is used in the washing (rinsing) step after exposure and development, these solvents, which have a particularly low evaporation rate, are likely to remain. Further, if this solvent is highly compatible with water, it will penetrate into the resist and peel or swell. As a result, leading to defects such as chipping at the ends. For this reason, the defect of a resist pattern can be prevented by restrict | limiting a residual solvent especially when these solvents are included. Examples of such a solvent include one or more selected from a polyhydric alcohol having a hydroxyl group, a polyhydric alcohol ether having a hydroxyl group, and a polyhydric alcohol ester having a hydroxyl group, and more specifically, propylene glycol monomethyl ether. And glycol solvents such as propylene glycol monomethyl ether acetate.

  As a method for forming the resist film by coating the resist material, a general coating method can be used, for example, spin coating method, casting method, dipping method, bar coating method, blade coating method, roll coating method. Method, gravure coating method, flexographic printing method, spray coating method and the like can be used.

  In the present invention, in the pattern formation of the resist portion, the resist residual solvent is 0.05% by mass or more and 1.0% by mass or less, preferably 0.8% or less, after the application of the resist and before the exposure. And a drying step. If it is less than 0.05% by mass, cracks due to drying tend to occur, which is not preferable, and if it exceeds 1.0% by mass, chipping becomes noticeable due to peeling of the end portion of the resist portion. When propylene glycol monomethyl ether is contained, the residual amount is preferably 0.4% by mass or less, and more preferably 0.3% by mass or less.

  For the adjustment of the residual solvent, a conventionally known drying step may be used. In the present invention, the so-called room temperature drying at 10 ° C. to 30 ° C., preferably 15 ° C. to 25 ° C., for 10 hours or more, preferably 20 hours or more. Is preferable from the viewpoint of suppressing the formation of a film that can inhibit drying unevenness and evaporation of the solvent.

  As a method for exposing the resist film in parallel strips, an electron beam drawing method or a laser drawing method used for normal photomask drawing can be used. Alternatively, a method of performing ultraviolet irradiation through a mask can be used. Of these, the laser drawing method is preferable. This is because even if the shape of the metal substrate is a roll shape, the pattern can be accurately exposed. Further, as a method for developing the resist film after exposure, a general developing method such as alkali development can be used.

  The film thickness of the resist portion 31 thus formed is preferably 1 μm or more and 10 μm or less. If the thickness is less than 1 μm, the film thickness unevenness is large, and the variation in the line width increases due to the difference in the shade of the resist color. Also, in the second layer rubbing process described later, the first layer titanium below the resist film It is not preferable because the resist penetrates into the film and is damaged. When the thickness exceeds 10 μm, the attenuation during exposure increases, the deep part of the resist becomes underexposed, and the step between the adjacent second layers is large (FIG. 2 ( d) a step between adjacent second layer films 20), and the tip of the rubbing cloth is less likely to enter the second layer having a low height in FIG. 2 (e). This is not preferable because a region oriented in one direction becomes narrow.

  Next, as shown in FIG. 2 (d), the second layer film 20 made of an inorganic material is preferably formed as a thin film with a thickness of 0.01 μm to 1 μm on the resist portion 31 and the non-resist portion 32. Thereby, a second layer pattern made of the second layer film 20 is formed in the recess of the non-resist portion 32. If the film thickness of the second layer film 20 is less than 0.01 μm, minute irregularities formed by polishing or rubbing on the surface of the first layer are not filled with the second layer film, and the minute irregularities of the first layer and the first layer It is not preferable because minute irregularities of two layers are mixed to cause poor alignment. When the thickness exceeds 1 μm, the step becomes large and the phase difference amount is not preferable. Examples of the thin film forming method include physical vapor deposition (PVD) such as sputtering, ion plating, and vacuum vapor deposition, vapor deposition (CVD), plating, and coating.

  The inorganic material may be the same as or different from the first layer 10 described above, but it is preferable to use the same inorganic material from the viewpoint of interlayer adhesion and productivity. Specifically, the first layer / second layer film is preferably composed of titanium / titanium, DLC / DLC, chromium / chromium, nickel / nickel, or the like. In addition, it is not necessary to stick to the same material in particular, and DLC / Ni, DLC / Cr, Cr / Ni, and Ni / Cr may be used.

