JP2013228684A - Device and method for exposure, and pattern film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce overlying failure and protect a mask to thereby obtain an excellent exposure pattern.SOLUTION: A first processing film is supported and transported by a backup roll. A mask 28 is provided close to the backup roll, and the first processing film is irradiated with light from a light source through a mask 28. The mask 28 includes a plurality of slits 29 aligned in a width direction, and comprises a rectangular substrate 28A, a mask film 28B formed on one surface of the substrate 28A, and a high refractive index layer 28C formed on the mask film 28B. The high refractive index layer 28C has transmissivity to light of the light source, and is formed of a material having a refractive index greater than that of the substrate 28A.

Description

  The present invention relates to an exposure apparatus and method, and a pattern film manufacturing method.

  A film or glass plate provided with a fine pattern is used for a retardation plate or the like used for a 3D display or the like. Moreover, in order to improve the manufacturing efficiency of the film provided with the fine pattern, it is desirable to form the fine pattern with the long length of the flexible web. In order to satisfy the low cost and high quality required for 3D displays and the like, it is required to further improve the precision of the fine pattern in the flexible web and to reduce the defects in the boundary region between the patterns. .

  There has been known an exposure apparatus in which a photoreactive film containing a photoreactive compound applied to a flexible web is irradiated with light to react the photoreactive film. Known photoreactions include alignment and curing of liquid crystal molecules by light. For example, in the exposure apparatus of Patent Document 1, an area irradiated with light is set to a portion supported by a backup roll in order to prevent wrinkling of the photoreactive film due to photoreaction.

  There is also known an exposure apparatus that irradiates only a part of the photoreactive film using a mask disposed between the light source and the photoreactive film (for example, Patent Document 2). The mask described in Patent Document 2 is provided with a plurality of slits. The plurality of slits extend in the longitudinal direction (conveying direction) of the web, and are arranged in the width direction of the web. According to this exposure apparatus, a so-called stripe-shaped exposure pattern can be efficiently formed on the photoreactive film while continuously conveying the web. That is, this exposure pattern is a pattern in which linear exposed portions where the photoreaction has progressed by exposure and linear unexposed portions where the photoreaction has not occurred due to unexposure are alternately arranged.

JP-A 63-19479 JP 09-274323 A

  However, even if exposure is performed through a mask after aligning light from a light source with an optical system such as a lens or a mirror as in the exposure apparatus described in Patent Document 2, the light source itself composed of a lamp, LED, etc. expands. Have. For this reason, no matter how high-precision optical systems and masks are used, fog failure that in principle extends to areas set as unexposed areas unless the mask is in close contact with the surface of the film being exposed. Cannot be avoided. The fogging failure in the exposure process appears as a defect in the boundary region between the striped patterns in the film. In order to satisfy the demand for high quality required for the film, it is necessary to reduce the fogging failure as much as possible in the exposure process. For this purpose, for example, the gap (gap) between the mask and the backup roll must be reduced.

  In general, quartz glass is used for the mask substrate. A light-shielding metal film having a pattern in which slits having a constant pitch are arranged in the width direction of the film is formed on the surface, and the film surface is exposed through the slits. In this case, if there are minute deposits on the front and back of the film or wrinkles on the film, the film or the minute deposits come into contact with the metal film of the mask, causing problems such as contamination and scratches on the surface. This problem can be improved by placing the mask at a certain distance from the film surface. However, this promotes the above-described fogging failure, which is a serious problem in obtaining a fine exposure pattern.

  As a result of intensive studies, the inventor has found an exposure apparatus and an exposure process that do not particularly reduce costs without reducing productivity. An object of the present invention is to provide an exposure apparatus and method capable of obtaining a good exposure pattern capable of protecting a mask while suppressing fogging failure, and a method for producing a pattern film.

  In order to achieve the above object, an exposure apparatus of the present invention has a peripheral surface that supports the back surface of a flexible web having a photoreactive film formed on the surface thereof, and conveys the supported flexible web. A backup roll, a light source that irradiates light that causes a photoreaction to the photoreactive film toward a photoreactive film formed on a supported flexible web, and a light source that is in proximity to the backup roll. A mask having a slit that is arranged between the backup roll and extends in the conveyance direction of the flexible web and is arranged at a constant pitch in the width direction of the flexible web and allows light from the light source to pass therethrough. A substrate transparent to light, a mask film formed of a material opaque to light on the back-up roll side surface of the substrate, and transparent to light and having a refractive index higher than that of the substrate Depending on the material with refractive index Characterized by having a high refractive index layer is formed to cover the mask film to the side forming a mask film on the substrate.

  The light emitted from the light source is preferably ultraviolet light. The substrate is preferably made of any one material selected from ozoneless quartz glass, synthetic quartz glass, and natural quartz glass. The mask film is preferably made of metal. Moreover, it is preferable that a metal is chromium. The mask film is preferably formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering.

The high refractive index layer is preferably formed of a thin film made of an inorganic material. In addition, the inorganic materials include fluorides such as BaF ₂ , DyF ₃ , GdF ₃ , LaF ₃ , NdF ₂ , TdF ₃ , YbF ₃ , YF ₃ , SiO ₂ , SiO, Al ₂ O ₃ , HfO ₂ , ZrO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , In ₂ O ₃ , WO ₃ oxide, SiON, Si ₃ N ₄ nitride, SiC, B ₄ C carbide, SiO ₂ / Al ₂ O ₃ , Al ₂ O ₃ / Pr ₆ O ₁₁ , Al ₂ O ₃ / La ₂ O ₃ , ZrO ₂ / Ta ₂ O ₅ , ZrO ₂ / MgO, ZrO ₂ / Al ₂ O ₃ , TiO ₂ / Pr ₆ O ₁₁ , TiO ₂ It is preferably at least one of a mixture of oxides such as / Al ₂ O ₃ and TiO ₂ / La ₂ O ₃ . The high refractive index layer is preferably formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering.

  In the exposure method of the present invention, the light source and the backup roll are in close proximity to the backup roll in the transport path for transporting while supporting the back surface of the flexible web having the photoreactive film formed on the surface by the backup roll. The photoreactive film is disposed toward the photoreactive film through a mask having a plurality of slits arranged in the width direction of the flexible web and arranged in a certain pitch in the width direction of the flexible web. The mask is formed of a substrate transparent to the light and a surface on the backup roll side of the substrate made of a material opaque to the light. A high refractive index formed by the mask film and a material that is transparent to light and has a refractive index equal to or higher than the refractive index of the substrate so that the mask film is formed on the side of the substrate on which the mask film is formed. With layers And wherein the Rukoto.

  Also in the exposure method of the present invention, as in the exposure apparatus, the light is an ultraviolet ray, and the photoreactive film preferably contains a compound having a property of reacting to the ultraviolet ray. The substrate is preferably made of any one material selected from ozoneless quartz glass, synthetic quartz glass, and natural quartz glass. The mask film is preferably made of metal. Moreover, it is preferable that a metal is chromium. The mask film is preferably formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering.