<Second polishing step>
Next, as shown in FIG. 2E, the entire surface of the second layer film 20, that is, the surface of the second layer film 20 on the resist part 31 and the non-resist part 32 is different from the first uneven structure region 12a. Then, the second concavo-convex structure region 21 a that is a fine line-shaped concavo-convex structure is formed on the surface of the second layer pattern 21. This process is basically the same process as the first polishing process described with reference to FIG. 1B except that the polishing direction is different from the first uneven structure region 12a. Therefore, detailed description other than the polishing direction is omitted.

  The first concavo-convex structure region 12a and the second concavo-convex structure region 21a are different in the formation direction of the minute line-shaped concavo-convex structure. In the first polishing step of FIG. 1B and the second polishing step of FIG. 2E, the formation directions θ of the minute line-shaped uneven structures on the XY plane are 135 degrees and 45 degrees, respectively. In the case of 90 degrees difference (see θ1 = 135 degrees and θ2 = 45 degrees in FIG. 2 (f), but not limited to this, for example, it may be different by 45 degrees. Note that θ1 = 0 degrees, θ2 = It may be 90 degrees.

  Finally, as shown in FIG. 2F, in this state, the resist portion 31 is peeled off by alkali treatment or solvent treatment. At this time, the second layer film 20 formed on the resist portion 31 is also removed to form the first uneven structure region 12a on the first layer 10 and the second uneven structure region 21a is formed on the surface. The second layer pattern 21 remains, and the master plate 100 for a three-dimensional display pattern alignment film is obtained.

  As shown in FIG. 2 (f), in the plan view A of the pattern alignment film original plate 100 for three-dimensional display, first uneven structure regions 12a and second uneven structure regions 21a are alternately formed in a strip shape. . In the cross-sectional view B, the second layer pattern 21 exists as a convex portion on the first layer 10, and a step corresponding to the film thickness h of the second layer pattern 21 is formed.

<Pattern alignment film / Pattern retardation film>
As shown in FIG. 3, the original plate 100 for a three-dimensional display pattern alignment film obtained in this way is a film having a small retardation made of TAC (triacetyl cellulose), COP (cyclic olefin resin), acrylic resin, or the like. The molded resin surface of a laminate in which a conventionally known molding resin 120 such as a UV curable resin is laminated on 110 is pressure-bonded, and the first concavo-convex structure region 12a and the second of the original plate 100 for a three-dimensional display pattern alignment film are pressed. A minute line-like uneven structure constituted by the uneven structure region 21a is transferred to the shaping resin surface 121 and then UV-cured. Thereby, the pattern alignment film 150 is obtained.

  Furthermore, as shown in FIG. 4, by applying a polymerizable liquid crystal compound 160 onto the surface of the shaping resin 121, liquid crystal molecules are aligned along a fine line-shaped uneven structure, and then polymerized and cured. By doing so, the pattern retardation film 200 is obtained.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  For example, the above embodiment has been described based on a plate having a step between the first concavo-convex structure region 12a and the second concavo-convex structure region 21a, but the present invention is not limited to this, and the first concavo-convex structure region and the first concavo-convex structure region The present invention can also be applied to a method for manufacturing a master plate for a three-dimensional display pattern alignment film in which two concavo-convex structure regions are alternately formed on the same plane.

  Further, for example, the description of the above embodiment has been described based on a flat plate, but the present invention is not limited to this, and can be applied to a roll plate.

  Hereinafter, the present invention will be specifically described with reference to examples. In the following examples, steps (a) to (f) shown in FIGS. 1 and 2 are applied to a cylindrical roll base material having a first layer on the outermost surface.

[Test Example 1]
<First polishing step>
FIGS. 1A and 1B: Rubbing is performed in the direction of +45 degrees from the circumferential direction of the cylinder with respect to the circumferential direction of the outermost chromium layer of 5 μm (first layer) of the cylindrical base material, and the first is applied to the entire surface. An uneven structure region was formed.