  Also in the exposure method of the present invention, it is preferable that the high refractive index layer is formed of a thin film made of an inorganic material, similarly to the exposure apparatus. Moreover, it is preferable that the same material as the material preferably used for the exposure apparatus is used for the inorganic material. In addition, it is preferable to use the same formation method as the exposure apparatus for forming the high refractive index layer.

  The method for producing a pattern film of the present invention includes a photoreactive film forming step of forming a photoreactive film on the surface of a flexible web, and an exposure step by the exposure method according to any one of claims 10 to 18. A process for producing a patterned film, comprising:

  The photoreactive film forming step preferably includes a photoreactive film coating step for applying a photoreactive film coating solution and a photoreactive film drying step for drying the photoreactive coating solution. Moreover, it is preferable to have the rubbing process which performs the rubbing process with respect to a photoreactive film in any one before and after an exposure process. Moreover, it is preferable to have the liquid crystal film application | coating process which apply | coats a liquid-crystal film coating liquid after the exposure process and a rubbing process, and the liquid crystal film hardening process which hardens | cures a liquid-crystal film coating liquid.

  According to the present invention, a good exposure pattern capable of protecting a mask while suppressing fogging failure can be obtained without particularly reducing the cost without increasing the cost.

It is a flowchart of the manufacturing process of the film (henceforth a pattern film) which provided the fine pattern in the flexible web which concerns on embodiment of this invention. It is a flowchart of another manufacturing process of a pattern film. It is the schematic of the film forming apparatus which performs the application | coating and drying process which concerns on embodiment of this invention. 1 is a schematic view of an exposure apparatus according to an embodiment of the present invention. It is a partial cross section figure which shows the outline of the exposure apparatus which concerns on embodiment of this invention. It is sectional drawing of the mask used for the exposure apparatus which concerns on embodiment of this invention. It is explanatory drawing explaining a mode that the light of a light source is irradiated with respect to a mask. It is explanatory drawing explaining a mode that the light of a light source is irradiated with respect to a mask.

(Pattern film manufacturing process)
As shown in FIG. 1A, the manufacturing process of the pattern film 13 includes a photoreactive film coating process S1 and a photoreactive film drying process S2. In the photoreactive film coating step S1, as shown in FIGS. 1A and 2, a rubbing alignment film 12 containing at least one photoacid generator is applied to the surface of one side of the base film 10 to form a rubbing alignment film 12. It is a process to do. The rubbing alignment film 12 formed by coating is a liquid film. Therefore, the photoreactive film drying step S2 is a step of obtaining the first treated film 10A by drying the rubbing alignment film 12 as shown in FIGS. 1A and 2. This first treated film 10 </ b> A includes a base film 10 and a rubbing alignment film 12. However, the rubbing alignment film 12 in the first treatment film 10A has not yet exhibited an alignment action for aligning liquid crystals, and exhibits an alignment action by the rubbing process in the rubbing step S5. In addition, the rubbing alignment film 12 in the first treatment film 10A is a photoreactive film that reacts with the light irradiated in the subsequent irradiation step S4, and the photoreactive film forming step includes the photoreactive film coating step S1. Photoreactive film drying step S2.

  Moreover, as shown to FIG. 1A, the manufacturing process of the pattern film 13 has conveyance process S3 and irradiation process S4. As shown in FIG. 1A and FIG. 3, the transporting step S <b> 3 is a step of transporting while supporting the base film 10 side of the first processing film 10 </ b> A by the backup roll 25. Irradiation process S4 is a process of obtaining the 2nd processing film 10B by irradiating an ultraviolet-ray with the UV light source 34 with respect to the application | coating side surface of a rubbing alignment film liquid. In the irradiation step S4, ultraviolet rays are irradiated from the UV light source 34 toward the first processing film 10A through the mask 28. A plurality of slits 29 arranged in the width direction are formed in the mask film 28B of the mask 28, so that the mask 28 irradiates the exposure part 4 with ultraviolet rays and does not irradiate the non-exposure part 5 with ultraviolet rays. Has a pattern. By the ultraviolet irradiation by the mask 28, an acid is generated from the photoacid generator in the exposure unit 4 to obtain the second processed film 10B.

  Further, as shown in FIG. 1A, the manufacturing process of the pattern film 13 includes a rubbing process S5, a liquid crystal film coating process S6, an aging process S7, and a UV curing process S8. The rubbing step S5 is a step of rubbing the surface on the application side of the rubbing alignment film solution in a specific rubbing alignment direction. The liquid crystal film coating step S6 is a step of coating a liquid that contains the discotic liquid crystal and forms the optically anisotropic layer 14 that is a liquid crystal film on the surface on the coating side of the rubbing alignment film liquid. The aging step S7 is a step of aligning the discotic liquid crystal. The UV curing step S8 is a step of irradiating the entire surface with ultraviolet rays and curing the discotic liquid crystal aligned in the respective directions by the exposed portion 4 and the non-exposed portion 5 so that the alignment direction does not change. The first retardation region 14 a of the optically anisotropic layer 14 is formed on the exposed portion 4, and the second retardation region 14 b is formed on the non-exposed portion 5. The first phase difference region 14a and the second phase difference region 14b extend in the depth direction of the paper surface of FIG. 1A. As shown in FIG. 1B, the rubbing step S5 may be between the photoreactive film drying step S2 and the transporting step S3.

[Photoacid generator]
As the photoacid generator, a compound that decomposes upon irradiation with light such as ultraviolet rays to generate an acidic compound, for example, a compound represented by Chemical Formula 1 or Chemical Formula 2 is used. When the photoacid generator is decomposed by light irradiation to generate an acidic compound, the alignment control ability of the rubbing alignment film 12 changes. Even if the change in the alignment control ability here is specified as a change in the alignment control ability of the rubbing alignment film 12 alone, the composition for forming the rubbing alignment film 12 and the optically anisotropic layer disposed thereon is used. It may be specified as a change in orientation control ability achieved by an additive or the like contained in the product, or may be specified as a combination thereof.

[Discotic liquid crystal compound having a polymerizable group]
As the discotic liquid crystal that can be used as the main raw material of the optically anisotropic layer, a compound having a polymerizable group is preferable. As the discotic liquid crystal, a compound represented by the following general formula (I) is preferable.
General formula (I): D (-LHQ) _n
In general formula (I), D is a discotic core, L is a divalent linking group, H is a divalent aromatic ring or heterocyclic ring, Q is a polymerizable group, and n is 3 Represents an integer of ~ 12.

  The discotic core (D) is preferably a benzene ring, naphthalene ring, triphenylene ring, anthraquinone ring, truxene ring, pyridine ring, pyrimidine ring, or triazine ring, and particularly a benzene ring, triphenylene ring, pyridine ring, pyrimidine ring, or triazine ring. preferable.

  L is preferably a divalent linking group selected from the group consisting of * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, and combinations thereof. Particularly preferred is a divalent linking group containing at least one of CH═CH— and * —C≡C—. Here, * represents a position bonded to D in the general formula (I).

  As the aromatic ring, H is preferably a benzene ring or a naphthalene ring, particularly preferably a benzene ring. As the heterocyclic ring, a pyridine ring and a pyrimidine ring are preferable, and a pyridine ring is particularly preferable. H is particularly preferably an aromatic ring.

  The polymerization reaction of the polymerizable group Q is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Of these, a (meth) acrylate group and an epoxy group are preferable.

  The discotic liquid crystal represented by the general formula (I) is particularly preferably a discotic liquid crystal represented by the following general formula (II) or (III).

  In the formula, L, H and Q have the same meanings as L, H and Q in the general formula (I), respectively, and preferred ranges thereof are also the same.

In the formula, Y ¹ , Y ² , and Y ³ are synonymous with Y ¹¹ , Y ¹² , and Y ¹³ in the general formula (IV) described later, and their preferred ranges are also the same. Further, L ¹ , L ² , L ³ , H ¹ , H ² , H ³ , R ¹ , R ² , and R ³ are also L ¹ , L ² , L ³ , H ¹ in the general formula (IV) described later. , H ² , H ³ , R ¹ , R ² , R ³ , and their preferred ranges are also the same.

  As will be described later, as represented by the general formulas (I), (II), (III) and (IV), the discotic liquid crystal having a plurality of aromatic rings in the molecule is an alignment control agent. Since an intermolecular π-π interaction occurs with an onium salt such as a pyridinium compound or an imidazolium compound used as a vertical alignment, vertical alignment can be realized. In particular, for example, in the general formula (II), when L is a divalent linking group containing at least one of * —CH═CH— or * —C≡C—, and the general formula In (III), when a plurality of aromatic rings and heterocycles are connected by a single bond, the free rotation of the bond is strongly constrained by the linking group, thereby maintaining the linearity of the molecule. For this reason, liquid crystallinity is improved, and stronger intermolecular π-π interaction occurs and stable vertical alignment is realized.

  As the discotic liquid crystal, a compound represented by the following general formula (IV) is preferable.

In the formula, Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom which may be substituted, and L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. , H ¹ , H ² and H ³ each independently represent a group of the general formula (IA) or (IB), and R ¹ , R ² and R ³ each independently represent the following general formula (I- R).

In general formula (IA), YA ¹ and YA ² each independently represents a methine or nitrogen atom, XA represents an oxygen atom, a sulfur atom, methylene or imino, and * represents L ¹ in the above general formula (IV). It represents the position at which the group bonds to ~L ³ side, and ** represents a position bonded with ^R 1 to R ³ side in the general formula (IV).

In the general formula (IB), YB ¹ and YB ² each independently represent a methine or nitrogen atom, XB represents an oxygen atom, a sulfur atom, methylene or imino, and * represents L ¹ in the general formula (IV). It represents the position at which the group bonds to ~L ³ side, and ** represents a position bonded with ^R 1 to R ³ side in the general formula (IV).

General formula (IR): *-(-L ²¹ -Q ² ) _n1 -L ²² -L ²³ -Q ¹
In the general formula (IR), * represents a position bonded to the H ^{1 to} H ³ side in the general formula (IV), L ²¹ represents a single bond or a divalent linking group, and Q ² is at least 1 Represents a divalent group (cyclic group) having a kind of cyclic structure. n1 represents the integer of 0-4. L ²² is **-O-, **-O-CO-, **-CO-O-, **-O-CO-O-, **-S-, **-NH-, ** —SO ₂ —, ** — CH ₂ —, ** — CH═CH— or ** — C≡C— is represented. L ²³ is —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and combinations thereof. Represents a divalent linking group selected from the group consisting of Q ¹ represents a polymerizable group or a hydrogen atom.

  Regarding preferred ranges of the respective symbols of the trisubstituted benzene-based discotic liquid crystalline compound represented by the formula (IV) and specific examples of the compound of the formula (IV), paragraphs [0013] to JP2010-244038A- [0077] Reference can be made to the description. However, the discotic liquid crystalline compound that can be used in the present invention is not limited to the trisubstituted benzene-based discotic liquid crystalline compound of the formula (IV).

  Examples of the triphenylene compound include compounds described in paragraphs [0062] to [0067] of JP-A-2007-108732, but the present invention is not limited thereto.

  The discotic liquid crystal represented by the general formula (IV) has a plurality of aromatic rings in the molecule. For this reason, a strong intermolecular π-π interaction occurs between the pyridinium compound or the imidazolium compound, which will be described later, and the tilt angle in the vicinity of the interface of the rubbing alignment film 12 of the discotic liquid crystal is increased. In particular, the discotic liquid crystal represented by the general formula (IV) has a highly linear molecular structure in which the rotational degrees of freedom of the molecules are constrained because a plurality of aromatic rings are connected by a single bond. Yes. As a result, a stronger intermolecular π-π interaction occurs with the pyridinium compound or imidazolium compound, and the tilt angle in the vicinity of the interface of the rubbing alignment film 12 of the discotic liquid crystal is increased to realize a vertical alignment state.

  In the present invention, the discotic liquid crystal is preferably vertically aligned. In the present specification, “vertical alignment” means that the disc surface and the layer surface of the discotic liquid crystal are vertical. However, it is not required to be strictly perpendicular, and in this specification, it means an orientation having an inclination angle of 70 degrees or more with a horizontal plane (layer surface). The inclination angle is preferably 85 to 90 degrees, more preferably 87 to 90 degrees, further preferably 88 to 90 degrees, and most preferably 89 to 90 degrees. Note that an additive that promotes vertical alignment of liquid crystal is preferably added to the above-described composition, and examples of the additive include [0055] to [0063] in JP-A-2009-222001. The compounds described in the above are included.

  The discotic liquid crystal may be in an orthogonal vertical alignment state by adding an onium salt. Furthermore, when the acid generated by light irradiation and its onium salt are anion-exchanged, the uneven distribution of the onium salt at the interface of the rubbing alignment film 12 is reduced, the orthogonal vertical alignment effect is reduced, and a parallel vertical alignment state is formed. There is a case. In this example, the optical anisotropic layer 14 contains an onium salt having such characteristics, and the rubbing alignment film 12 includes a photoacid generator having such characteristics. Is selected and used. Various compounds are used so that the rubbing alignment film 12 adopts a polyvinyl alcohol-based compound, and the ester portion is decomposed by an acid generated by light irradiation to change the interfacial unevenness of the onium salt rubbing alignment film 12. It may be selected and used. Of course, the present invention is not limited thereto, and any combination of compounds having the same technical idea is within the scope of the present invention. Using such a technical idea, a pattern film 13 is obtained in which the orientation direction of the discotic liquid crystal in the exposed portion 4 and that in the non-exposed portion 5 are in different directions.