<Second layer forming step>
As a resist material, a positive resist containing the above styrene-maleic acid resin and an infrared absorbing dye was diluted with the following solvent so as to have a solid content of 5%.
PGME (evaporation rate 0.75): 40% by mass
MeOH (evaporation rate 6.1: 20% by mass
MEK (Evaporation rate 4.52: 20% by mass
IPA (evaporation rate 1.59: 20% by mass

  The resist was coated in the circumferential direction and dried at 15 to 25 ° C. for a predetermined time (drying step in the present invention). The total residual solvent amount and the residual amount of each solvent at that time are shown in FIG. In the drying time on the horizontal axis in FIG. 6, as shown in Table 1 (the numerical values in the table are% by mass), 1 hour (residual solvent 1.89% by mass, PGME residual amount 1.35% by mass) and 3 Those after drying for 1.3 hours (residual solvent 1.31% by weight, PGME residual amount 0.82% by weight) are Comparative Examples 1 and 2, respectively, and for 16 hours (residual solvent 0.69% by weight, PGME residual amount 0 .26 mass%), 24 hours (residual solvent 0.61 mass%, PGME residual amount 0.18 mass%), 40 hours (residual solvent 0.43% mass, PGME residual amount 0.08 mass%), 48 hours Examples after drying (residual solvent 0.54 mass%, PGME residual amount 0.08 mass%) are Examples 1 to 4, respectively.

  Then, about an Example and a comparative example, a pattern is formed in a parallel strip | belt shape of 360 micrometers width | variety with an infrared laser exposure method, and it develops with an alkaline solution, and removes the resist residue with water as washing | cleaning after that. Non-resist portions having a width of 360 μm and first resist portions having a pitch of 360 μm and a height of 5 μm were alternately formed on the chromium layer.

  At this time, when the resist shape was visually observed, no chipping was found in Examples with low residual solvent, but in Comparative Examples with high residual solvent, defects such as resist stripe pattern breakage and chipping at the edge of the resist were found. It has occurred.

  FIG. 1D: A chromium layer having a height of 0.1 μm was formed as a second layer film by sputtering on the first resist portion and the non-resist portion.

<Second polishing step>
FIG. 2E: The second concavo-convex structure region was formed by rubbing the entire surface of the second layer film in the direction of +135 degrees from the circumferential direction of the cylinder.

<Resist stripping process>
FIG. 2F: The resist portion and the second layer film on the resist portion are peeled off with a mixed solvent of MEK, IPA, and methanol, and the first uneven structure region and the second uneven structure region are alternately arranged at a pitch of 360 μm. Then, a master plate for a three-dimensional display pattern alignment film of the present invention was obtained.

<Preparation of pattern alignment film>
Acrylic ultraviolet curable resin composition having a solid content of 45% and 2500 mPa · s diluted with a diluent solvent in which MEK and MIBK are mixed at a mass ratio of 4: 1 to TAC of 60 μm as a transparent film substrate. The film was coated to a thickness of 8 μm, and the solvent was dried and evaporated at 80 ° C. for 30 seconds. Then, the plate prepared above was pressed with a rubber roll under a load of 1000 MPa / cm, and then irradiated with ultraviolet rays to be solidified. Thereafter, it was peeled off to obtain a substrate (pattern alignment film) having a pattern alignment layer.

  When the surface of the obtained pattern alignment film was measured for the surface irregularity using an atomic force microscope (AFM), the period (pitch) of the minute line-shaped irregular structure was random within a range of about 5 nm to 500 μm. It was distributed in. Moreover, the height of the fine line-shaped uneven structure was in the range of 1 nm to 100 nm, and the width was in the range of 5 nm to 500 nm. Thus, it was confirmed that the pattern alignment film can be easily formed in Example 1.

[Test Example 2]
The same test as in Test Example 1 was performed except that the resist solvent was PGME: MeOH = 50: 50 and the outermost surface layer of the cylindrical base material and the second layer film were nickel layers. In the second layer forming step, a 360 μm wide non-resist portion and a 360 μm pitch first resist portion having a height of 5 μm were alternately formed on the nickel layer. The results of the residual solvent in the drying process at that time are shown in FIG. As in Test Example 1, the drying times of 1 hour and 3 hours are Comparative Examples 3 and 4, respectively, and the drying times of 16 hours, 24 hours, 40 hours and 48 hours are Examples 5 to 8, respectively.