[Onium salt compound (alignment control agent on alignment film)]
In the present invention, as described above, it is preferable to add an onium salt in order to realize vertical alignment of a discotic liquid crystal having a polymerizable group. The onium salt is unevenly distributed at the interface with the rubbing alignment film 12 and acts to increase the tilt angle of the liquid crystal molecules near the interface with the rubbing alignment film 12.

As the onium salt, a compound represented by the following general formula (1) is preferable.
Formula _{(1) Z- (Y-L-} ) n Cy + · X -
In the formula, Cy is a 5- or 6-membered onium group, and L, Y, Z, and X are L ²³ , L ²⁴ , Y ²² , Y ²³ , Z in the general formulas (2a) and (2b) described later. ²¹ and X are synonymous, and their preferred ranges are also the same, and n represents an integer of 2 or more.

  The 5- or 6-membered onium group (Cy) is preferably a pyrazolium ring, an imidazolium ring, a triazolium ring, a tetrazolium ring, a pyridinium ring, a pyridinium ring, a pyrimidinium ring, or a triazinium ring, and particularly preferably an imidazolium ring or a pyridinium ring.

The 5- or 6-membered onium group (Cy) preferably has a group having an affinity for the material of the rubbing alignment film 12. Furthermore, it is preferable that the onium salt compound has a high affinity with the material of the rubbing alignment film 12 at a temperature T ₁ ° C, while the affinity is reduced at a temperature T ₂ ° C. Since the hydrogen bond can be in a bonded state or a state in which the bond has disappeared within the actual temperature range for aligning the liquid crystal (room temperature to about 150 ° C.), it is preferable to use the affinity due to the hydrogen bond. . However, it is not limited to this example.

  For example, in an embodiment in which polyvinyl alcohol is used as the rubbing alignment film 12 material, it is preferable to have a hydrogen bonding group in order to form a hydrogen bond with the hydroxyl group of polyvinyl alcohol. As a theoretical interpretation of hydrogen bonding, for example, H.H. Unneyama and K.M. There are reports in Morokuma, Journal of American Chemical Society, Vol. 99, pp. 1316-1332, 1977. Specific examples of hydrogen bonding include J.I. N. There is a style described in Israel Ativiri, Yasu Kondo, Hiroyuki Oshima, intermolecular force and surface force, McGraw Hill, 1991, page 98, FIG. Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angewent Chemistry International Edition England, Vol. 34, p. 2311, 1995.

  In addition to the hydrophilic effect of the onium group, the 5- or 6-membered onium group having a hydrogen bonding group increases the surface unevenness at the interface of the rubbing alignment film 12 by hydrogen bonding to the polyvinyl alcohol, and polyvinyl alcohol. Promotes the function of imparting orthogonal orientation to the main chain. Preferred hydrogen-bonding groups include amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl groups, benzimidazolyl groups, Pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil group, barbituric acid group And hydantoin group, maleic hydrazide group, isatin group, uramil group and the like. More preferred hydrogen bonding groups include amino groups and pyridyl groups.

  Moreover, it is also preferable that the 5- or 6-membered onium ring contains an atom having a hydrogen bonding group, such as a nitrogen atom of an imidazolium ring.

  n is preferably an integer of 2 to 5, more preferably 3 or 4, and particularly preferably 3. A plurality of L and Y may be the same as or different from each other. When n is 3 or more, the onium salt represented by the general formula (1) has three or more 5- or 6-membered rings, and therefore has a strong intermolecular π-π interaction with the discotic liquid crystal. Therefore, the vertical alignment of the discotic liquid crystal, in particular, the orthogonal vertical alignment with respect to the polyvinyl alcohol main chain can be realized on the rubbing alignment film 12 of polyvinyl alcohol.

  The onium salt represented by the general formula (1) is particularly preferably a pyridinium compound represented by the following general formula (2a) or an imidazolium compound represented by the following general formula (2b). The compounds represented by the general formulas (2a) and (2b) are mainly for the purpose of controlling the orientation of the discotic liquid crystal represented by the general formulas (I) to (IV) at the interface of the rubbing alignment film 12. When added, it acts to increase the tilt angle of the discotic liquid crystal molecules in the vicinity of the interface with the rubbing alignment film 12. The general formula (2) refers to the general formulas (2a) and (2b).

In the formula, L ²³ and L ²⁴ each represent a divalent linking group. L ²³ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH—, —N═. N-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O- CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO-AL-CO-O-. Preferably, AL is an alkylene group having 1 to 10 carbon atoms. L ²³ represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO- AL-CO-O- is preferable, a single bond or -O- is more preferable, and -O- is most preferable.

L ²⁴ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH— or —N═. N- is preferred, and -O-CO- or -CO-O- is more preferred. When m is 2 or more, it is more preferable that the plurality of L ²⁴ are alternately —O—CO— and —CO—O—.

R ²² is a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 1 to 20 carbon atoms. When R ²² is a dialkyl-substituted amino group, two alkyl groups may be bonded to each other to form a nitrogen-containing heterocycle. The nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring. R ²³ is more preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 12 carbon atoms, and a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted group having 2 to 8 carbon atoms. Even more preferred is an amino group. When R ²³ is an unsubstituted amino group or a substituted amino group, the 4-position of the pyridinium ring is preferably substituted.

  X is an anion. X is preferably a monovalent anion. Examples of anions include halide ions (fluorine ions, chlorine ions, bromine ions, iodine ions) and sulfonate ions (eg, methanesulfonate ion, p-toluenesulfonate ion, benzenesulfonate ion).

Y ²² and Y ²³ are each a divalent linking group having a 5- or 6-membered ring as a partial structure. The aforementioned 5- or 6-membered ring may have a substituent. Preferably, at least one of Y ²² and Y ²³ is a divalent linking group having a 5- or 6-membered ring having a substituent as a partial structure. Y ²² and Y ²³ are preferably each independently a divalent linking group having a 6-membered ring which may have a substituent as a partial structure. The 6-membered ring includes an aliphatic ring, an aromatic ring (benzene ring) and a heterocyclic ring. Examples of the 6-membered aliphatic ring include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring. Examples of 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiin ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. Including. Another 6-membered ring or 5-membered ring may be condensed to the 6-membered ring.

Examples of the substituent that the 5- or 6-membered ring has include a halogen atom, cyano, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms. The substituent is preferably an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms. The number of substituents may be 2 or more. For example, when Y ²² and Y ²³ are phenylene groups, the number of carbon atoms of 1 to 4 is 1 to 12 (more preferably 1 to 6, more preferably 1 to The alkyl group of 3) may be substituted.

Note that m is 1 or 2, and is preferably 2. When m is 2, the plurality of Y ²³ and L ²⁴ may be the same as or different from each other.

Z ²¹ is halogen-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, phenyl substituted with an alkyl group having 1 to 10 carbon atoms, phenyl substituted with an alkoxy group having 2 to 10 carbon atoms, carbon atom An alkyl group having 1 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and 7 to 26 carbon atoms And a monovalent group selected from the group consisting of an arylcarbonyloxy group having 7 to 26 carbon atoms.

When m is 2, Z ²¹ is preferably cyano, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and is an alkoxy group having 4 to 10 carbon atoms. More preferably. When m is 1, Z ²¹ is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an acyl-substituted alkyl group having 7 to 12 carbon atoms, or 7 carbon atoms. It is preferably an acyl-substituted alkoxy group of -12, an acyloxy-substituted alkyl group having 7-12 carbon atoms, or an acyloxy-substituted alkoxy group having 7-12 carbon atoms.

  The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

p is an integer of 1-10. It is particularly preferable that p is 1 or 2. C _p H _2p means a chain alkylene group which may have a branched structure. C _p H _2p is preferably a linear alkylene group (— (CH ₂ ) _p —).

In formula (2b), R ³⁰ is a hydrogen atom or an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.

  Among the compounds represented by the formula (2a) or (2b), compounds represented by the following formula (2a ′) or (2b ′) are preferable. The general formula (2 ′) refers to the general formulas (2a ′) and (2b ′).

In the formulas (2a ′) and (2b ′), the same symbols as those in the formula (2) have the same meaning, and the preferred ranges are also the same. L ²⁵ is synonymous with L ²⁴ and the preferred range is also the same. L ²⁴ and L ²⁵ are preferably —O—CO— or —CO—O—, L ²⁴ is preferably —O—CO—, and L ²⁵ is preferably —CO—O—.

R ²³ , R ²⁴ and R ²⁵ are each an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, more preferably 1 to 3). n ₂₃ is _{0-4, n 24} is 1 to 4, and _{n 25} represents 0 to 4. In n ₂₃ and _{n 25} is _0, it is preferred that _{n 24} is 1 to 4 (more preferably 1 to 3). R ³⁰ is preferably an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.

  Specific examples of the compound represented by the general formula (2) include compounds described in [0058] to [0061] in the specification of JP-A-2006-113500.

Specific examples of the compound represented by the general formula (2 ′) are shown below. However, the anion (X ⁻ ) was omitted in the following formula.

  The compounds of the formulas (2a) and (2b) can be produced by a general method. For example, the pyridinium derivative of the formula (2a) is generally obtained by alkylating the pyridine ring (Menstokin reaction). Moreover, the addition amount of onium salt does not exceed 5 mass% with respect to a liquid crystal compound, and it is preferable that it is about 0.1-2 mass%.

The onium salts represented by the general formulas (2a) and (2b) are unevenly distributed on the surface of the rubbing alignment film 12 of the aforementioned hydrophilic polyvinyl alcohol because the pyridinium group or the imidazolium group is hydrophilic. In particular, a pyridinium group is further substituted with an amino group which is a substituent of an acceptor of a hydrogen atom (in the general formulas (2a) and (2a ′), R ²² is an unsubstituted amino group or a substituent having 1 to 20 carbon atoms) When the amino group is substituted, intermolecular hydrogen bonds are generated between the polyvinyl alcohol and the surface of the rubbing alignment film 12 with a higher density, and the pyridinium derivative is converted into polyvinyl alcohol by the effect of the hydrogen bonds. Since the liquid crystal is oriented in a direction perpendicular to the main chain, the liquid crystal is oriented perpendicularly to the rubbing direction. Since the aforementioned pyridinium derivative has a plurality of aromatic rings in the molecule, a strong intermolecular π-π interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the rubbing of the discotic liquid crystal. An orthogonal orientation in the vicinity of the interface of the alignment film 12 is induced. In particular, as represented by the general formula (2a ′), when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect.

  Furthermore, when the onium salts represented by the general formulas (2a) and (2b) are used in combination, the liquid crystal is aligned with its slow axis parallel to the rubbing direction by heating above a certain temperature. , Can promote parallel orientation. This is because the heat bond caused by heating breaks the hydrogen bond with polyvinyl alcohol, the onium salt is uniformly dispersed in the rubbing alignment film 12, the density on the surface of the rubbing alignment film 12 is lowered, and the rubbing alignment film 12 itself is regulated. This is because the liquid crystal is aligned by force.

  The film forming apparatus 11 according to the photoreactive film coating step S1 and the photoreactive film drying step S2 will be described. As shown in FIG. 2, the film forming apparatus 11 includes a die 20 and a drying device 22. The die 20 applies the rubbing alignment film liquid to the base film 10 in the photoreactive film application step S1. The drying device 22 applies hot air to dry the rubbing alignment film 12 in the photoreactive film drying step S2 to obtain the first processed film 10A. The film forming apparatus 11 is provided with transport rollers 23 for transporting the base film 10, the first processing film 10A, and the like. The conveyance roller 23 is also provided in the exposure device 24 and the like in order to convey a second processing film 10B described later.

  The die 20 is always supplied with a liquid containing a rubbing alignment film liquid from a supply port (not shown). The drying device 22 is provided with an exhaust device (not shown), and exhausts the organic solvent evaporated from the rubbing alignment film 12.

  The exposure apparatus 24 according to the transport process S3 and the irradiation process S4 will be described. As shown in FIGS. 3 and 4, the exposure apparatus 24 includes a backup roll 25, a drive shaft 26, a mask 28, a slit 29 provided in the mask 28, a mask folder 30, and a UV light source 34. Prepare. A drive source (not shown) is connected to the drive shaft 26 to rotate the backup roll. The mask 28 is patterned so that the exposed portion 4 is exposed and the non-exposed portion 5 is not exposed. The mask folder 30 supports the mask 28. The UV light source 34 irradiates the first processing film 10 </ b> A supported by the backup roll 25 through the mask 28 with ultraviolet rays.

  As shown in FIG. 5, the mask 28 is formed, for example, by forming a mask film 28B on one surface of a rectangular substrate 28A, forming a high refractive index layer 28C thereon, and a backup roll for the high refractive index layer 28C. It is obtained by polishing the surface on the 25th side. The substrate 28A is transparent to ultraviolet rays and has no reactivity. The mask film 28B is formed on the surface of the substrate 28A on the backup roll 25 side by vapor deposition or sputtering of a material that is opaque to ultraviolet rays and has no reactivity. A high refractive index layer 28C is formed by depositing a high refractive index material on the mask film 28B, and the mask 28 is obtained by polishing the surface on the backup roll 25 side.