  Even in this case, when the resist shape after pattern formation was visually observed, no chipping was found in the examples with low residual solvent. Defects such as chipping occurred.

[Test Example 3]
The same test as in Test Example 1 was performed except that the resist solvent was PGME: MEK = 70: 30 and the outermost surface layer of the cylindrical base material and the second layer film were titanium layers. In the second layer forming step, 360 μm wide non-resist portions and 360 μm pitch first resist portions having a height of 5 μm were alternately formed on the titanium layer. The results of the residual solvent in the drying process at that time are shown in FIG. As in Test Example 1, the drying times of 1 hour and 3 hours are Comparative Examples 5 and 6, respectively, and the drying times of 16 hours, 24 hours, 40 hours, and 48 hours are Examples 9 to 12, respectively.

  Even in this case, when the resist shape after pattern formation was visually observed, no chipping was found in the examples with low residual solvent. Defects such as chipping occurred.

[Test Example 4]
The same test as in Test Example 1 was performed except that the resist solvent was PGME = 100% and the outermost surface layer and the second layer film of the cylindrical base material were chromium layers. In the second layer forming step, 360 μm wide non-resist portions and first resist portions having a pitch of 360 μm and a height of 5 μm were alternately formed on the chromium layer. The results of the residual solvent in the drying process at that time are shown in FIG. As in Test Example 1, the drying times of 1 hour and 3 hours are Comparative Examples 7 and 8, respectively, and the drying times of 16 hours, 24 hours, 40 hours and 48 hours are Examples 13 to 16, respectively.

  Even in this case, when the resist shape after pattern formation was visually observed, no chipping was found in the examples with low residual solvent. Defects such as chipping occurred.

DESCRIPTION OF SYMBOLS 10 1st layer 12a 1st uneven | corrugated structure area | region 20 2nd layer film 21 2nd layer pattern 21a 2nd uneven | corrugated structure area | region 31 Resist part 32 Non-resist part 100 Three-dimensional display pattern orientation film original 110 Film 110 with small phase difference Molding resin 121 Molding resin surface 150 Pattern alignment film 160 Liquid crystal compound 200 Pattern retardation film

Claims (9)

A strip-shaped first concavo-convex structure region in which a minute line-shaped concavo-convex structure is formed in a substantially constant direction; and a strip-shaped second concavo-convex structure region in which a micro-line concavo-convex structure is formed in a direction different from the first concavo-convex structure; Is a method for producing a master for a pattern alignment film for three-dimensional display in which are alternately formed,
A step of patterning a resist portion for temporary masking on one band-shaped concavo-convex structure region or on a region where the concavo-convex structure is formed later,
In the pattern formation of the resist portion, a three-dimensional display use comprising a drying step in which the residual solvent of the resist is 0.05% by mass or more and 1.0% by mass or less after application of the resist and before exposure. A method for producing an original plate for a pattern alignment film.   The method for producing an original plate for a three-dimensional display pattern alignment film according to claim 1, wherein a residual solvent of the resist in the drying step is 0.05% by mass or more and 0.8% by mass or less.   The method for producing an original plate for a three-dimensional display pattern alignment film according to claim 1, wherein the residual solvent of the resist includes a solvent having an evaporation rate of 1 or less when butyl acetate is 1.   The residual solvent for the resist includes at least one selected from a polyhydric alcohol having a hydroxyl group, a polyhydric alcohol ether having a hydroxyl group, and a polyhydric alcohol ester having a hydroxyl group. A method for producing an original for a pattern alignment film for dimension display.   The method for producing a master for a three-dimensional display pattern alignment film according to any one of claims 1 to 4, comprising propylene glycol monomethyl ether as a residual solvent for the resist.   The method for producing an original plate for a three-dimensional display pattern alignment film according to claim 5, wherein the residual amount of the propylene glycol monomethyl ether in the drying step is 0.4 mass% or less.   7. The method for producing an original plate for a three-dimensional display pattern alignment film according to claim 1, wherein the resist portion has a thickness of 1 μm to 10 μm.   The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of claims 1 to 7, wherein the resist contains a styrene-maleic acid resin.   The method for producing an original plate for a three-dimensional display pattern alignment film according to any one of claims 1 to 8, wherein the drying step is performed at 10 to 30 ° C for 10 hours or more.

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