  The substrate 28A is preferably one that has excellent ultraviolet transmittance and is stable to heat from the ultraviolet light source. For example, ozone-less quartz glass, synthetic quartz glass, and natural quartz glass are preferred. For the mask film 28B, it is desirable to use a material that is easy to form and has no reactivity to ultraviolet rays, and for example, a metal is desirable. The method of forming the mask film 28B is preferably one of vacuum vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma vapor deposition, and sputtering. The mask film 28B is preferably one that does not deteriorate due to gas generated from the rubbing alignment film 12 during the exposure process. For example, chromium that forms a dense surface oxide film against a strong acid is desirable.

  The high refractive index layer 28C has a higher refractive index than the substrate 28A. The high refractive index layer 28C is desirably formed of a thin film made of an inorganic material. The film forming method of the high refractive index layer 28C is preferably any one of vacuum vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma vapor deposition, and sputtering. Note that a plate of a material having a high refractive index may be simply provided instead of the high refractive index layer 28C.

Inorganic material for forming the high refractive index layer 28C _{is, BaF 2, DyF 3, GdF} 3, LaF 3, NdF 2, fluorides such _{TdF 3, YbF 3, YF 3} , SiO 2, SiO, Al 2 O 3, HfO ₂ , oxides such as ZrO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , In ₂ O ₃ and WO ₃ , nitrides such as SiON and Si ₃ N ₄ , carbides such as SiC and B ₄ C, SiO ₂ / Al ₂ O ₃ , Al ₂ O ₃ / Pr ₆ O ₁₁ , Al ₂ O ₃ / La ₂ O ₃ , ZrO ₂ / Ta ₂ O ₅ , ZrO ₂ / MgO, ZrO ₂ / Al ₂ O ₃ , TiO ₂ / Pr It is desirable to be at least one of a mixture of oxides such as ₆ O ₁₁ , TiO ₂ / Al ₂ O ₃ , and TiO ₂ / La ₂ O ₃ .

As the UV light source 34, for example, at least one ultraviolet lamp can be used. Examples of the ultraviolet lamp include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp. Illuminance of UV light source 34 is, for example, 500 mW / cm ² or more 1000 mW / cm ² or less. The UV light source 34 is preferably parallel light with respect to the pattern from the viewpoint of preventing fogging. The parallelism (θ in FIG. 6B) is preferably 10 ° or less, and more preferably 5 ° or less in the width direction with respect to the substrate 28A. There are no particular limitations on the means for collimating the light, but various optical devices such as mirrors and lenses can be used. Further, it is preferable that the light irradiation range is only a portion of the mask 28 where the mask pattern is formed. As a result, the frequency of fog failure due to thermal expansion and contraction due to an increase in the surface temperature of the mask is also reduced. There is no particular limitation on the means for exposure, but light condensing using a mirror or lens or a light shielding plate can be used.

The operation of the present invention will be described below. The rubbing alignment film liquid is applied on the base film 10 at 14 cc / m ² by the die 20 applied in the photoreactive film application step S1, and the rubbing alignment film 12 is formed as a liquid film. Then, in the photoreactive film drying step S2, the first treatment film 10A is obtained by drying the rubbing alignment film 12 with hot air of 110 degrees applied for about 1 minute by the drying device 22.

Furthermore, 10 A of 1st process films are provided to irradiation process S4 in the state by which the base film 10 side of 10 A of 1st process films was supported by the backup roll 25 in conveyance process S3. That is, the irradiation step S4 is in the transport step S3. In the irradiation step S4, the surface on the application side of the rubbing alignment film liquid of the first processing film 10A supported on the backup roll 25 is irradiated with ultraviolet rays from the UV light source 34 through the mask 28, and the second processing film. 10B is obtained. The mask 28 has a slit 29 having a pattern that irradiates the exposed portion 4 with ultraviolet rays and does not irradiate the non-exposed portion 5 with ultraviolet rays. By irradiating the UV light source 34 with ultraviolet rays having an energy of about 10 mJ / cm ² and generating an acid only from the photoacid generator in the exposed portion 4, the second processed film 10B is obtained. In the present embodiment, the pattern width in the web width direction of the exposed portion 4 and the non-exposed portion 5 is about 280 μm.

  The mask 28 is exposed to a gas generated from the rubbing alignment film 12, but the high refractive index layer 28C acts as a protective film for protecting the mask film 28B, whereby the mask film 28B generates a gas generated from the rubbing alignment film 12, etc. Protected from. Therefore, as shown in FIGS. 6A and 6B, the mask 28 of FIG. 6B can be arranged in a state where the distance D from the first processing film 10A is smaller than the mask 35 of FIG. 6A.

  The light emitted from the UV light source 34 has a component that is not completely perpendicular to the surface of the mask 28 as shown in FIGS. 6A and 6B. For this reason, in the conventional exposure apparatus and method, the region RF that is exposed in the region set in the unexposed portion is formed large as shown in FIG. 6A. However, in the mask 28, in addition to being arranged in a state where the distance D is smaller than that of the mask 35, the high refractive index of the high refractive index layer 28C is set to an unexposed portion as shown in FIG. 6B. The area RF that is exposed in the exposed area is greatly reduced.

  Specifically, as shown in FIG. 6A, for the mask 35 that does not have the high refractive index layer 28C, light that is not completely perpendicular to the mask 35 irradiated from the UV light source 34 passes through the mask film 28B. After spreading. However, as shown in FIG. 6B, the mask 28 having the high refractive index layer 28C has a high refractive index layer 28C after light that is not completely perpendicular to the mask 28 irradiated from the UV light source 34 passes through the mask film 28B. Can greatly reduce the spread. If the refractive index of the high refractive index layer 28C is higher than the refractive index of the atmosphere between the mask 28 and the first processing film 10A, there is a certain effect of narrowing the region RF. However, by making the high refractive index layer 28C have a higher refractive index than that of the substrate 28, the region RF is further narrowed.

In the rubbing step S5, the second treatment film 10B is rubbed in a desired direction with respect to the surface on the application side of the rubbing alignment film liquid. In the liquid crystal film application step S6, a liquid containing discotic liquid crystal and forming the optically anisotropic layer 14 is applied at 5 cc / m ² to the surface on the application side of the rubbing alignment film liquid. Further, a two-stage ripening step S7 is performed. In the first stage, the discotic liquid crystal is aligned in a direction perpendicular to the rubbing alignment direction by being placed in an environment of 75 ° C., and the vertical alignment agent and acid are reacted in the exposed portion 4. In the second stage, the discotic liquid crystal is aligned in the rubbing alignment direction in the exposure section 4 under an environment of 110 ° C. Finally, in the UV curing step S8, the entire surface of the coating film made of the liquid for forming the optically anisotropic layer 14 is irradiated with ultraviolet rays having an energy of 500 mJ / cm ² in the exposed portion 4 and the non-exposed portion 5, respectively. The discotic liquid crystal aligned in the direction is cured so that the alignment direction does not change. Thereby, the desired pattern film 13 (refer FIG. 1A) is obtained.

  For this reason, light that is not completely perpendicular to the mask irradiated from the light source is reflected by the flexible web or the backup roll, the reflected light is further reflected by the mask, and the light is applied to the region set in the unexposed portion. The frequency of fog failure due to irradiation is greatly reduced.

  Moreover, in the said embodiment, it described about the exposure apparatus 24 and the exposure process which are a manufacturing apparatus of a flexible web provided with the fine pattern used for phase difference plates etc. which are used for 3D displays etc., and a part of manufacturing process. Yes. However, the present invention is not limited to this, and the same can be applied to the production of color patterns such as color filters and light shielding patterns.

  In order to confirm the effect of the present invention, examples and comparative examples for the present invention were performed.

(Experiment 1)
<Preparation of base film 10>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acylate solution A.
───────────────────────────────────────
Composition of Cellulose Acylate Solution A───────────────────────────────────────
Cellulose acetate with a substitution degree of 2.86 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) ) 54 parts by mass 1-butanol 11 parts by mass ──────────────────────────────────────

The following composition was charged into another mixing tank, stirred while heating to dissolve each component, and an additive solution B was prepared.
───────────────────────────────────────
Composition of additive solution B ───────────────────────────────────────
The following compound B1 (Re reducing agent) 40 parts by mass The following compound B2 (wavelength dispersion controlling agent) 4 parts by mass Methylene chloride (first solvent) 80 parts by mass Methanol (second solvent) 20 parts by mass ──────── ───────────────────────────────

<< Production of Substrate Film 10 Made of Cellulose Acetate >>
40 parts by mass of the additive solution B was added to 477 parts by mass of the cellulose acylate solution A, and the dope was prepared by sufficiently stirring. The dope was cast from a casting port of a casting die (not shown) onto a drum cooled to 0 ° C. The film is peeled off in a state where the solvent content is 70% by mass, both ends in the width direction of the film are fixed with a pin tenter (a pin tenter described in FIG. 3 of JP-A-4-1009), and the solvent content is 3 to 5% by mass Then, the film was dried while maintaining an interval at which the stretching ratio in the lateral direction (direction perpendicular to the conveying direction) was 3%. Then, it dried further by conveying between the rolls of the heat processing apparatus, and produced the base film 10 made of cellulose acetate having a thickness of 60 μm. This substrate film 10 made of cellulose acetate did not contain a UV absorber, Re (550) was 0 nm, and Rth (550) was 12.3 nm.

<< Alkaline saponification treatment >>
The substrate film 10 made of cellulose acetate was passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature was raised to 40 ° C. Thereafter, an alkali solution having the composition shown below was applied to one side of the film using a bar coater at a coating amount of 14 ml / m ² , heated to 110 ° C., and steam-type far infrared manufactured by Noritake Company Limited. It was conveyed for 10 seconds under the heater. Subsequently, pure water was applied at 3 ml / m ² using the same bar coater. Next, washing with a fountain coater and draining with an air knife were repeated three times. Thereafter, the substrate film 10 made of cellulose acetate subjected to alkali saponification treatment was produced by transporting to a drying zone at 70 ° C. for 10 seconds and drying.

───────────────────────────────────────
Composition of alkaline solution (parts by mass)
───────────────────────────────────────
Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight Surfactant SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H 1.0 parts by weight Propylene glycol 14. 8 parts by mass ────────────────────────────────────────

<Production of Mask 28>
Chromium is applied to one surface of the ozoneless quartz glass so as to have a pattern extending in the conveying direction of the flexible web (base film 10) and having a plurality of slits arranged at a constant pitch in the width direction of the flexible web. It was formed by sputtering. Then, BaF ₂ was further deposited on the surface by plasma deposition, and a mask 28 used for the exposure apparatus 24 of the example according to the present invention was produced.

<Formation of rubbing alignment film>
A rubbing alignment film solution having the following composition was continuously applied with a # 8 wire bar to the surface of the base film 10 thus prepared. The rubbing alignment film 12 was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, a mask 28 having a lateral stripe width of 285 μm of the transmission part (slit 29) and a horizontal stripe width of 285 μm of the shielding part (between the slits 29 and 29) was disposed on the rubbing alignment film 12. Under a room temperature air, UV light is irradiated for 4 seconds using an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.) having an illuminance of 2.5 mW / cm ² in the UV-C region, and the photoacid generator is decomposed and acidic. A compound was generated. Thereby, the rubbing alignment film 12 for the first retardation region 14a (see FIG. 1A) was formed. Thereafter, rubbing treatment was performed once in one direction at 500 rpm while maintaining an angle of 45 ° with respect to the stripe of the stripe mask, and a transparent support (base film 10) with the rubbing alignment film 12 was produced. The film thickness of the rubbing alignment film 12 was 0.5 μm.

───────────────────────────────────────
Composition of rubbing alignment film solution ───────────────────────────────────────
Polymer material for alignment film 3.9 parts by mass (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Photoacid generator (S-2) 0.1 parts by weight Methanol 36 parts by weight Water 60 parts by weight ──────────────────────────── ───────────
In addition, a photo-acid generator (S-2) is the following compound.

<Formation of patterned optically anisotropic layer 14>
The following coating liquid for optically anisotropic layer was applied at a coating amount of 4 ml / m ² using a bar coater. Next, after aging at a film surface temperature of 110 ° C. for 2 minutes, the film was cooled to 80 ° C. and irradiated with ultraviolet rays for 20 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm ^{2 in} the air. Then, the patterned optical anisotropic layer A was formed by fixing the orientation state. In the first retardation region 14a (see FIG. 1A) on the mask exposure portion 4, the discotic liquid crystal is vertically aligned with the slow axis direction parallel to the rubbing direction, and the second retardation on the non-exposure portion 5 is obtained. In the region 14b (see FIG. 1A), it was vertically aligned perpendicularly. The film thickness of the optically anisotropic layer 14 was 0.9 μm.

───────────────────────────────────────
Composition of coating solution for optically anisotropic layer ───────────────────────────────────────
Discotic liquid crystal E-1 100 parts by weight Alignment film interface aligner (II-1) 3.0 parts by weight Air interface aligner (P-1) 0.4 parts by weight Photopolymerization initiator 3.0 parts by weight (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 400 parts by weight ───────────────────────── ──────────────

Comparative example

(Experiment 2)
In Experiment 2, a pattern in which a plurality of slits are arranged on one surface of ozoneless quartz glass in the conveyance direction of the flexible web (base film 10) and arranged at a constant pitch in the width direction of the flexible web, Thus, a mask produced by forming chromium by sputtering was produced. The test was performed under the same conditions as in Experiment 1 except that the mask 28 in Experiment 1 was replaced with this mask.

  In Experiment 1 and Experiment 2, the magnitude of the fogging failure was evaluated as the width of the boundary region between adjacent patterns in the pattern film. In Experiment 1, this fogging failure was suppressed to a level where there was no practical problem at the beginning of the experiment, and this level was maintained even after the pattern film 13 was manufactured 3000 m. On the other hand, in Experiment 2, a fog failure at a level causing a practical problem even in the initial stage of the experiment occurred, and after the pattern film was manufactured 3000 m, a larger fog fault occurred than in the initial stage. Furthermore, in Experiment 1, no deterioration was found in the mask film of the mask used, but in Experiment 2, the mask film of the mask used was deteriorated.

DESCRIPTION OF SYMBOLS 4 Exposed part 5 Non-exposed part 10 Base film 10A 1st process film 10B 2nd process film 12 Rubbing alignment film 13 Pattern film 14a 1st phase difference area 14b 2nd phase difference area 20 Die 22 Drying device 23 Conveyance roller 25 Backup Roll 26 Drive shaft 28 Mask 28A Substrate 28B Mask film 28C High refractive index layer 29 Slit 30 Mask folder 34 UV light source 40 UV light path

Claims (22)

A backup roll having a peripheral surface for supporting the back surface of the flexible web having a photoreactive film formed on the surface, and transporting the supported flexible web;
A light source for irradiating the photoreactive film with light that causes a photoreaction toward the photoreactive film formed on the supported flexible web;
Located between the light source and the backup roll in a state of being close to the backup roll, extends in the conveyance direction of the flexible web, and is arranged in a plurality at a constant pitch in the width direction of the flexible web. And a mask having a slit through which light passes.
The mask is
A substrate transparent to the light;
A mask film formed of a material opaque to the light on the surface of the substrate on the backup roll side;
High refraction formed so as to cover the mask film with respect to the side of the substrate on which the mask film is formed, by a material that is transparent to the light and has a refractive index equal to or higher than the refractive index of the substrate. An exposure apparatus comprising a rate layer.   The exposure apparatus according to claim 1, wherein the light emitted from the light source is ultraviolet light.   3. The exposure apparatus according to claim 1, wherein the substrate is made of any one material selected from ozoneless quartz glass, synthetic quartz glass, and natural quartz glass.   The exposure apparatus according to claim 1, wherein the mask film is made of metal.   5. An exposure apparatus according to claim 4, wherein the metal is chromium.   6. The exposure apparatus according to claim 1, wherein the mask film is formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering. .   The exposure apparatus according to claim 1, wherein the high refractive index layer is formed of a thin film made of an inorganic material. The inorganic materials include BaF ₂ , DyF ₃ , GdF ₃ , LaF ₃ , NdF ₂ , TdF ₃ , YbF ₃ , YF ₃ fluorides, SiO ₂ , SiO, Al ₂ O ₃ , HfO ₂ , ZrO ₂ , Ta _2. O ₅ , Nb ₂ O ₅ , TiO ₂ , In ₂ O ₃ , WO ₃ oxides, SiON, Si ₃ N ₄ nitrides, SiC, B ₄ C carbides, SiO ₂ / Al ₂ O ₃ , Al ₂ O ₃ / Pr ₆ O ₁₁ , Al ₂ O ₃ / La ₂ O ₃ , ZrO ₂ / Ta ₂ O ₅ , ZrO ₂ / MgO, ZrO ₂ / Al ₂ O ₃ , TiO ₂ / Pr ₆ O ₁₁ , TiO ₂ / _{al 2 O 3, TiO 2 /} La exposure apparatus according to claim 7, wherein the at least one of a mixture of 2 _{O 3} such oxides.   The high refractive index layer is formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering. Exposure device. In the transport path for transporting while supporting the back surface of the flexible web with the photoreactive film formed on the surface by the backup roll,
A plurality of slits arranged between the light source and the backup roll in the vicinity of the backup roll and extending in the conveyance direction of the flexible web and arranged at a constant pitch in the width direction of the flexible web. An irradiation step of irradiating light that causes a photoreaction to the photoreactive film from a light source toward the photoreactive film through a mask having,
The mask is
A substrate transparent to the light;
A mask film formed of a material opaque to the light on the surface of the substrate on the backup roll side;
High refraction formed so as to cover the mask film with respect to the side of the substrate on which the mask film is formed, by a material that is transparent to the light and has a refractive index equal to or higher than the refractive index of the substrate. And an exposure layer.   11. The exposure method according to claim 10, wherein the light is ultraviolet light, and the photoreactive film contains a compound having a property of reacting to ultraviolet light.   12. The exposure method according to claim 10, wherein the substrate is made of any one material selected from ozoneless quartz glass, synthetic quartz glass, and natural quartz glass.   The exposure method according to claim 10, wherein the mask film is made of metal.   The exposure method according to claim 13, wherein the metal is chromium.   The exposure method according to claim 10, wherein the mask film is formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering. .   The exposure method according to claim 10, wherein the high refractive index layer is formed of a thin film made of an inorganic material. The inorganic materials include BaF ₂ , DyF ₃ , GdF ₃ , LaF ₃ , NdF ₂ , TdF ₃ , YbF ₃ , YF ₃ fluorides, SiO ₂ , SiO, Al ₂ O ₃ , HfO ₂ , ZrO ₂ , Ta _2. O ₅ , Nb ₂ O ₅ , TiO ₂ , In ₂ O ₃ , WO ₃ oxides, SiON, Si ₃ N ₄ nitrides, SiC, B ₄ C carbides, SiO ₂ / Al ₂ O ₃ , Al ₂ O ₃ / Pr ₆ O ₁₁ , Al ₂ O ₃ / La ₂ O ₃ , ZrO ₂ / Ta ₂ O ₅ , ZrO ₂ / MgO, ZrO ₂ / Al ₂ O ₃ , TiO ₂ / Pr ₆ O ₁₁ , TiO ₂ / The exposure method according to claim 16, wherein the exposure method is at least one of a mixture of oxides such as Al ₂ O ₃ and TiO ₂ / La ₂ O ₃ .   18. The high refractive index layer is formed by any one of vacuum deposition, electron beam deposition, ion beam deposition, plasma deposition, and sputtering. Exposure method. A photoreactive film forming step of forming the photoreactive film on the surface of the flexible web;
The manufacturing method of a pattern film characterized by having an exposure process by the exposure method of any one of Claims 10-18. The photoreactive film forming step includes
A photoreactive film coating step of applying a photoreactive film coating solution;
The method for producing a pattern film according to claim 19, further comprising a photoreactive film drying step of drying the photoreactive coating solution.   21. The method for producing a patterned film according to claim 19, further comprising a rubbing step for rubbing the photoreactive film before or after the exposure step.   The liquid crystal film coating process for coating a liquid crystal film coating liquid after the exposure process and the rubbing process are performed, and the liquid crystal film curing process for curing the liquid crystal film coating liquid. The manufacturing method of the pattern film as described in any one of -21.

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